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Intense electromagnetic fields localized within resonant photonic nanostructures provide versatile opportunities for engineering nonlinear optical effects on a subwavelength scale. For dielectric structures, optical bound states in the continuum (BICs, resonant nonradiative modes that exist within the radiation continuum) are an emerging strategy to localize and intensify fields. Here, we report efficient second and third harmonic generation from Si nanowires (NWs) encoded with BIC and quasi-BIC resonances. In situ dopant modulation during vapor-liquid-solid NW growth was followed by wet-chemical etching to periodically modulate the diameter of the Si NWs and create cylindrically symmetric geometric superlattices (GSLs) with precisely defined axial and radial dimensions. By variation of the GSL structure, BIC and quasi-BIC resonant conditions were created to span visible and near-infrared optical frequencies. To probe the optical nonlinearity of these structures, we collected linear extinction spectra and nonlinear spectra from single-NW GSLs, demonstrating that quasi-BIC spectral positions at the fundamental frequency are directly correlated with enhanced harmonic generation at second and third harmonic frequencies. Interestingly, we find that deliberate geometric detuning from the BIC condition leads to a quasi-BIC resonance with maximal harmonic generation efficiency by providing a balance between the capacity to trap light and the capacity to couple to the external radiation continuum. Moreover, under focused illumination, as few as 30 geometric unit cells are required to achieve more than 90% of the approximate maximum theoretical efficiency of an infinite structure, indicating that nanostructures with projected areas smaller than ∼10 µm2 can support quasi-BICs for efficient harmonic generation. The results represent an important step toward the design of efficient harmonic generation at the nanoscale and further highlight the photonic utility of BICs at optical frequencies in ultracompact one-dimensional nanostructures.

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Over the last century, quantum theories have revolutionized our understanding of material properties. One of the most striking quantum phenomena occurring in heterogeneous media is the quantum tunneling effect, where carriers can tunnel through potential barriers even if the barrier height exceeds the carrier energy. Interestingly, the tunneling process can be accompanied by the absorption or emission of light. In most tunneling junctions made of noble metal electrodes, these optical phenomena are governed by plasmonic modes, i.e., light-driven collective oscillations of surface electrons. In the emission process, plasmon excitation via inelastic tunneling electrons can improve the efficiency of photon generation, resulting in bright nanoscale optical sources. On the other hand, the incident light can affect the tunneling behavior of plasmonic junctions as well, leading to phenomena such as optical rectification and induced photocurrent. Thus, plasmonic tunneling junctions provide a rich platform for investigating light-matter interactions, paving the way for various applications, including nanoscale light sources, sensors, and chemical reactors. In this paper, we will introduce recent research progress and promising applications based on plasmonic tunneling junctions.

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Many cancer vaccines are not successful in clinical trials, mainly due to the challenges associated with breaking immune tolerance. Herein, we report a new strategy using an adjuvant-protein-antigen (three-in-one protein conjugates with built-in adjuvant) as an anticancer vaccine, in which both the adjuvant (small-molecule TLR7 agonist) and tumor-associated antigen (mucin 1, MUC1) are covalently conjugated to the same carrier protein (BSA). It is shown that the protein conjugates with built-in adjuvant can increase adjuvant's stimulation, prevent adjuvant's systemic toxicities, facilitate the codelivery of adjuvants and antigens, and enhance humoral and cellular immune responses. The IgG antibody titers elicited by the self-adjuvanting three-in-one protein conjugates were significantly higher than those elicited by the vaccine mixed with TLR7 agonist (more than 15-fold) or other traditional adjuvants. Importantly, the potent immune responses against cancer cells suggest that this new vaccine construct is an effective strategy for the personalized antitumor immunotherapy.

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The tumor-associated antigen mucin 1 (MUC1) has been pursued as an attractive target for cancer immunotherapy, but the poor immunogenicity of the endogenous antigen hinders the development of vaccines capable of inducing effective anti-MUC1 immunodominant responses. Herein, we prepared synthetic anti-MUC1 vaccines in which the hydrophilic MUC1 antigen was N-terminally conjugated to one or two palmitoyl lipid chains (to form amphiphilic Pam-MUC1 or Pam2 -MUC1). These amphiphilic lipid-tailed MUC1 antigens were self-assembled into liposomes containing the NKT cell agonist αGalCer as an adjuvant. The lipid-conjugated antigens reshaped the physical and morphological properties of liposomal vaccines. Promising results showed that the anti-MUC1 IgG antibody titers induced by the Pam2 -MUC1 vaccine were more than 30- and 190-fold higher than those induced by the Pam-MUC1 vaccine and the MUC1 vaccine without lipid tails, respectively. Similarly, vaccines with the TLR1/2 agonist Pam3 CSK4 as an adjuvant also induced conjugated lipid-dependent immunological responses. Moreover, vaccines with the αGalCer adjuvant induced significantly higher titers of IgG antibodies than vaccines with the Pam3 CSK4 adjuvant. Therefore, the non-covalent assembly of the amphiphilic lipo-MUC1 antigen and the NKT cell agonist αGalCer as a glycolipid adjuvant represent a synthetically simple but immunologically effective approach for the development of anti-MUC1 cancer vaccines.

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Methylated cytosine is proved to have an important role as an epigenetic signal in gene regulation and is often referred to "the fifth base of DNA". A comprehensive understanding of the electronic excited state relaxation in cytosine and its methylated derivatives is crucial for revealing UV-induced photodamage to the biological genome. Because of the existence of multiple closely lying "bright" and "dark" excited states, the decay pathways in these DNA nucleosides are the most complex and the least understood so far. In this study, femtosecond transient absorption with different excitation wavelengths (240-296 nm) was used to study the relaxation of excited electronic states of 5-methylcytosine (5mC) and 2'-deoxy-5-methylcytidine (5mdCyd) in phosphate buffered aqueous solution and in acetonitrile solution. Two distinct nonradiative decay channels were directly observed. The first one is a several picosecond internal conversion channel that involves two bright ππ* states (ππ*2 and ππ*1) when ππ*2 state is initially populated. The second channel contains the lower energy ππ*1 state and a so far experimental unidentified long-lived state which exhibits a several nanosecond lifetime. The long-lived state can only be accessed by the initially excited ππ*1 state. Inspired by this new discovery in 5mC and 5mdCyd, we revisited the decay of excited state of 2'-deoxycytidine (dCyd), revealing very similar decay pathways. Additionally, a well-known dark nOπ* state (carbonyl lone pair) with ∼30 ps lifetime is present in both decay channels in dCyd. With our detailed experimental results, we successfully reconcile the long history debate of cytosine excited state relaxation mechanism by pointing out that the reason for the complex dynamics under traditional 266 nm excitation is mixed signals from the above-mentioned two distinct decay pathways. Our findings lead to a dramatically different and new picture of electronic energy relaxation in 5mdCyd/dCyd and could help to understand photostability as well as UV-induced photodamage of these nucleotides and related DNAs.

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We numerically studied the optical properties of spherical nanostructures made of an emitter core coated by a silver shell through the generalized Mie theory. When there is a strong coupling between the localized surface plasmon in the metallic shell and the emitter exciton in the core, the extinction spectra exhibit two peaks. Upon adsorption of analytes on these core-shell nanostructures, the intensities of the two peaks change with opposite trends. This property makes them potential sensitive ratiometric sensors. Molecule adsorption on these nanostructures can be quantified through a very simple optical configuration likely resulting in a much faster acquisition time compared with systems based on the traditional metal nanoparticle surface plasmon resonance (SPR) biosensors.

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Engineering near-infrared (NIR) light-sensitive enzymes remains a huge challenge. A photothermal effect-associated method is developed for tailoring the enzymatic activity of enzymes by exposure to NIR light. An ultrasmall platinum nanoparticle was anchored in an enzyme to generate local heating upon NIR irradiation, which enhanced the enzyme activity without increasing bulk temperature. Following NIR irradiation, the enzyme activity was tailored rapidly and reversibly, and was modulated by varying laser power density and irradiation time. Four enzymes were engineered, including glucoamylase, glucose oxidase, catalase, and proteinase K with NIR-light sensitivity, and demonstrated their utility in practical applications such as photolithography and NIR light-responsive antibacterial or anticancer actions. Our investigation suggests that this approach could be broadly used to engineer enzymes with NIR-light sensitivity for many biological applications.

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