Tag: Nanoparticles

  • Nanoparticle therapy offers hope for aortic aneurysm treatment

    Nanoparticle therapy offers hope for aortic aneurysm treatment

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    Aortic aneurysms are bulges in the aorta, the largest blood vessel that carries oxygen-rich blood from the heart to the rest of the body. Smoking, high blood pressure, diabetes, or injury can all increase the risk of aneurysms, which tend to occur more often in Caucasian male smokers over the age of 65. 

    The soft tissues that make up blood vessels act essentially like rubber bands, and it’s the elastic fibers within these tissues that allow them to stretch and snap back. These fibers are produced primarily before and just after birth. After that, they don’t regenerate or undergo natural repair after injury. So when they become injured or diseased, the tissue weakens and causes an aneurysm, which can grow over time. After about seven to 10 years, it typically reaches the rupture stage.”


    Professor Anand Ramamurthi, Chair of the Department of Bioengineering in Lehigh University’s P.C. Rossin College of Engineering and Applied Science

    During that period, there is no treatment. Patients are screened regularly via imaging to monitor the rate of the aneurysm’s growth. Once it’s deemed big enough to potentially rupture (an occurrence that is fatal 90 percent of the time), surgery is the only option. But it’s a risky one for elderly patients.

    Ramamurthi and his team are working on minimally invasive ways to regenerate and repair these elastic fibers using polymeric or biological nanocapsules, called nanoparticles, that are designed to release novel regenerative therapeutics. Their innovative techniques could enable treatment soon after an aneurysm is detected and potentially slow, reverse, or even stop its growth. Findings from their most recent paper, published in the Journal of Biomedical Materials Research, build on their earlier work and represent a step toward a future where surgery is no longer the best, and only, treatment option. 

    “In previous research, we’ve identified drugs and gene-silencing agents that can actually coax adult diseased vascular cells to produce new elastic fibers and inhibit the enzymes that break down existing fibers,” he says. “We’ve also been working on how to deliver these therapeutics efficiently only at the site of tissue repair.”

    The team has also developed a nanoparticle design called active-targeting that incorporates small protein fragments, or peptides, on the nanoparticle’s surface. “These peptides recognize components that are unique to the aneurysm tissue. So when the nanoparticles are injected into the bloodstream, they stick only to the aneurysm wall, where they slowly degrade and release the drug.

    For this paper, he says, the researchers “investigated how the nanoparticles actually penetrate the blood vessel wall to deliver the drug to the affected tissue.”

    All blood vessels are lined with a protective barrier made of endothelial cells, which can become “leaky” as inflammation from tissue damage or disease breaks down the endothelium and creates gaps between the cells. These gaps allow white blood cells to move in and start the tissue repair process, and they also serve as the entry point for nanoparticles that accelerate healing.

    “We wanted to know how the shape and the aspect ratio of these nanoparticles affect their ability to cross that endothelial cell barrier,” says Ramamurthi. 

    It was a critical question to answer because not all nanoparticles are created alike, and if they can’t penetrate the barrier, they can’t repair the tissue.

    Ramamurthi and his team developed a novel cell culture model in which they simulated disease and then examined mechanisms of transport: specifically, how nanoparticles of different kinds interacted with endothelial cells and moved through them. Did they enter through gaps among the endothelial cells (a process called extravasation) or through the cells themselves (what’s known as translocation)?

    “Let’s say a nanoparticle goes through an endothelial cell. Some of it might stay within that cell and not come out the other side, which means you lose that particle, and it’s no longer useful to the healing process. The goal is transportation with minimal retention.”

    The team found that rod-shaped particles, as opposed to spherical particles, with a high aspect ratio (i.e., long and skinny versus short and stubby) were selectively taken up by diseased endothelial cells. “And they showed very little uptake into healthy endothelial cells compared with the spheres, which is good because we don’t want them interacting with healthy vessel walls,” he says.

    They also found that particles reached the tissue primarily by extravasation (or via the cell gaps). “The longer and skinnier they were, the less likely they were to remain within the endothelial cell layer, which means they’re getting through to the affected tissue for more effective therapy.”

    The team will now integrate these findings with their work on active targeting-;incorporating components on the surface of nanoparticles that recognize proteins expressed by diseased cells-;in animal models.

    The ultimate goal is to develop a nonsurgical regenerative therapy capable of slowing aneurysm growth. For example, increasing the current growth-to-rupture stage from seven years to 15 years. An even more ambitious outcome, says Ramamurthi, would be to revert that growth. 

    “Regression of aneurysm growth would be the preferred long-term outcome,” he says. “That’s a long way off, but we’re excited because these findings will help guide us on how to design our nanoparticles for more efficient delivery to the aneurysm wall. It’s an opportunity to get closer to that reality.”

    Source:

    Journal reference:

    Yau, J., et al. (2024). Assessing trans‐endothelial transport of nanoparticles for delivery to abdominal aortic aneurysms. Journal of Biomedical Materials Research Part A. doi.org/10.1002/jbm.a.37667.

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  • Penn engineers develop targeted lung delivery system using lipid nanoparticles

    Penn engineers develop targeted lung delivery system using lipid nanoparticles

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    Penn Engineers have developed a new means of targeting the lungs with lipid nanoparticles (LNPs), the miniscule capsules used by the Moderna and Pfizer-BioNTech COVID-19 vaccines to deliver mRNA, opening the door to novel treatments for pulmonary diseases like cystic fibrosis. 

    In a paper in Nature Communications, Michael J. Mitchell, Associate Professor in the Department of Bioengineering, demonstrates a new method for efficiently determining which LNPs are likely to bind to the lungs, rather than the liver.

    The way the liver is designed. LNPs tend to filter into hepatic cells, and struggle to arrive anywhere else. Being able to target the lungs is potentially life-changing for someone with lung cancer or cystic fibrosis.”


    Michael J. Mitchell, Associate Professor, Department of Bioengineering, Penn

    Previous studies have shown that cationic lipids -; lipids that are positively charged -; are more likely to successfully deliver their contents to lung tissue. “However, the commercial cationic lipids are usually highly positively charged and toxic,” says Lulu Xue, a postdoctoral fellow in the Mitchell Lab and the paper’s first author. Since cell membranes are negatively charged, lipids with too strong a positive charge can literally rip apart target cells. 

    Typically, it would require hundreds of mice to individually test the members of a “library” of LNPs -; chemical variants with different structures and properties -; to find one with a low charge that has a higher likelihood of delivering a medicinal payload to the lungs.

    Instead, Xue, Mitchell and their collaborators used what is known as “barcoded DNA” (b-DNA) to tag each LNP with a unique strand of genetic material, so that they could inject a pool of LNPs into just a handful of animal models. Then, once the LNPs had propagated to different organs, the b-DNA could be scanned, like an item at the supermarket, to determine which LNPs wound up in the lungs. 

    After identifying an LNP that successfully penetrated lung cells, Xue, Mitchell and their collaborators administered the molecule to mice suffering from lung cancer: the treatment had a pronounced and positive effect, drastically reducing tumor size by delivering a strand of mRNA and gRNA that suppresses the growth of lung tumors.

    “This technology will help to accelerate the development of mRNA therapeutics beyond the liver,” says Xue, pointing to the speed, low cost and efficacy of the technique. 

    This study was conducted at the University of Pennsylvania School of Engineering and Applied science and supported by a US National Institutes of Health (NIH) Director’s New Innovator Award (DP2 TR002776), a Burroughs Wellcome Fund Career Award at the Scientific Interface (CASI), a US National Science Foundation CAREER Award (CBET-2145491) and an American Cancer Society Research Scholar Grant (RSG-22-122-01-ET).

    Other co-authors include Alex G. Hamilton, Rakan El-Mayta, Xuexiang Han, Ningqiang Gong, Junchao Xu, Christian G. Figueroa-Espada, Sarah J. Shepherd and Alvin J. Mukalel of Penn Engineering; Gan Zhao, Zebin Xiao and Andrew E. Vaughan of Penn Vet; Xinhong Xiong and Jiaxi Cui of Yangtze Delta Region Institute (Huzhou); Karin Wang of Temple University; and Mohamed-Gabriel Alameh and Drew Weissman of the Perelman School of Medicine at Penn.

    Source:

    Journal reference:

    Xue, L., et al. (2024). High-throughput barcoding of nanoparticles identifies cationic, degradable lipid-like materials for mRNA delivery to the lungs in female preclinical models. Nature Communications. doi.org/10.1038/s41467-024-45422-9.

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  • Directive giant upconversion by supercritical bound states in the continuum

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    Theory

    In the section ‘TCMT: critical coupling for an isolated mode’, the local field enhancement at critical coupling for an isolated resonant mode is demonstrated. In the section ‘Open-resonator TCMT’, the non-Hermitian Hamiltonian formalism of TCMT for FW-BIC formation is used. It will be shown that, as the asymptotic condition of BIC cannot be ideally reached, the FW quasi-BIC originates from non-orthogonal modes. This understanding will then be used in the section ‘Supercritical coupling’ to evaluate the coupling between the dark FW quasi-BIC and the bright leaky partner, demonstrating the analogy to EIT and the equation for supercritical local field enhancement. In the section ‘RCWA validation’, we validate the TCMT results using RCWA.

    TCMT: critical coupling for an isolated mode

    The basic equation describing the evolution of the mode amplitude A1 (oscillator 1) in a resonating system with a characteristic angular frequency ω1 = 2πc/λ1, is

    $$\frac{{\rm{d}}{A}_{1}}{{\rm{d}}t}=\,j{\omega }_{1}{A}_{1}-\left(\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{r}}}}\right){A}_{1},$$

    (2)

    in which energy can be lost through absorption (or other additive non-radiative channels, such as scattering by dielectric fluctuations or in-plane leakage) with decay rate γa = 1/τa, as well as through direct far-field coupling with external radiation in the outer space with a decay rate γr = 1/τr. The amplitude is normalized such that |A1|2 represents the energy of the mode15. When adding the driving field of power |s+|2 and monochromatic time dependence exp(int), associated with the external excitation and coupled with the resonator with coefficient κi, the equation becomes

    $$\frac{{\rm{d}}{A}_{1}}{{\rm{d}}t}=\,j{\omega }_{1}{A}_{1}-\left(\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{r}}}}\right){A}_{1}+{\kappa }_{{\rm{i}}}\,{s}_{+}.$$

    (3)

    The solution is

    $${A}_{1}({\omega }_{{\rm{in}}})=\frac{{\kappa }_{{\rm{i}}}\,{s}_{+}}{j({\omega }_{{\rm{in}}}-{\omega }_{1})+\left(\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{r}}}}\right)}.$$

    (4)

    It is possible to demonstrate that the input power coupling must be related to the radiation decay as \({\kappa }_{{\rm{i}}}=\sqrt{2/{\tau }_{{\rm{r}}}}\) by invoking energy conservation and time-reversal symmetry of Maxwell’s equations. On resonance, that is, when the input frequency 2πc/λin = ωin is set at the peak ω1, it follows that

    $${A}_{1}({\omega }_{1})=\frac{\sqrt{2/{\tau }_{{\rm{r}}}}{s}_{+}}{1/{\tau }_{{\rm{a}}}+1/{\tau }_{{\rm{r}}}}.$$

    (5)

    Now let us consider that the quality factor Q of a resonator is defined as the ratio between the stored (W) and the lost energy fractions. Indeed, for the absorption-related power loss Pabs (or, more generally, all non-radiative losses) and the radiation loss Prad, the following holds true

    $$\frac{1}{Q}=\frac{1}{{Q}_{{\rm{a}}}}+\frac{1}{{Q}_{{\rm{r}}}}=\frac{{P}_{{\rm{abs}}}}{{\omega }_{1}W}+\frac{{P}_{{\rm{rad}}}}{{\omega }_{1}W}=\frac{2}{{\omega }_{1}}\left(\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{r}}}}\right)=\frac{2}{{\omega }_{1}}\left({\gamma }_{{\rm{a}}}+{\gamma }_{{\rm{r}}}\right).$$

    (6)

    The driving field has amplitude Ei = s+/Ac, in which Ac is a normalized cross-section, which we define as Ac = 1, for simplicity. The local field of the resonant mode has amplitude given by \({E}_{{\rm{loc}}}={A}_{1}/\sqrt{{V}_{{\rm{eff}}}}\), with Veff the normalized effective mode volume. Thus, from equation (5), it follows that the local field enhancement G is given by

    $$G=\frac{| {E}_{{\rm{loc}}}{| }^{2}}{| {E}_{{\rm{i}}}{| }^{2}}\simeq \frac{{Q}^{2}}{{Q}_{{\rm{r}}}{V}_{{\rm{eff}}}}=\frac{{Q}_{{\rm{a}}}^{2}{Q}_{{\rm{r}}}^{2}}{{Q}_{{\rm{r}}}{({Q}_{{\rm{r}}}+{Q}_{{\rm{a}}})}^{2}{V}_{{\rm{eff}}}},$$

    (7)

    and depends on the ratio between the total quality factor Q = 1/(1/Qa + 1/Qr) = QaQr/(Qa + Qr) and the radiation quality factor Qr. Clearly, if QrQa as for the ideal BIC with Qr → ∞, then asymptotically \(G\approx {Q}_{{\rm{a}}}^{2}/{Q}_{{\rm{r}}}\to 0\). The maximum enhancement Gcr is reached when Qr = Qa, at the critical coupling condition, for which

    $${G}_{{\rm{cr}}}\approx \frac{{Q}_{{\rm{a}}}^{4}}{{Q}_{{\rm{a}}}^{3}{V}_{{\rm{eff}}}}=\frac{{Q}_{{\rm{a}}}}{{V}_{{\rm{eff}}}}.$$

    (8)

    The above result has been applied to BICs in several papers13 and its origin dates to the general theory of optical and electrical resonators discussed in textbooks15. Supposing a nearly ideal resonator with Qr = Qa, the maximum field enhancement would reach the physical capacity limit imposed by the unavoidable system losses represented by Qa. In dielectric resonators sustaining quasi-BICs, the critical coupling point can be approached by breaking the in-plane symmetry of the system to tune the radiation quality factor that scales quadratically with the asymmetry parameter5, which requires precise nanostructure engineering and knowledge of the system losses.

    Open-resonator TCMT

    The theory of FW-BIC formation owing to coupling of two leaky modes has been reviewed in ref. 47. The demonstration based on the non-Hermitian Hamiltonian of temporal coupled modes can be found in recent papers19. The formation of FW-BICs has gained attention particularly in the context of photonic-crystal slabs with vertical asymmetry, in which TM-like and TE-like modes couple and interfere48,49. However, it is worth noting that the existence of non-radiating modes arising from the interference of vector TE-like and TM-like eigenmodes was first discussed in ref. 17. It was found that, in 2D holey textured slabs, TE and TM modes can couple at virtually any point in the first Brillouin zone, leading to anticrossing of their dispersion and formation of a mode with zero imaginary part of its eigenfrequency, known as an FW-BIC2. In this study, a photonic-crystal slab placed over a dielectric waveguide substrate with air cladding was considered, breaking vertical symmetry and favouring the coupling of vector TE-like and TM-like modes. The same system was used in our previous work10, in which we experimentally observed and applied the FW quasi-BIC, and it is also used in the present study.

    To develop what we term the ‘supercritical enhancement equation’, we start from the non-Hermitian Hamiltonian of coupled waves25,48. By generalizing equation (3), the dynamic equations for resonance amplitudes can be written in the following form

    $$\frac{{\rm{d}}{\bf{A}}}{{\rm{d}}t}=(\,j\hat{\varOmega }-{\hat{\varGamma }}_{{\rm{r}}}-{\hat{\varGamma }}_{{\rm{a}}}){\bf{A}}+{\hat{K}}_{{\rm{i}}}^{{\rm{T}}}{{\bf{s}}}^{+},$$

    (9)

    $${{\bf{s}}}^{-}=\hat{C}{{\bf{s}}}^{+}+\hat{D}{\bf{A}},$$

    (10)

    in which both \(\hat{\varOmega }\) and \({\hat{\varGamma }}_{{\rm{r}}}\) matrices are Hermitian matrices representing the resonance frequencies and the radiation decay, respectively. On the other hand, \({\hat{\varGamma }}_{{\rm{a}}}\) represents non-radiative losses and is initially set to zero \({\hat{\varGamma }}_{{\rm{a}}}=0\) to isolate the radiative rate associated with an ideal BIC. The resonant mode is excited by the incoming far-field waves s+ coupled to the resonator with coefficients denoted by \({\hat{K}}_{{\rm{i}}}\). The outgoing waves s depend on the direct scattering channel \(\hat{C}\) and the resonant modes A by means of the decay port coefficients in \(\hat{D}\). Energy conservation and time-reversal symmetry imply that \({\hat{K}}_{{\rm{i}}}=\hat{D}\) and that the coupling with the port is linked with radiation loss, implying that \({\hat{D}}^{\dagger }\hat{D}=2{\hat{\varGamma }}_{{\rm{r}}}\). These relationships determine the elements of \({\hat{K}}_{{\rm{i}}}^{{\rm{T}}}\) and imply that \({\rm{r}}{\rm{a}}{\rm{n}}{\rm{k}}({\hat{\varGamma }}_{{\rm{r}}})={\rm{r}}{\rm{a}}{\rm{n}}{\rm{k}}({\hat{D}}^{\dagger }\hat{D})={\rm{r}}{\rm{a}}{\rm{n}}{\rm{k}}(\hat{D})\). Also, \(\hat{D}=-\,\hat{C}\,{\hat{D}}^{\star }\). Let us consider a system denoted by A = (A1, A2)T, in which A1 and A2 represent the amplitudes of two modes with frequencies ω1 and ω2, respectively. These resonances have radiative lifetimes τr1 = 1/γr1 and τr2 = 1/γr2. Moreover, both resonances may experience absorption loss, characterized by 1/τa = γa. It is important to note that, for the specific case of the avoided crossing point, the absorption terms for both modes are the same, as we demonstrate below. Then, in general, γ1,2 = γr1,r2 + γa, but for now, let’s turn γa = 0.

    Recall that the modes of the resonator are defined as the eigenmodes of the non-Hermitian Hamiltonian operator \(\hat{H}=j\hat{\varOmega }-{\hat{\varGamma }}_{{\rm{r}}}\) (neglecting non-radiative loss). Only Hermitian matrices allow for a diagonal representation with orthogonal eigenvectors, whereas non-Hermitian matrices may have linearly dependent or linearly independent but non-orthogonal eigenvectors, or they may have orthogonal eigenvectors depending on specific properties such as parity–time symmetry. The Hamiltonian and its eigenvalues are functions of the in-plane momentum k = ko(sinθcosϕ, sinθsinϕ). A previous study demonstrated that the eigenvectors of the non-Hermitian Hamiltonian are always non-orthogonal when the total number of independent decay ports is less than the number of optical modes and both modes are coupled to the decay ports25. The crucial concept here is that of independent decay ports, which are related to the sharing of the vertical symmetry of the modes. In the case of evolving TE-like and TM-like modes, the inversion of their character at the avoided crossing can occur at any point in energy–momentum space. We know that the eigenmodes of a matrix form an orthogonal basis if and only if \({\hat{H}}^{\dagger }\hat{H}=\hat{H}{\hat{H}}^{\dagger }\). Because both \(\hat{\varOmega }\) and \({\hat{\varGamma }}_{{\rm{r}}}\) are Hermitian, this is equivalent to the relation \(\hat{\varOmega }\,{\hat{\varGamma }}_{{\rm{r}}}={\hat{\varGamma }}_{{\rm{r}}}\,\hat{\varOmega }\), which implies that \(\hat{\varOmega }\) and \({\hat{\varGamma }}_{{\rm{r}}}\) can be simultaneously diagonalized. When considering two eigenmodes and a single independent radiation channel, in which \({\rm{r}}{\rm{a}}{\rm{n}}{\rm{k}}({\hat{\varGamma }}_{{\rm{r}}})=1\), one of the orthogonal eigenmodes of the matrix will have a pure imaginary eigenvalue. This indicates that one of the two modes has an infinite lifetime (BIC) and does not couple to the decay port. As a non-zero coupling with the single decay port exists, the two eigenvectors in the resonator system will always be non-orthogonal25. Therefore, the modes are generally non-orthogonal if a single radiation channel is involved. However, they can satisfy the orthogonality condition at a specific point in momentum space. This point is referred to as an ideal FW-BIC point kBIC when the Hamiltonian (\(\hat{H}=j\hat{\varOmega }-{\hat{\varGamma }}_{{\rm{r}}}\), defined below) has a purely imaginary eigenvalue (or, equivalently, \(\hat{\varOmega }+j{\hat{\varGamma }}_{{\rm{r}}}\) has a purely real eigenvalue). This allows for the simultaneous diagonalization of the Hermitian matrices \(\hat{\varOmega }\) and \({\hat{\varGamma }}_{{\rm{r}}}\).

    FW condition

    The Hamiltonian of a two-waves-two-ports system is represented as:

    $$\hat{H}=j(\begin{array}{cc}{\omega }_{1} & \kappa \\ \kappa & {\omega }_{2}\end{array})-(\begin{array}{cc}{\gamma }_{{\rm{r}}1} & X\\ {X}^{\star } & {\gamma }_{{\rm{r}}2}\end{array})=j(\begin{array}{cc}{\omega }_{1}+j{\gamma }_{{\rm{r}}1} & \kappa +jX\\ \kappa +j{X}^{\star } & {\omega }_{2}+j{\gamma }_{{\rm{r}}2}\end{array})\equiv j(\begin{array}{cc}{\mathop{\omega }\limits^{ \sim }}_{1} & {\mathop{\omega }\limits^{ \sim }}_{12}\\ {\mathop{\omega }\limits^{ \sim }}_{21} & {\mathop{\omega }\limits^{ \sim }}_{2}\end{array}),$$

    (11)

    in which κ measures the near-field coupling and X represents the coupling mediated by the continuum between the two closed, uncoupled channel resonances of frequencies ω1 and ω2. Following the calculation in refs. 19,25, X can be expressed as

    $$X=\sqrt{{\gamma }_{{\rm{r1}}}{\gamma }_{{\rm{r2}}}}{{\rm{e}}}^{j\psi },$$

    (12)

    in which the phase angle ψ describes the relative phase of the coupling with the open channel and in general with the two ports (up and down). The eigenvalues of the two diagonal frequency and decay matrices of the Hamiltonian at the BIC point, defined by

    $$\hat{{H}^{{\rm{r}}}}({{\bf{k}}}_{{\rm{B}}{\rm{I}}{\rm{C}}})=\hat{\varOmega }+j{\hat{\varGamma }}_{{\rm{r}}}=(\begin{array}{cc}{\mathop{\omega }\limits^{ \sim }}_{+} & 0\\ 0 & {\mathop{\omega }\limits^{ \sim }}_{-}\end{array})+j(\begin{array}{cc}{\mathop{\gamma }\limits^{ \sim }}_{+} & 0\\ 0 & {\mathop{\gamma }\limits^{ \sim }}_{-}\end{array}),$$

    (13)

    and associated with the collective modes \({\widetilde{A}}_{+},{\widetilde{{\rm{A}}}}_{-}\), are related to the uncoupled mode frequency and decay rates by

    $${\mathop{\omega }\limits^{ \sim }}_{\pm }+{j\mathop{\gamma }\limits^{ \sim }}_{\pm }=({\omega }_{1}+{\omega }_{2})/2+j({\gamma }_{{\rm{r}}1}+{\gamma }_{{\rm{r}}2})/2\,+$$

    (14)

    $$\pm \frac{1}{2}\sqrt{{\left[({\omega }_{1}-{\omega }_{2})+j({\gamma }_{{\rm{r}}1}-{\gamma }_{{\rm{r}}2})\right]}^{2}+4{\left(\kappa +j\sqrt{{\gamma }_{{\rm{r}}1}{\gamma }_{{\rm{r}}2}}{{\rm{e}}}^{j\psi }\right)}^{2}}.$$

    (15)

    This relation allows us to determine the asymptotic FW condition as a function of the uncoupled mode frequency, the decay rate and the coupling rate among closed channel modes κ

    $$\kappa ({\gamma }_{{\rm{r}}1}-{\gamma }_{{\rm{r}}2})=\sqrt{{\gamma }_{{\rm{r}}1}{\gamma }_{{\rm{r}}2}}{{\rm{e}}}^{j\psi }({\omega }_{1}-{\omega }_{2}),$$

    (16)

    $$\psi =m{\rm{\pi }},\,m\in {\mathscr{Z}}$$

    (17)

    Substituting (γr1 − γr2) from equation (16) into equation (15), it is possible to find that the third term with the square root is exactly equal to the second term in equation (14) and cancels, or adds with it, depending on the sign ±. The dark mode acquires ideally zero radiation loss (say, \({\widetilde{\omega }}_{-}\) without loss of generality). At this condition, the eigenvalues are

    $${\mathop{\omega }\limits^{ \sim }}_{+}{+j\mathop{\gamma }\limits^{ \sim }}_{+}=\frac{{\omega }_{1}+{\omega }_{2}}{2}+\frac{\kappa ({\gamma }_{{\rm{r}}1}+{\gamma }_{{\rm{r}}2})}{2\sqrt{{\gamma }_{{\rm{r}}1}{\gamma }_{{\rm{r}}2}}{{\rm{e}}}^{j\psi }}+\,j({\gamma }_{{\rm{r}}1}+{\gamma }_{{\rm{r}}2}),$$

    (18)

    $${\mathop{\omega }\limits^{ \sim }}_{-}+\,j{\mathop{\gamma }\limits^{ \sim }}_{-}=\frac{{\omega }_{1}+{\omega }_{2}}{2}-\frac{\kappa ({\gamma }_{{\rm{r}}1}+{\gamma }_{{\rm{r}}2})}{2\sqrt{{\gamma }_{{\rm{r}}1}{\gamma }_{{\rm{r}}2}}{{\rm{e}}}^{j\psi }},\,\,\,{\rm{w}}{\rm{i}}{\rm{t}}{\rm{h}}\,{\mathop{\gamma }\limits^{ \sim }}_{-}=0,$$

    (19)

    in which the wave of amplitude \({\widetilde{A}}_{-}\) has no radiative loss and becomes the ideal FW-BIC (ideally dark mode), whereas all radiative loss is transferred to the bright mode \({\widetilde{A}}_{+}\). At this point in momentum space (k = kBIC), \(\hat{\varOmega }\) and \({\hat{\varGamma }}_{{\rm{r}}}\) are both diagonal, and because \({\rm{r}}{\rm{a}}{\rm{n}}{\rm{k}}({\hat{\varGamma }}_{{\rm{r}}})=1\) (only a single independent decay port exists), the resonant states interfere to annihilate the coupling with the radiation channel of the BIC mode, which guarantees energy conservation, as any coupling among the final orthogonal modes asymptotically vanishes47.

    However, arbitrarily close to the BIC point in the momentum, both modes experience non-zero radiative loss. The modes are coupled with a single independent radiation channel and, thus, are non-orthogonal because their coupling guarantees energy conservation. This behaviour holds true in any real system, particularly with momentum close to ideal FW-BICs, referred to as FW quasi-BICs. It is worth mentioning that, in the presence of non-negligible absorption loss, the modes are always non-orthogonal. If we perturb the ideal FW-BIC condition by moving in momentum space, in the representation in which \(\hat{\varOmega }\) is diagonal, in general, \({\hat{\Gamma }}_{r}\) must have non-zero off-diagonal terms to ensure energy conservation, or similarly, in the representation in which \({\hat{\varGamma }}_{{\rm{r}}}\) is diagonal, \(\hat{\varOmega }\) must have non-zero off-diagonal terms, κ12,21, which represent the near-field coupling. This is a key concept that implies that \(\forall {\bf{k}}:{\bf{k}}\simeq {{\bf{k}}}_{{\rm{BIC}}}\), the new perturbed Hamiltonian \(\hat{{H}^{{\rm{r}}}}({\bf{k}}\simeq {{\bf{k}}}_{{\rm{B}}{\rm{I}}{\rm{C}}})\) for the final coupled modes, the FW quasi-BIC \({A}_{-}({\bf{k}}\simeq {{\bf{k}}}_{{\rm{B}}{\rm{I}}{\rm{C}}})\) and bright \({A}_{+}({\bf{k}}\simeq {{\bf{k}}}_{{\rm{B}}{\rm{I}}{\rm{C}}})\) modes, can be represented with non-zero off-diagonal terms in \(\hat{\varOmega }({\bf{k}}\simeq {{\bf{k}}}_{{\rm{B}}{\rm{I}}{\rm{C}}})\), when \({\hat{\varGamma }}_{{\rm{r}}}\) is diagonal because of energy conservation, as described below (Extended Data Fig. 1a).

    The same non-Hermitian Hamiltonian can also describe the effect of coupled-resonance-induced transparency resulting from the interference of non-orthogonal eigenvectors, that is, at a wavevector different from the ideal FW-BIC condition. Hsu et al. demonstrated that, when several resonances (two or more) are connected to a single independent decay port, a transparency window, known as coupled-resonance-induced transparency, always occurs regardless of the radiation loss values of the resonances because of the off-diagonal terms21. Therefore, this coupling, also necessary for any FW quasi-BIC point, can give rise to coupled-resonance-induced transparency in special cases. The condition for EIT can, in principle, also occur with momentum near the ideal FW-BIC point, for example, when kEIT = kBIC + δk (Extended Data Fig. 1a). At the EIT point, the slow light condition increases the photon–matter interaction time, enhancing emission properties.

    Supercritical coupling

    Coupled-resonance-induced transparency in far-field representation

    We first describe the occurrence of the transparency condition in the far-field representation and its link with the near-field representation. We then consider the perturbation of the Hamiltonian close to the FW-BIC to explicitly demonstrate that the FW quasi-BIC, despite being a quasi-dark mode, can reach the maximum physical limit of the local field enhancement under the supercritical coupling condition, thanks to the near-field coupling with its bright partner. The calculations presented here follow refs. 21,25 for clarity of description, but with harmonic time dependence convention exp(int). Let us first restate the TCMT problem by writing the dynamical equations for the two modes that are non-orthogonal in the representation in which \(\hat{\varOmega }({\bf{k}})\) is diagonal, with a single radiation channel. Because the representation is changed with respect to equation (11), we consider different symbols for elements in the matrices and we adopt this representation only because the condition for EIT emergence is rather simple to show:

    $$\frac{{\rm{d}}}{{\rm{d}}t}\left(\begin{array}{c}{A}_{1}\\ {A}_{2}\end{array}\right)=\left[j\left(\begin{array}{cc}{\bar{\omega }}_{1} & 0\\ 0 & {\bar{\omega }}_{2}\end{array}\right)-\left(\begin{array}{cc}{\bar{\gamma }}_{{\rm{r}}1} & {\gamma }_{12}\\ {\gamma }_{12} & {\bar{\gamma }}_{{\rm{r}}2}\end{array}\right)-\left(\begin{array}{cc}{\gamma }_{{\rm{a}}} & 0\\ 0 & {\gamma }_{{\rm{a}}}\end{array}\right)\right]\left(\begin{array}{c}{A}_{1}\\ {A}_{2}\end{array}\right)+\left(\begin{array}{c}{d}_{1}\\ {d}_{2}\end{array}\right){s}^{+},$$

    (20)

    $${s}^{-}={c}_{21}{s}^{+}+{d}_{1}{A}_{1}+{d}_{2}{A}_{2}.$$

    (21)

    In equation (20), the off-diagonal terms γ12 in the radiative decay matrix must be non-zero for energy conservation if both modes decay in the channel, meaning that the decay matrix and the frequency matrix cannot have diagonal forms simultaneously21,25. In equation (21), s is the transmitted wave and we have, owing to the presence of the substrate-breaking vertical symmetry, that the direct scattering matrix elements are c11 = −c22 = (1 − n)/(1 + n), with n index of the substrate and \({c}_{12}={c}_{21}=2\sqrt{n}/(1+n)\). Equation (21) simplifies when the system is mirror symmetric because n = 1 (ref. 21). Invoking again energy conservation and time-reversal symmetry and using the relations between \({\hat{\varGamma }}_{{\rm{r}}}\), \(\hat{C}\) and \(\hat{D}\):

    $${d}_{1,2}=j\sqrt{2{\bar{\gamma }}_{{\rm{r}}1,{\rm{r}}2}/(n+1)},$$

    (22)

    $${\gamma }_{12}=\sqrt{{\bar{\gamma }}_{{\rm{r}}1}{\bar{\gamma }}_{{\rm{r}}2}}.$$

    (23)

    Let us keep using a mirror-symmetric system to determine the condition of induced transparency. The experimental case is then calculated with RCWA, showing that the condition for induced transparency also holds for vertical asymmetry. The complex transmission coefficient at regime is25

    $$t={{\rm{c}}}_{21}\mp \frac{({c}_{11}\pm {c}_{12})[\,j({\omega }_{{\rm{in}}}-{\bar{\omega }}_{2})+{\gamma }_{{\rm{a}}}]{\bar{\gamma }}_{{\rm{r}}1}+[\,j({\omega }_{{\rm{in}}}-{\bar{\omega }}_{1})+{\gamma }_{{\rm{a}}}]{\bar{\gamma }}_{{\rm{r}}2}}{[\,j({\omega }_{{\rm{in}}}-{\bar{\omega }}_{1})+{\gamma }_{{\rm{a}}}+{\bar{\gamma }}_{{\rm{r}}1}][\,j({\omega }_{{\rm{in}}}-{\bar{\omega }}_{2})+{\gamma }_{{\rm{a}}}+{\bar{\gamma }}_{{\rm{r}}2}]-{\bar{\gamma }}_{{\rm{r}}1}{\bar{\gamma }}_{{\rm{r}}2}},$$

    (24)

    in which |c11 + c12| = |c22 − c12| and we have already established that absorption is the same for both modes and given by γa. The top (bottom) signs are used when both modes are even (odd) with respect to vertical symmetry. In the limit \({\gamma }_{{\rm{a}}}\ll {({\bar{\omega }}_{1}-{\bar{\omega }}_{2})}^{2}/\max ({\bar{\gamma }}_{{\rm{r}}1},{\bar{\gamma }}_{{\rm{r}}2})\), the absorptive decay rate is sufficiently small that the transmission coefficient approaches 1 (EIT condition) when the numerator of the second term becomes zero at the transparency frequency ωt, given by

    $${\omega }_{{\rm{in}}}=\frac{{\bar{\omega }}_{1}{\bar{\gamma }}_{{\rm{r}}2}+{\bar{\omega }}_{2}{\bar{\gamma }}_{{\rm{r}}1}}{{\bar{\gamma }}_{{\rm{r}}1}+{\bar{\gamma }}_{{\rm{r}}2}}\doteq {\omega }_{{\rm{t}}}.$$

    (25)

    This condition is always fulfilled when \({\bar{\omega }}_{1} < {\omega }_{{\rm{in}}} < {\bar{\omega }}_{2}\) provided that the resonances are sufficiently close, regardless of their radiative damping. In a real system for γa ≠ 0, the approximation to this condition is a consequence of the optical theorem, for which t cannot reach ideally 1. Nonetheless, the fast dispersion induced at the transparency frequency leads to an enhancement of the local optical field50,51,52. Indeed, when the EIT is approached, light is substantially slowed down, which favours light–matter interactions and enhances the optical-emission process. With this simple demonstration, we have proved that FW-BIC and EIT can be close in principle in the momentum space. Indeed, the induced transparency arises from the coupling of two optical modes to the same radiation channel, which is also the same framework near FW-BIC.

    Near-field representation

    Although the diagonal frequency matrix representation is useful for finding the transparency condition, the next one will provide more insight into the mode coupling. Let us now rewrite the dynamic equations (20) in the representation in which the radiative decay is diagonal. We will indicate the final eigenvector waves at k = kEIT with amplitudes A+ and A (not to be confused with the amplitudes \({\widetilde{A}}_{+},{\widetilde{{\rm{A}}}}_{-}\) at the FW-BIC wavevector k = kBIC in equation (13). As mentioned earlier, \({\rm{r}}{\rm{a}}{\rm{n}}{\rm{k}}({\hat{\varGamma }}_{{\rm{r}}})={\rm{r}}{\rm{a}}{\rm{n}}{\rm{k}}(\hat{D})=1\). Thus, in its diagonal representation, \({\hat{\varGamma }}_{{\rm{r}}}\) has only one non-trivial element because the determinant must be zero. It is straightforward to demonstrate that, in this equivalent representation (with c21 = 1),

    $$\frac{{\rm{d}}}{{\rm{d}}t}\left(\begin{array}{c}{{A}^{{\prime} }}_{+}\\ {{A}^{{\prime} }}_{-}\end{array}\right)=\left[j\left(\begin{array}{cc}{{\omega }^{{\prime} }}_{+} & {{\kappa }^{{\prime} }}_{12}\\ {{\kappa }^{{\prime} }}_{12} & {{\omega }^{{\prime} }}_{-}\end{array}\right)-\left(\begin{array}{cc}{{\gamma }^{{\prime} }}_{+} & 0\\ 0 & 0\end{array}\right)-\left(\begin{array}{cc}{{\gamma }^{{\prime} }}_{{\rm{a}}} & {{\zeta }^{{\prime} }}_{12}\\ {{\zeta }^{{\prime} }}_{21} & {{\gamma }^{{\prime} }}_{{\rm{a}}}\end{array}\right)\right]\left(\begin{array}{c}{{A}^{{\prime} }}_{+}\\ {{A}^{{\prime} }}_{-}\end{array}\right)+\left(\begin{array}{c}{{d}^{{\prime} }}_{1}\\ 0\end{array}\right){s}^{+},$$

    (26)

    $${s}^{-}={s}^{+}+{{d}^{{\prime} }}_{1}\,{{A}^{{\prime} }}_{+},$$

    (27)

    in which the connection with the previous representation of the diagonal frequency matrix is given by:

    $${{\omega }^{{\prime} }}_{+}=\frac{{\bar{\omega }}_{1}{\bar{\gamma }}_{{\rm{r}}1}+{\bar{\omega }}_{2}{\bar{\gamma }}_{{\rm{r}}2}}{{\bar{\gamma }}_{{\rm{r}}1}+{\bar{\gamma }}_{{\rm{r}}2}},$$

    (28)

    $${{\omega }^{{\prime} }}_{-}=\frac{{\bar{\omega }}_{1}{\bar{\gamma }}_{{\rm{r}}2}+{\bar{\omega }}_{2}{\bar{\gamma }}_{{\rm{r}}1}}{{\bar{\gamma }}_{{\rm{r}}1}+{\bar{\gamma }}_{{\rm{r}}2}},$$

    (29)

    $${{\kappa }^{{\prime} }}_{12}=\frac{({\bar{\omega }}_{2}-{\bar{\omega }}_{1})\sqrt{{\bar{\gamma }}_{{\rm{r}}1}{\bar{\gamma }}_{{\rm{r}}2}}}{{\bar{\gamma }}_{{\rm{r}}1}+{\bar{\gamma }}_{{\rm{r}}2}},$$

    (30)

    $${{\gamma }^{{\prime} }}_{+}={\bar{\gamma }}_{{\rm{r}}1}+{\bar{\gamma }}_{{\rm{r}}2},$$

    (31)

    $${{\gamma }^{{\prime} }}_{-}=0,$$

    (32)

    $${d}_{1}^{{\prime} }=\sqrt{{d}_{1}^{2}+{d}_{2}^{2}}.$$

    (33)

    The above relations are useful because they directly state that the transparency frequency ωt = ω, that is, it corresponds to the final dark mode. This link is important: at the transparency frequency, the fast dispersion slows down the light and enhances the local field, which corresponds to the dark mode. Although in the previous representation we were dealing with non-orthogonal modes in which their coupling was expressed in the far field, in this second representation, we can see that a non-radiative dark mode with γ = 0 is coupled by means of a non-zero near-field constant κ12 to a bright leaky wave with a decay rate \({{\gamma }^{{\prime} }}_{+}={\bar{\gamma }}_{{\rm{r}}1}+{\bar{\gamma }}_{{\rm{r}}2}\). These identities must not be confused with equations (18) and (19) that express the relations between the diagonal dark and bright modes at the FW-BIC point k = kBIC with the original uncoupled modes. Instead, the above equations refer to two different representations of the same modes at fixed and same wavevector k = kEIT ≠ kBIC. Here, when the drive field is turned off, the dark-mode amplitude decays to zero. In the linear regime, exchange energy occurs between the modes. We see below that, while the drive field is on, energy flows from the bright mode to the dark mode. As the drive field is turned off, energy flows from the dark mode to the bright mode. Consequently, the dark mode undergoes decay in the far field owing to its nearly zero direct coupling with the radiation channel and its non-zero near-field coupling with the bright mode53. In this alternative representation, it is the near-field coupling between a dark mode and the bright mode that gives rise to the transparency condition. This formulation aligns with the general framework used in the subradiant–superradiant model, which illustrates the analogue of EIT in photonic and plasmonic systems50,51,52.

    Maximum enhancement at the FW quasi-BIC

    The FW-BIC and classical analogue of EIT formalisms are derived from the same original framework of modes coupled to a single radiation channel: the EIT with non-zero off-diagonal terms, whereas the ideal FW-BIC is a limit of this framework with zero off-diagonal terms. Because the EIT occurs at the avoided crossing, FW-BIC must not be at the avoided crossing, which implies that the radiative decay rates of the closed channel modes in equation (16) differ, γr1 ≠ γr2. Thus, the ideal FW-BIC is not at the avoided crossing (ω1 = ω2) but is shifted in its vicinity. Both conditions can be fulfilled, in principle, for close wavevectors when, for example, γr1 5γr2 (see the simulated linewidths when the modes do not cross each other in Extended Data Fig. 3; orientation angle of the photonic crystal ϕ = 45°). This also means that the realization of EIT is possible when the involved dark mode is a perturbation of the FW-BIC mode, that is, it exhibits characteristics of an FW quasi-BIC. Although this will be shown using RCWA in our system, let us now explore the consequences for enhancing the local optical field.

    As shown in the scheme of Extended Data Fig. 1a, let us write explicitly the dynamical equations (13) and add the perturbation of the diagonal representation (FW-BIC point) of the Hamiltonian as we move away from the ideal BIC wavevector towards the EIT point. Because the radiative Q factor of a BIC scales as |k − kBIC|α with α ≥ 2, for any wavevector close to the BIC point, k = kBIC + ΔqkBIC, it is necessary to admit a finite non-zero decay rate of the dark mode A, that is, 1/γ = τR1 with γ → ε 0 and, as such, it is necessary to include a non-zero mode coupling κ12 ≠ 0 to guarantee energy conservation, as both modes are coupled to a single independent radiation channel. The perturbed Hamiltonian is \(\hat{{H}^{{\rm{r}}}}({{\bf{k}}\simeq {\bf{k}}}_{{\rm{B}}{\rm{I}}{\rm{C}}})=(\begin{array}{cc}{\omega }_{+} & {\kappa }_{12}\\ {\kappa }_{12} & {\omega }_{-}\end{array})+j(\begin{array}{cc}{\gamma }_{+} & 0\\ 0 & {\gamma }_{-}\end{array})\). It is important to note that the modes are the final coupled modes: their frequencies are considered shifted with respect to the exact frequencies of bright and dark modes of the FW point k = kBIC in equation (14). The finite decay rate of the dark mode turns it into a quasi-dark mode (FW quasiBIC), and this non-zero coupling to the radiation channel \((\sqrt{2{\gamma }_{-}}=\sqrt{2/{\tau }_{{\rm{R}}1}})\) will imply non-zero near-field (κ12) or far-field (γ12) coupling with the shifted bright partner, depending on the representation used. The bright mode has amplitude A+, with a decay rate 1/γ+ = τR2τR1. Generally, the off-diagonal terms can be kept complex to include both near-field and far-field coupling, but we have verified by RCWA that the coupling is real with good approximation in the next section. Here we assume the representation with near-field coupling κ12. Considering the general dynamical equations with both modes having the same losses included all in γa = 1/τa, it is possible to write, \(\forall {\bf{k}}:{\bf{k}}\simeq {{\bf{k}}}_{{\rm{BIC}}}\) that

    $$\frac{{\rm{d}}{A}_{-}}{{\rm{d}}t}=j{\omega }_{-}\,{A}_{-}-\left(\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{R}}1}}\right){A}_{-}+j{\kappa }_{12}{A}_{+}+\sqrt{\frac{2}{{\tau }_{{\rm{R}}1}}}{s}_{+},$$

    (34)

    $$\frac{{\rm{d}}{A}_{+}}{{\rm{d}}t}=j{\omega }_{+}\,{A}_{+}-\left(\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{R}}2}}\right){A}_{+}+j{\kappa }_{12}A\_+\sqrt{\frac{2}{{\tau }_{{\rm{R}}2}}}{s}_{+}.$$

    (35)

    This set of equations is valid for any system (for example, plasmonic modes, whispering-gallery modes, guided modes, defect modes). Considering \(\frac{{\rm{d}}}{{\rm{d}}t}\to j{\omega }_{{\rm{in}}}\) and solving for A in equation (34), substituting it in equation (35) and then substituting the resulting A+ again in equation (34), we find, at the steady state, that

    $$\begin{array}{l}\frac{{A}_{-}({\omega }_{{\rm{in}}})}{{s}_{+}}=\frac{\sqrt{\frac{2}{{\tau }_{{\rm{R}}1}}}}{j({\omega }_{{\rm{in}}}-{\omega }_{-})+\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{R}}1}}}+\\ +\frac{j/{\tau }_{\kappa }\sqrt{\frac{2}{{\tau }_{{\rm{R}}2}}}}{\left[j({\omega }_{{\rm{in}}}-{\omega }_{-})+\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{R}}1}}\right]\left[j({\omega }_{{\rm{in}}}-{\omega }_{+})+\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{R}}2}}+\frac{1/{\tau }_{\kappa }^{2}}{j({\omega }_{{\rm{in}}}-{\omega }_{-})+1/{{\rm{\tau }}}_{a}+1/{{\rm{\tau }}}_{R1}}\right]}+\\ -\frac{1/{{\rm{\tau }}}_{{\rm{\kappa }}}^{2}\sqrt{\frac{2}{{{\rm{\tau }}}_{R1}}}}{{\left[j({\omega }_{{\rm{in}}}-{\omega }_{-})+\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{R}}1}}\right]}^{2}\left[j({\omega }_{{\rm{in}}}-{\omega }_{+})+\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{R}}2}}+\frac{1/{\tau }_{\kappa }^{2}}{j({\omega }_{{\rm{in}}}-{\omega }_{-})+1/{\tau }_{{\rm{a}}}+1/{\tau }_{{\rm{R}}1}}\right]},\end{array}$$

    (36)

    $$\begin{array}{l}\frac{{A}_{+}({\omega }_{{\rm{in}}})}{{s}_{+}}=\frac{\sqrt{\frac{2}{{\tau }_{{\rm{R}}2}}}}{j({\omega }_{{\rm{in}}}-{\omega }_{+})+\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{R}}2}}+\frac{1/{\tau }_{\kappa }^{2}}{j({\omega }_{{\rm{in}}}-{\omega }_{-})+1/{\tau }_{{\rm{a}}}+1/{\tau }_{{\rm{R}}1}}}+\\ +\frac{j/{\tau }_{\kappa }\sqrt{\frac{2}{{\tau }_{{\rm{R}}1}}}}{\left[j({\omega }_{{\rm{in}}}-{\omega }_{-})+\frac{1}{{\tau }_{a}}+\frac{1}{{\tau }_{{\rm{R}}1}}\right]\left[j({\omega }_{{\rm{in}}}-{\omega }_{+})+\frac{1}{{\tau }_{{\rm{a}}}}+\frac{1}{{\tau }_{{\rm{R}}2}}+\frac{1/{\tau }_{\kappa }^{2}}{j({\omega }_{{\rm{in}}}-{\omega }_{-})+1/{\tau }_{{\rm{a}}}+1/{\tau }_{{\rm{R}}1}}\right]}.\end{array}$$

    (37)

    Above, we have explicitly defined the near-field coupling lifetime \({{\rm{\tau }}}_{{\rm{\kappa }}}=\frac{1}{{{\rm{\kappa }}}_{12}}\) and the associated quality factor τκ = 2Qκ/ω. We can see that the quasi-dark mode A can be excited by means of internal coupling κ12 more than what is expected from the isolated resonance response of the dark mode, represented by the first term in equation (36) (in Supplementary Information section 1.2 and Supplementary Fig. 4, the mediated drive term is also made explicit in the original quantum model)2. In Extended Data Fig. 1b–d, the behaviour for both mode intensities for a specific set of informative values, QR1 = 5 × 109, QR2 = 200, Qa = 5,000 is plotted to capture the main insight. In Extended Data Fig. 1b, the intensity field enhancement

    $$G=\frac{{\left|{A}_{\pm }\right|}^{2}}{{\left|{s}_{+}/\sqrt{{\omega }_{{\rm{in}}}}\right|}^{2}{V}_{{\rm{eff}}}}$$

    (38)

    is plotted for both modes (solid red line for the dark A and blue line for the bright A+), showing that the dark mode on resonance (ωin = ω) reaches the maximum limit of field enhancement possible in a real-world resonator with non-radiative loss, Gmax = Qa/Veff, even if

    $${Q}_{{\rm{R}}1}\gg {Q}_{{\rm{a}}},$$

    (39)

    which would be impossible in case of a single dark resonance, that is, not coupled to another wave (dashed red line). This condition occurs at the supercritical coupling point defined by

    $${\bar{\tau }}_{\kappa }=\sqrt{{\tau }_{{\rm{R}}2}{\tau }_{{\rm{a}}}},$$

    (40)

    or

    $${\bar{Q}}_{\kappa }=\sqrt{{{Q}_{{\rm{R}}2}Q}_{{\rm{a}}}}.$$

    (41)

    Indeed, assuming τR1τa, τR2, τκ and τR2 < τa in equation (36) and considering ωin = ω (on resonance with the dark mode) and |ωin − ω+|  2κ12 = 2/τκ (the coupling affects the split in frequencies, thus the pump is shifted from the bright mode when on resonance with the dark one), the relation simplifies as

    $$\frac{{A}_{-}\left({\omega }_{{\rm{in}}}={\omega }_{-}\right)}{{s}_{+}}\to {\left[\frac{j/{\tau }_{\kappa }\sqrt{\frac{2}{{\tau }_{{\rm{R}}2}}}}{j/\left({\tau }_{\kappa }{\tau }_{{\rm{a}}}\right)+1/{\tau }_{{\rm{a}}}^{2}+1/\left({\tau }_{{\rm{R}}2}{\tau }_{{\rm{a}}}\right)+1/{\tau }_{\kappa }^{2}}\right]}_{{\bar{{\rm{\tau }}}}_{\kappa }=\sqrt{{\tau }_{{\rm{R}}2}{\tau }_{{\rm{a}}}}}\to j\sqrt{{\tau }_{{\rm{a}}}/2},$$

    (42)

    in which the first two terms in the denominator were neglected, as they are smaller when τR2 < τa. The above relation proves that the dark-mode intensity enhancement \(G={| \frac{{A}_{-}\left({\omega }_{{\rm{in}}}={\omega }_{-}\right)}{{s}_{+}/\sqrt{{\omega }_{{\rm{in}}}}}| }^{2}\frac{1}{{V}_{{\rm{eff}}}}={Q}_{{\rm{a}}}/{V}_{{\rm{eff}}}={G}_{\max }\), that is, it can reach the maximum imposed by non-radiative losses even in extreme situations with mismatched quality factors. It is worth mentioning that, when Qκ → ∞ (κ12 → 0), we again obtain the correct case of uncoupled resonances and the dark-mode field goes to the level it could gain if it were isolated (dashed red line). Indeed, in the plot, we have specified that the near-field coupling rate affects the spectral separation among resonances, as it is proportional to their distance: ω± = ωo ± κ12 = ωo[1 ± 1/(2Qκ)] Thus, for Qκ → ∞, the resonant frequencies coincide and cross. Even when out of perfect spectral tuning, the maximum gain achieved by the quasi-dark mode A is orders of magnitudes larger than what possible in a single dark mode, as shown in Extended Data Fig. 1c,d. In case ωin = ωo = 1/2(ω+ + ω), the optimum shifts to larger Q*κQa. When QR2 → Qa and ωin = ω, the bright mode is critically coupled with the pump, but there is still energy going into the dark mode up to 0.3Gmax at a certain \({{Q}^{* }}_{\kappa }\lesssim {\bar{Q}}_{\kappa }={Q}_{{\rm{a}}}\). Furthermore, by inspecting the ratio between the solid red line and the dashed red line, it is possible to appreciate how, even if Qκ does not reach the optimum, the intensity of the coupled dark resonance is orders of magnitude larger than that of the single resonance.

    Further discussion

    The supercritical coupling mechanism guarantees the possibility of achieving the maximum level of local field enhancement when the coupling (Qκ) is optimally tuned, and always in the highest Q-factor mode, even under the conditions of coupling, for both bright and dark modes, which would be unfavourable in the case of single isolated modes. To give an example, let QR2 = 103Qa = 106 QR1 = 1010, thus none of the modes matches Qa; by contrast, they have completely unmatched quality factors. If \({Q}_{\kappa }=\sqrt{{10}^{3}\times {10}^{6}}\simeq 3\times {10}^{4}\) (say, Veff = 1 for brevity), the dark mode reaches the maximum intensity enhancement Gmax = 106, although the intensity enhancement of the single dark resonance would be only 102, that is, four orders of magnitude less, as shown in Fig. 1e. Also, the supercritical coupling condition is independent of the highest Q-factor resonance, unlike the critical coupling condition (QR1 = Qa); the model converges to the critical-coupling result if QR1 → Qa and can ensure a higher level of enhancement in the dark mode, with a considerable advantage over the single-dark-resonance case, even when QR2 and Qκ vary over a considerably large range of values. This is shown for fixed \({\bar{Q}}_{\kappa }=\sqrt{{{Q}_{{\rm{R2}}}Q}_{{\rm{a}}}}\) in Extended Data Fig. 1e.

    This mechanism holds true for all wavevectors that span the range from an FW quasi-BIC to the EIT point (if this is also present in the system), with correspondingly varied values of the parameters involved (coupled mode frequencies, decay rates and near-field coupling). Far from this momentum region, the mode coupling becomes progressively negligible (as it can be easily calculated numerically) and the isolated single mode response is restored.

    Turning to the parallel with coupled-resonance-induced transparency, we understand that, at the dark mode frequency ωt = ω′ (equations (25) and (29)), in which the transparency window occurs, the fast dispersion leads to slow light and an enhanced field that, with suitable coupling between modes, could reach the maximum field enhancement of the system, as indicated by supercritical coupling. We recall that EIT is not a necessary condition for the FW mechanism, although it may widen, if present, the wavevector span of an enhanced field.

    RCWA validation

    The validity of TCMT is confirmed through numerical simulations using full 3D RCWA. RCWA simulations are performed using the Fourier modal expansion method (Ansys Lumerical, RCWA module). Validation is performed by evaluating the exact transmittance spectra, the 3D-vector-field distribution of the interfering modes, their complex coupling constant, their evolution with momentum, the near-field coupling at EIT, FW quasi-BIC and FW-BIC points in momentum space. The modes belonging to the dispersion curves are a linear combination of tens to hundreds of Fourier plane waves in each xy-periodic, z-homogeneous layer satisfying the continuity boundary conditions in each z layer of the structure (with forward and backward propagating factors along the z axis), providing the exact solution of the problem, including material dispersion, matching the experimental transmittance spectrum measured to reconstruct the energy–momentum band diagrams for both s-polarized (vector TE-like character) and p-polarized (vector TM-like character) excitation. RCWA is indeed used as a benchmark for validating other numerical techniques such as resonant-state expansion, quasi-normal modes and other methods. It provides the 3D vector fields and the exact solution, which can be analytically approximated by the leaky TE-like and TM-like modes of the effective waveguide, or TCMT. Further details are in Supplementary Information with measured refractive index dispersion (Supplementary Fig. 1) and details on fitting, giving imaginary refractive index used for simulations nI = 10−4 over the spectral range 700–1,200 nm.

    Extended Data Fig. 2a shows the theoretical TE bands expected for a uniform film of upconversion nanoparticles (UCNPs) with a refractive index of 1.45, matching the experimental absorption band of UCNPs in Extended Data Fig. 2b. Extended Data Fig. 2c shows the mode distribution, whereas Extended Data Fig. 2d evaluates the mode energy fraction superimposed on the nonlinear material as a function of refractive index, for one layer (1L), two layers (2L) and with a cladding of air or silicone oil. The silicone oil promotes vertical symmetry, which means that it increases the field overlap with the UCNPs and helps minimize scattering losses, but it cannot affect the vertical symmetry of the TE-like and TM-like modes, which is determined mainly by the different refractive index of the glass substrate, silicon nitride and UCNPs index. Indeed, the energy fraction with silicone oil only changes from 8% to 9% (Extended Data Fig. 2d). Nonetheless, silicone oil was often useful to better observe the side emission, as the silicone layer acted as a partially opaque screen crossing the outcoupled light (as shown in Fig. 3b). Note that the silicone oil layer was not used in Fig. 4b.

    Extended Data Fig. 3 shows the evolution of the transmittance spectra by changing the azimuthal angle of incidence ϕ. The avoided crossing stops only when the two modes no longer intersect, as shown clearly in Extended Data Fig. 3b at ϕ = 45°, at which it is also possible to observe that the uncoupled mode 1 has linewidth larger than mode 2, that is, γr1γr2. Extended Data Fig. 3c,d shows the details of FW quasi-BIC and avoided crossing.

    Extended Data Fig. 4 shows that vector TE-like and TM-like modes evolve and change symmetry along the momentum; they are, in general, non-orthogonal and nearly coincident at the avoided crossing (and approximately even with respect to the z-mirror symmetry). Because the modes are nearly coincident, the approximation γa = 1/τa in the above model, that is, the same for both modes, is correct. Also, because the input intensity is Iinput = 1, the resonance field intensity is much larger than what would be expected on the basis of critical coupling (material absorption loss, nI = 10−4 is included in the simulation), providing an estimate of the field enhancement (I1 > 3 × 104Iinput).

    Extended Data Fig. 5a shows the spectral coincidence of the coupled-resonance-induced transparency (EIT) frequency (for θ = 2.7° at the avoided crossing) with the FW quasi-BIC frequency at θ = 3.15° for the angle mismatch <0.5° (mismatched momentum kEIT = kBIC + δk). The existence of coupled-resonance-induced transparency can only occur for non-orthogonal modes25, and the proximity in momentum space to the BIC point proves that FW-BIC is an ideal condition originating from the evolution of non-orthogonal modes. Extended Data Fig. 5b shows the near-field coupling constant normalized to ω = 2πc/λmodel calculated using the formula in ref. 54 (equation (4.13), page 162, including material distribution), for θ from 2.7° (EIT) to 3.24° (nearly ideal FW-BIC). The phase mismatch is minimal, thus the two modes also exchange energy along the propagation (Pendellösung effect), as it commonly occurs between two modes of the same waveguide coupled by a periodic modulation15,54. The near-field coupling was calculated as

    $${\kappa }_{12}=\frac{1}{4}\sqrt{\frac{{\varepsilon }_{{\rm{o}}}}{{\mu }_{{\rm{o}}}}}\frac{{k}_{{\rm{o}}}}{\sqrt{{N}_{1}{N}_{2}}}\int \left(\varepsilon -{\varepsilon }_{{\rm{o}}}\right){{{\bf{E}}}_{1}}^{\star }\cdot {{\bf{E}}}_{2}{\rm{d}}A,$$

    in which \({N}_{{\rm{1,2}}}=\frac{1}{2}| \int ({{{\bf{E}}}^{* }}_{1,2}\times {{\bf{H}}}_{1,2}+{\bf{c}}.{\bf{c}}.)\cdot \widehat{z}{\rm{d}}A| \) are optical power normalizations. The integral is over the unitary cell area A. Note that the calculation provides the complex κ12, in which the imaginary part of κ12 is to be understood as a representation of ζ12 in equation (26) above. We estimated that ζ12 < 10−4κ12 for all modes in the range θ (0°, 5°), thus ζ12 0. Also, we found that κ12κ21, as expected. The near-field coupling is stronger at the EIT point, whereas it decreases at the ideal FW-BIC, in agreement with the behaviour expected from the temporally coupled mode theory. As the incidence angle varies from the EIT point (2.7°) to the ideal position of the BIC (3.24°), Qκ = τκ ω/2 varies accordingly and is characterized by a \({Q}_{\kappa }\approx ({10}^{3},{10}^{4})\approx \sqrt{{Q}_{{\rm{R2}}}{Q}_{{\rm{a}}}}\) at the FW quasi-BIC mode (dashed black line, 3.15°). As the near-field coupling is modulated, the fulfilment of the supercritical coupling condition can be tuned.

    Supplementary Fig. 2 shows the evolution of the interference process as a function of κ12 and describes how the coupling changes at the edge. The effect of the finite boundary on resonance was investigated using near-field scanning optical microscopy (Witec Alpha RAS 300) and shown in Supplementary Fig. 3.

    Supplementary Fig. 4 shows theoretical linewidths calculated with the original FW quantum model2, revealing that the open-channel wave acts as a drive field in the coupled BIC equation, for representative near-field coupling values.

    Fabrication

    Extended Data Fig. 6 shows the energy-level scheme of the produced UCNPs. All materials and synthesis details of NPs, NP characterization, PCNS fabrication and characterization are in Supplementary Information sections 2–4 and Supplementary Figs. 5 and 6.

    Optical characterization

    Dispersion-band-diagram measurements, experimental interrogation and detection scheme of upconversion are provided, respectively, in Supplementary Information sections 5 and 6 and Supplementary Figs. 7–10. For upconversion, the pulsed (150-fs) Ti:Sa oscillator, with central wavelength λin = 810 nm and full-width at half-maximum of 6 nm, is tuned to the FW quasi-BIC and focused to a 6-µm spot on the PCNS. The power coupled with NPs was 5%, corresponding to 48 kW cm−2 at a pulse energy of 6.25 nJ (103 kW cm−2).

    Photoluminescence, enhancement-factor and radiance-enhancement estimation

    Enhancement-factor estimation, spectral emission datasets from samples and radiance-enhancement-factor estimation are provided, respectively, in Supplementary Information section 7 and Supplementary Figs. 11 and 12.

    FDTD simulations

    The radiation properties of the PCNS were evaluated using the FDTD method in Ansys Lumerical. A single dipole source was used to compute the isofrequency map using the Z-transform of the local optical field retrieved within the finite-structure domain with the 3D full-field monitor. The intensity of the Z-transform determines the strength of radiation in the momentum space and better represents the radiation properties associated with the PCNS. To validate the results found with this approach, we first simulated a literature case discussed in ref. 44, that is, supercollimation resulting from flat-band dispersion in the momentum space, which is shown in Supplementary Fig. 13. The isofrequency far-field intensity map in momentum space showed, in our case, non-trivial vanishing strips along orthogonal arms (cross of zeros; Fig. 3 and Extended Data Fig. 7). The near-field intensity map showed self-collimation as occurring when flat dispersion is involved. In Extended Data Fig. 7e, the experimental proof is reported using a rescaled geometry of the PCNS (using the fit in Extended Data Fig. 2e) to move the FW-BIC at 532 nm and make the beam easily visible. At this stage, the radiation properties were examined by placing an array of dipole sources (18 × 18) at the boundary of the finite PCNS with a uniform slab covering an area of several microns squared. The results are shown in Fig. 3c and Extended Data Fig. 8. The sources collectively add up their field and coherently emit radiation in the plane of the slab, as shown in Extended Data Fig. 8a, in which the field propagates along the direction (+1, 0) with intensity enhancement as large as 1.5 × 104 (normalized to the number of emitters). The emission was always pointing towards the non-textured slab, thus—on the opposite edge—the propagation was along the direction (−1, 0). It was found that, at shorter wavelengths, other preferential directions of propagation were also possible, such as (1, ±1). The divergence was evaluated along 1 mm of propagation from the edge, as shown in Extended Data Fig. 8b, which showed a divergence of 0.02° (Extended Data Fig. 8c), which is even lower than the experimental values. Analysis of the whole visible and near-infrared spectrum revealed that the typical value of the divergence is less than 0.5° (Extended Data Fig. 8d), demonstrating that this regime of narrow radiation is expected to be common in this type of photonic structure. Indeed, as shown in Extended Data Fig. 8e, the full width at half maximum of the beam periodically contracts and expands  along the propagation, which is because of a mechanism of self-healing that compensates for diffraction.

    Directivity measurements

    Extended Data Fig. 9a shows the microscopy inspection of light propagation near the edge. Extended Data Fig. 9b shows the experimental results on the divergence of the side beam (directed along the outer edge versor), with a polar plot of the edge emission in Extended Data Fig. 9c, in agreement with simulation in Extended Data Fig. 8 in the upconverted emission.

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  • Butterfly Wings Inspire Breakthrough in Catalyst Design

    Butterfly Wings Inspire Breakthrough in Catalyst Design

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    Butterfly Wings Catalyst Chemical Reaction

    New research inspired by the intricate structure of butterfly wings has led to a method for fine-tuning catalytic reactions, enhancing selectivity and efficiency in chemical production. This breakthrough underscores the potential for bioinspired designs to drive industrial innovation. Credit: SciTechDaily.com

    Researchers expand ways to improve the selectivity of catalytic reactions.

    Researchers from the Harvard John A. Paulson School of Engineering and Applied Sciences (SEAS), Harvard Department of Chemistry & Chemical Biology, and Utrecht University have reported on a previously elusive way to improve the selectivity of catalytic reactions, adding a new method of increasing the efficacy of catalysts for a potentially wide range of applications in various industries including pharmaceuticals, cosmetics and much more.

    The research will be published today (February 16) in Nature Catalysis.

    Challenges in Catalytic Processes

    The chemical industry relies on catalysts for over 90 percent of its processes and nearly all these catalysts consist of nanoparticles dispersed on top of a substrate. Researchers have long suspected that the size of individual nanoparticles and the distance between them play important roles in the speed of, and the products produced in the catalytic reaction, but because nanoparticles are prone to moving around and agglomerating during catalysis, it’s been difficult to study exactly how.

    Over the past decade, Joanna Aizenberg, the Amy Smith Berylson Professor of Materials Science and Professor of Chemistry & Chemical Biology, and her lab have been drawing inspiration from nature to build highly ordered, porous materials for a wide range of catalytic reactions. Inspired by the structure of butterfly wings, the researchers designed a new catalyst platform that partially embeds nanoparticles into the substrate, trapping them so they don’t move around during catalysis, while leaving the rest of the nanoparticles’ surface exposed, enabling them to perform the catalytic reactions efficiently and without agglomeration.

    Efficient Catalysts Smaller Average Interparticle Distance

    Smaller average interparticle distance. Gold, silver, white, and red spheres represent gold, palladium, Silicon, and oxygen atoms, respectively. Credit: Harvard SEAS, edited

    Enhancing Reaction Selectivity

    The researchers found that the distance between particles had a huge impact on the selectivity of the reaction.

    “Many industrially-relevant chemical reactions follow a cascade whereby chemical A is turned to chemical B which can then be turned into chemical C and so forth,” said Kang Rui Garrick Lim, a graduate student in the Aizenberg Lab and first author of the study. “In some catalytic processes, the intermediate chemical, chemical B, is the goal, while in others it is the end product, chemical C. The selectivity of the catalyst refers to whether it favors the production of chemical B or chemical C.”

    A good example of this is the production of benzyl alcohol, a chemical used in everything from shellacs, paints, and leather production to intravenous medications, cosmetics, and topical drugs.

    Benzyl alcohol is the intermediate chemical B, derived from the hydrogenation of benzaldehyde (chemical A), before the reaction creates toluene (chemical C), another commonly used chemical but of lower value. In order to produce benzyl alcohol efficiently, the formation of toluene needs to be suppressed.

    Currently, to make the more useful benzyl alcohol, the catalytic hydrogenation reaction is slowed down, or not run to completion, to ensure that the reaction will stop at B and form as little toluene as possible.

    “Generally, to make these intermediate chemicals, you make the catalyst less reactive and the overall reaction slower, which is not productive at all,” said Lim. “Catalysts are meant to speed things up, not slow them down.”

    Implications and Future Directions

    The researchers demonstrated their platform in the catalytic formation of benzyl alcohol. Lim and the team found that when catalytic metal nanoparticles were placed further apart on the substrate, the reaction was more selective towards benzyl alcohol, the intermediate chemical. When the nanoparticles were closer together, the reaction was more selective towards toluene, the end product. Given that the distance between nanoparticles can be adjusted synthetically using the bioinspired catalyst platform, the research suggests that the same catalyst platform can be easily adapted for a range of intermediate or end-product chemicals.

    Catalysis is central to the production of a whole range of extremely important materials that are used in pharmaceuticals, consumer products, and in manufacturing many products all of us use in everyday life,” said Aizenberg.

    “Adding this selectivity-improving tool to the chemist’s arsenal is extremely important. It will allow more effective tuning of catalytic processes, more economical use of the feedstocks accompanied by the reduction of energy consumption and waste generation. We hope that chemists will use our platform in further optimization of new and existing catalytic processes.”

    Next, the team will use the same platform to understand how the size of nanoparticles impacts the reaction at fixed distances between nanoparticles.

    Reference: 16 February 2024, Nature Catalysis.
    DOI: 10.1038/s41929-023-01104-1

    Harvard’s Office of Technology Development has protected the intellectual property of Professor Aizenberg’s lab, which is the underlying technology of this research.

    The research was co-authored by Selina K. Kaiser, Haichao Wu, Sadhya Garg, Marta Perxes Perich, Jessi E. S. van der Hoeven and Michael Aizenberg. It was supported in part by the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under award number DE-SC0012573 and by the US Defense Threat Reduction Agency (DTRA) under award number HDTR1211001612.



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  • New research shows promise for urine-based test to detect ovarian cancer

    New research shows promise for urine-based test to detect ovarian cancer

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    New research by Joseph Reiner and colleagues at Virginia Commonwealth University shows promise for a urine-based test for ovarian cancer. Reiner will present their research at the 68th Biophysical Society Annual Meeting, to be held February 10 – 14, 2024 in Philadelphia, Pennsylvania.

    Previous research showed that there are thousands of small molecules, called peptides, in the urine of people with ovarian cancer. While it is possible to detect those molecules using certain well-established techniques, those techniques aren’t straightforward or cost effective. Reiner sought a new approach to more easily detect those peptides. 

    He turned to nanopore sensing, which has the potential to simultaneously detect multiple peptides. The basic idea of nanopore sensing involves passing molecules through a tiny pore, or nanopore, and measuring the changes in electrical current or other properties as the molecules move through.

    To harness the nanopore technology to detect various peptides, Reiner used gold nanoparticles that can partially block the pore. Peptides, like those in the urine of people with ovarian cancer, will then “stick to the gold particle and basically dance around and show us a unique current signature,” Reiner explained.

    The method is capable of simultaneously identifying multiple peptides, and in their study they identified and analyzed 13 peptides, including those derived from LRG-1, a biomarker found in the urine of ovarian cancer patients. Of those 13 peptides, Reiner said, “we now know what those signatures look like, and how they might be able to be used for this detection scheme. It’s like a fingerprint that basically tells us what the peptide is.”

    Clinical data shows a 50-75% improvement in 5-year survival when cancers are detected at their earliest stages. This is true across numerous cancer types.”


    Joseph Reiner and colleagues, Virginia Commonwealth University

    Their ultimate goal is to develop a test that, combined with other information like CA-125 blood tests, transvaginal ultrasound, and family history, could improve early-stage ovarian cancer detection accuracy in the future.

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  • Italian Scientists Develop New System for Producing Green Hydrogen Cheaply and Efficiently

    Italian Scientists Develop New System for Producing Green Hydrogen Cheaply and Efficiently

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    A New System for Producing Green Hydrogen Cheaply and Efficiently

    IIT and BeDimensional’s researchers used nanoparticles of ruthenium, a noble metal that is similar to platinum in its chemical behavior but far cheaper, to serve as the active phase of the electrolyser’s cathode, leading to an increased efficiency of the overall electrolyzer. Credit: IIT-Istituto Italiano di Tecnologia

    A collaborative research effort between IIT and its spin-off BeDimensional has discovered a method utilizing ruthenium particles in conjunction with a solar-powered electrolysis system.

    What does it take to produce green hydrogen more efficiently and cheaply? Apparently, small ruthenium particles and a solar-powered system for water electrolysis. This is the solution identified by a joint team involving the Istituto Italiano di Tecnologia (Italian Institute of Technology, IIT) of Genoa, and BeDimensional S.p.A. (an IIT spin-off).

    The technology, developed in the context of the Joint-lab’s activities and recently published in two high-impact factor journals (Nature Communications and the Journal of the American Chemical Society) is based on a new family of electrocatalysts that could reduce the costs of green hydrogen production on an industrial scale.

    Hydrogen is considered as a sustainable energy vector, an alternative to fossil fuels. But not all hydrogen is the same when it comes to environmental impact. Indeed, the main way hydrogen is produced nowadays is through the methane steam reforming, a fossil fuel-based process that releases carbon dioxide (CO2) as a by-product.

    The hydrogen produced by this process is classified as “grey” (when CO2 is released into the atmosphere) or “blue” (when CO2 undergoes capture and geological storage). To significantly reduce emissions to zero by 2050 these processes must be replaced with more environmentally sustainable ones that deliver “green” (i.e. net-zero emissions) hydrogen. The cost of “green” hydrogen critically depends on the energy efficiency of the setup (the electrolyzer) that splits water molecules into hydrogen and oxygen.

    Technological Innovations in Hydrogen Production

    The researchers from the joint team of this discovery have developed a new method that guarantees greater efficiency than currently known methods in the conversion of electrical energy (the energy bias exploited to split water molecules) into the chemical energy stored in the hydrogen molecules that are produced. The team has developed a concept of catalyst and have used renewable energy sources, such as the electrical energy produced by a solar panel.

    Liberato Manna, Francesco Bonaccorso, Yong Zuo, Sebastiano Bellani, Marilena Zappia, Michele Ferri

    The new solution has been identified by a joint team involving the Istituto Italiano di Tecnologia (Italian Institute of Technology, IIT) of Genoa, and BeDimensional S.p.A. (an IIT spin-off). In the picture: Liberato Manna (IIT), Francesco Bonaccorso (BeDimensional), Yong Zuo (IIT), Sebastiano Bellani (BeDimensional), Marilena Zappia (BeDimensional), Michele Ferri (IIT). Credit: IIT-Istituto Italiano di Tecnologia

    “In our study, we have shown how it is possible to maximise the efficiency of a robust, well-developed technology, despite an initial investment that is slightly greater than what would be needed for a standard electrolyzer. This is because we are using a precious metal such as ruthenium”, commented Yong Zuo and Michele Ferri from the Nanochemistry Group at IIT in Genoa.

    The researchers used nanoparticles of ruthenium, a noble metal that is similar to platinum in its chemical behavior but far cheaper. Ruthenium nanoparticles serve as the active phase of the electrolyzer’s cathode, leading to an increased efficiency of the overall electrolyzer.

    “We have run electro-chemical analyses and tests under industrially-significant conditions that have enabled us to assess the catalytic activity of our materials. Additionally, theoretical simulations allowed us to understand the catalytic behavior of ruthenium nanoparticles at the molecular level; in other words, the mechanism of water splitting on their surfaces,” explained Sebastiano Bellani and Marilena Zappia from BeDimensional, who were involved in the discovery. “Combining the data from our experiments with additional process parameters, we have carried out a techno-economic analysis that demonstrated the competitiveness of this technology, when compared to state-of-the-art electrolyzers.”

    Cost-Effectiveness of the New Technology

    Ruthenium is a precious metal that is obtained in small quantities as a by-product of platinum extraction (30 tonnes per year, as compared to the annual production of 200 tonnes of platinum) but at a lower cost (18.5 dollars per gram as opposed to 30 dollars for platinum). The new technology involves the use of just 40 mg of ruthenium per kilowatt, in stark contrast with the extensive use of platinum (up to 1 gram per kilowatt) and iridium (between 1 and 2.5 grams per kilowatt, with iridium price being around 150 dollars per gram) that characterize proton-exchange membrane electrolyzers.

    By using ruthenium, the researchers at IIT and BeDimensional have improved the efficiency of alkaline electrolyzers, a technology that has been used for decades due to its robustness and durability. For example, this technology was on board of the Apollo 11 capsule that brought humanity to the moon in 1969. The new family of ruthenium-based cathodes for alkaline electrolyzers that has been developed is very efficient and has a long operating life, being therefore capable of reducing the production costs of green hydrogen.

    “In the future, we plan to apply this and other technologies, such as nanostructured catalysts based on sustainable two-dimensional materials, in up-scaled electrolyzers powered by electrical energy from renewable sources, including electricity produced by photovoltaic panels,” concluded the researchers.

    Reference: “Ru–Cu Nanoheterostructures for Efficient Hydrogen Evolution Reaction in Alkaline Water Electrolyzers” by Yong Zuo, Sebastiano Bellani, Gabriele Saleh, Michele Ferri, Dipak V. Shinde, Marilena Isabella Zappia, Joka Buha, Rosaria Brescia, Mirko Prato, Roberta Pascazio, Abinaya Annamalai, Danilo Oliveira de Souza, Luca De Trizio, Ivan Infante, Francesco Bonaccorso and Liberato Manna, 25 September 2023, Journal of the American Chemical Society.
    DOI: 10.1021/jacs.3c06726

    “High-performance alkaline water electrolyzers based on Ru-perturbed Cu nanoplatelets cathode” by Yong Zuo, Sebastiano Bellani, Michele Ferri, Gabriele Saleh, Dipak V. Shinde, Marilena Isabella Zappia, Rosaria Brescia, Mirko Prato, Luca De Trizio, Ivan Infante, Francesco Bonaccorso and Liberato Manna, 4 August 2023, Nature Communications.
    DOI: 10.1038/s41467-023-40319-5



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  • The New Nanosheet Method Catalyzing a Green Energy Revolution

    The New Nanosheet Method Catalyzing a Green Energy Revolution

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    One Pot Nanosheet Method

    Japanese researchers have innovated a “one-pot” method to produce palladium nanosheets, offering significant improvements in energy efficiency and catalytic activity. This breakthrough in nanotechnology could transform the use of palladium in various industries, marking a significant step towards more sustainable energy solutions. Credit: Minoru Osada

    A team from the Institute for Future Materials and Systems at Nagoya University, Japan, has innovated a new “one-pot” technique for creating nanosheets using less rare metals. This advancement promises to make the process of generating energy more environmentally friendly. The findings were recently published in the journal ACS Nano.

    Producing clean energy is important because it helps reduce global warming and contributes to building a carbon-neutral society. A potential source of clean energy uses hydrogen catalysts, such as palladium (Pd). Industries use Pd in electrolysis to separate water into hydrogen and oxygen. Afterward, the hydrogen in fuel cells is used to create electricity. The only byproduct is water.

    Advancements in Nanotechnology

    Pd is commonly used in a spherical ‘nanoparticle’ form for catalyst use. However, a flatter, thinner surface would use fewer precious metals and increase the available surface area for the reaction.

    Minoru Osada at Nagoya University and his research group have developed a new way to make Pd nanosheets. They named it the “one-pot method” because it can be done in a single glass bottle. The resulting sheets were so thin (1~2 nm) that they can be compared to the size of a single molecule or DNA strand.

    The “One-Pot” Method

    According to Osada, “Our newly developed method is a safe, simple, and energy-saving process. Nanosheets can be synthesized at a low temperature of 75°C in a single hour with no special reaction vessel. Although the conventional synthesis method struggles to synthesize nanosheets with a uniform thickness and size, our one-pot method can easily do this.”

    These nanosheets offer great improvements over existing technology. “Our 2D nanosheets have 2.8 times more surface area than spherical nanoparticles because of their sheet-like shape,” said Osada. “They had over twice the catalytic activity of the current generation of hydrogen evolution catalysts in performance tests.”

    Since hydrogen reactions are important for many industries, this research promises to have a transformative impact. Osada expressed hope that the new Pd nanosheets would be used not only in renewable energy but also in a wide range of industries. “To date, Pd nanoparticles have been widely used as important catalysts for various chemical reactions ranging from gas purification to pharmaceutical synthesis. Pd nanosheets may potentially replace conventional Pd catalysts and revolutionize these processes.”

    Reference: “Facile Synthesis of Pd Nanosheets and Implications for Superior Catalytic Activity” by Sumiya Ando, Eisuke Yamamoto, Makoto Kobayashi, Akichika Kumatani and Minoru Osada, 6 November 2023, ACS Nano.
    DOI: 10.1021/acsnano.3c07861



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  • Revolutionizing Industries With Super-Durable Gold Catalysts

    Revolutionizing Industries With Super-Durable Gold Catalysts

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    Gold Chemistry Nanoparticles Concept Illustration

    A new protective layer developed by researchers improves gold catalysts’ durability, potentially expanding their industrial applications and efficiency. Credit: SciTechDaily.com

    A protective layer applied to gold nanoparticles can boost its resilience.

    For the first time, researchers including those at the University of Tokyo discovered a way to improve the durability of gold catalysts by creating a protective layer of metal oxide clusters. The enhanced gold catalysts can withstand a greater range of physical environments compared to unprotected equivalent materials.

    This could increase their range of possible applications, as well as reduce energy consumption and costs in some situations. These catalysts are widely used throughout industrial settings, including chemical synthesis and the production of medicines, these industries could benefit from improved gold catalysts.

    The Unique Appeal of Gold

    Everybody loves gold: athletes, pirates, bankers — everybody. It’s historically been an attractive metal to craft things from, like medals, jewelry, coins, and so on.

    The reason gold appears so shiny and alluring to us is that it’s chemically resilient to physical conditions that might otherwise tarnish other materials, for example, heat, pressure, oxidation, and other detriments.

    Paradoxically, however, at nanoscopic scales, tiny particles of gold reverse this trend and become very reactive, so much so that for a long time now they have been essential to realize different kinds of catalysts, intermediary substances that accelerate or in some way enable a chemical reaction to take place. In other words, they’re useful or necessary to turn one substance into another, hence their widespread use in synthesis and manufacture.

    Gold Nanoparticles Compared

    Thiol and organic polymer protection are two existing ways to add resilience to gold nanoparticles. On the right is a representation of the researchers’ new method using polyoxometalate. Credit: ©2024 Suzuki et al.

    The Innovation Behind Enhanced Gold Catalysts

    “Gold is a wonderful metal and is rightly praised in society, and especially in science,” said Associate Professor Kosuke Suzuki from the Department of Applied Chemistry at the University of Tokyo.

    “It’s great for catalysts and can help us synthesize a range of things, including medicines. The reasons for this are that gold has a low affinity for absorbing molecules and is also highly selective about what it binds with, so it allows for very precise control of chemical synthesis processes. Gold catalysts often operate at lower temperatures and pressures compared to traditional catalysts, requiring less energy and reducing environmental impact.”

    Gold Nanoparticle Annular Dark-Field Scanning Transmission Electron Microscopy

    Atomic resolution image of the researchers’ novel nanoparticle made using a technique called annular dark-field scanning transmission electron microscopy. Credit: ©2024 Suzuki et al.

    As good as gold is, though, it does have some drawbacks. It becomes more reactive the smaller particles are made of it, and there is a point at which a catalyst made with gold can begin to suffer negatively from heat, pressure, corrosion, oxidation, and other conditions. Suzuki and his team thought they could improve upon this situation and devised a novel protective agent that could allow a gold catalyst to maintain its useful functions but across a greater range of physical conditions that usually hinder or destroy a typical gold catalyst.

    “Current gold nanoparticles used in catalysts have some level of protection, thanks to agents such as dodecanethiols and organic polymers. But our new one is based on a cluster of metal oxides called polyoxometalates and it offers far superior results, especially in regard to oxidative stress,” said Suzuki.

    “We are currently investigating the novel structures and applications of polyoxometalates. This time we applied the polyoxometalates to gold nanoparticles and ascertained the polyoxometalates improve the nanoparticles’ durability. The real challenge was applying a wide range of analytical techniques to test and verify all this.”

    A Comprehensive Analytical Approach

    The team used a variety of techniques collectively known as spectroscopy. It employed no less than six spectroscopic methods which vary in the kinds of information they reveal about a material and its behavior. But generally speaking, they work by casting some kind of light onto a substance and measuring how that light changes in some way with specialized sensors. Suzuki and his team spent months running various tests and different configurations of their experimental material until they found what they were seeking.

    Future Directions and Societal Benefits

    “We’re not just driven by trying to improve some methods of chemical synthesis. There are many applications of our enhanced gold nanoparticles that could be used to benefit society,” said Suzuki.

    “Catalysts to break down pollution (many gasoline cars already have a familiar catalytic converter), less impactful pesticides, green chemistry for renewable energy, medical interventions, sensors for foodborne pathogens, the list goes on. But we also want to go further.

    “Our next steps will be to improve the range of physical conditions we can make gold nanoparticles more resilient to, and also see how we can add some durability to other useful catalytic metals like ruthenium, rhodium, rhenium and, of course, something people prize even more highly than gold: platinum.”

    Reference: “Ultra-stable and highly reactive colloidal gold nanoparticle catalysts protected using multi-dentate metal oxide nanoclusters” by Kang Xia, Takafumi Yatabe, Kentaro Yonesato, Soichi Kikkawa, Seiji Yamazoe, Ayako Nakata, Ryo Ishikawa, Naoya Shibata, Yuichi Ikuhara, Kazuya Yamaguchi and Kosuke Suzuki, 6 February 2024, Nature Communications.
    DOI: 10.1038/s41467-024-45066-9

    The study had financial support from JST FOREST (JPMJFR213M for K.S., JPMJFR2033 for R.I.), JST PRESTO (JPMJPR18T7 for K.S., JPMJPR19T9 for S.Y., JPMJPR20T4 for A.N., JPMJPR227A for T.Y.), JSPS KAKENHI (22H04971 for K.Ya), and the JSPS Core-to-Core program. XAFS measurements were conducted at SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (proposal numbers: 2023A1732, 2023A1554, 2022B1860, 2022B1684). A part of this work was supported by Advanced Research Infrastructure for Materials and Nanotechnology in Japan (ARIM) of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Grant Number JPMXP1222UT0184 and JPMXP1223UT0029.



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  • Unveiling the Power of Air in Revolutionary “Plasmonic Black Gold” Catalysis

    Unveiling the Power of Air in Revolutionary “Plasmonic Black Gold” Catalysis

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    Black Gold Catalyst and Solar Light's Airborne Victory

    The first highly efficient, air-stable, and plasmonically activated catalyst for acetylene semi-hydrogenation. Credit: Ms. Gunjan Sharma and Prof. Vivek Polshettiwar, edited

    A breakthrough plasmonic catalyst, stable in air, revolutionizes acetylene semi-hydrogenation, marking a significant advance in sustainable catalysis.

    In a significant breakthrough, Prof. Polshettiwar’s group at TIFR, Mumbai has developed a novel “Plasmonic Reduction Catalyst Stable in Air,” defying the common instability of reduction catalysts in the presence of air. The catalyst merges platinum-doped ruthenium clusters, with ‘plasmonic black gold’. This black gold efficiently harvests visible light and generates numerous hot spots due to plasmonic coupling, enhancing its catalytic performance.

    Superior Performance in Semi-Hydrogenation

    What sets this catalyst apart is its remarkable performance in the semi-hydrogenation of acetylene, an important industrial process. In the presence of excess ethene, and using only visible light illumination without any external heating, the catalyst achieved an ethene production rate 320 mmol g−1 h−1 with around 90% selectivity. This efficiency surpasses all known plasmonic and traditional thermal catalysts.

    Unique Air Stability and Mechanism Insight

    Surprisingly, this catalyst exhibits its best performance only when air is introduced alongside the reactants. This unique requirement leads to an unprecedented stability for at least 100 hours. The researchers attribute this to plasmon-mediated simultaneous reduction and oxidation processes at the active sites during the reaction.

    Further enhancing our understanding of this catalyst, finite-difference time-domain (FDTD) simulations revealed a five-fold increase in the electric field compared to pristine DPC. This field enhancement, due to the near-field coupling between the RuPt nanoparticles and DPC, plays a crucial role in activating chemical bonds.

    The catalyst’s effectiveness is also evident in its kinetic isotope effect (KIE), which is larger under light than in darkness at all temperatures. This indicates the significant role of non-thermal effects alongside photothermal activation of the reactants.

    In-depth in-situ DRIFTS and DFT studies provided insights into the reaction mechanism over the oxide surface, particularly highlighting the role of intermediates in selectivity. The partially oxidized RuPt catalyst surface generates di-σ-bonded acetylene, which then transforms through several steps to produce ethene.

    Implications for Sustainable Catalysis

    This research marks the first report of a highly efficient, air-stabilized, and plasmonically activated catalyst for acetylene semi-hydrogenation, with potential applications in a variety of other reduction reactions. The findings offer significant contributions to the understanding of plasmonic catalysis and pave the way for developing sustainable and energy-efficient catalytic systems.

    Reference: “Pt-doped Ru nanoparticles loaded on ‘black gold’ plasmonic nanoreactors as air stable reduction catalysts” by Gunjan Sharma, Rishi Verma, Shinya Masuda, Khaled Mohamed Badawy, Nirpendra Singh, Tatsuya Tsukuda and Vivek Polshettiwar, 24 January 2024, Nature Communications.
    DOI: 10.1038/s41467-024-44954-4



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