Ultranarrow plasmon resonances from annealed nanoparticle lattices.

This paper reports how the spectral linewidths of plasmon resonances can be narrowed down to a few nanometers by optimizing the morphology, surface roughness, and crystallinity of metal nanoparticles (NPs) in two-dimensional (2D) lattices. We developed thermal annealing procedures to achieve ultranarrow surface lattice resonances (SLRs) with full-width at half-maxima linewidths as narrow as 4 nm from arrays of Au, Ag, Al, and Cu NPs. Besides annealing, we developed a chemical vapor deposition process to use Cu NPs as catalytic substrates for graphene growth. Graphene-encapsulated Cu NPs showed the narrowest SLR linewidths (2 nm) and were stable for months. These ultranarrow SLR nanocavity modes supported even narrower lasing emission spectra and high nonlinearity in the input-output light-light curves.

The PsbJ protein is required for photosystem II activity in centers lacking the PsbO and PsbV lumenal subunits.

Photosystem II (PS II) of oxygenic photosynthesis is found in the thylakoid membranes of plastids and cyanobacteria. The mature PS II complex comprises a central core of four membrane proteins that bind the majority of the redox-active cofactors. In cyanobacteria the central core is surrounded by 13 low-molecular-weight (LMW) subunits which each consist of one or two transmembrane helices. Three additional hydrophilic subunits known as PsbO, PsbU and PsbV are found associated with hydrophilic loops belonging to the core proteins protruding into the thylakoid lumen. During biogenesis the majority of the LMW subunits are known to initially associate with individual pre-assembly complexes consisting of one or more of the core proteins; however, the point at which the PsbJ LMW subunit binds to PS II is not known. The majority of models for PS II biogenesis propose that the three extrinsic proteins and PsbJ bind in the final stages of PS II assembly. We have investigated the impact of creating the double mutants ∆PsbJ:∆PsbO, ∆PsbJ:∆PsbU and ∆PsbJ:∆PsbV to investigate potential cooperation between these subunits in the final stages of biogenesis. Our results indicate that PsbJ can bind to PS II in the absence of any one of the extrinsic proteins. However, unlike their respective single mutants, the ∆PsbJ:∆PsbO and ∆PsbJ:∆PsbV strains were not photoautotrophic and were unable to support oxygen evolution suggesting a functional oxygen-evolving complex could not assemble in these strains. In contrast, the PS II centers formed in the ∆PsbJ:∆PsbU strain were capable of photoautotrophic growth and could support oxygen evolution when whole-chain electron transport was supported by the addition of bicarbonate.

Plasmonic Photoelectrocatalysis in Copper-Platinum Core-Shell Nanoparticle Lattices.

This paper reports that strongly coupled bimetallic core-shell nanoparticle arrays show photoelectrocatalytic activity for hydrogen evolution reactions (HER). We fabricated large-area Cu-Pt nanoparticle lattices by combining top-down lithography and solution-based chemistry. These coupled lattices support two different types of plasmon modes, localized surface plasmons from individual particles and surface lattice resonances (SLRs) from the 2D lattice, that increased HER catalytic activity under white-light illumination up to 60%. Comparing photoelectrocatalytic performances of the two plasmon modes at different wavelength ranges, we found that SLRs had two-fold activity enhancement over that from localized surface plasmons.

Nanoparticle Shape Determines Dynamics of Targeting Nanoconstructs on Cell Membranes.

Nanoparticle carriers are effective drug delivery vehicles. Along with other design parameters including size, composition, and surface charge, particle shape strongly influences cellular uptake. How nanoparticle geometry affects targeted delivery under physiologically relevant conditions, however, is inconclusive. Here, we demonstrate that nanoconstruct core shape influences the dynamics of targeting ligand-receptor interactions on cancer cell membranes. By single-particle tracking of translational and rotational motion, we compared DNA aptamer AS1411 conjugated gold nanostars (AS1411-AuNS) and 50 nm gold spheres (AS1411-50NPs) on cells with and without targeted nucleolin membrane receptors. On nucleolin-expressing cells, AS1411-AuNS exhibited faster velocities under directed diffusion and translated over larger areas during restricted diffusion compared to AS1411-50NPs, despite their similar protein corona profiles. On nucleolin-inhibited cells, AS1411-AuNS showed faster rotation dynamics over smaller translational areas, while AS1411-50NPs did not display significant changes in translation. These differences in translational and rotational motions indicate that nanoparticle shape affects how targeting nanoconstructs bind to cell-membrane receptors.

Creation of Single-Photon Emitters in WSe2 Monolayers Using Nanometer-Sized Gold Tips.

Due to their tunable bandgaps and strong spin-valley locking, transition metal dichalcogenides constitute a unique platform for hosting single-photon emitters. Here, we present a versatile approach for creating bright single-photon emitters in WSe2 monolayers by the deposition of gold nanostars. Our molecular dynamics simulations reveal that the formation of the quantum emitters is likely caused by the highly localized strain fields created by the sharp tips of the gold nanostars. The surface plasmon modes supported by the gold nanostars can change the local electromagnetic fields in the vicinity of the quantum emitters, leading to their enhanced emission intensities. Moreover, by correlating the emission energies and intensities of the quantum emitters, we are able to associate them with two types of strain fields and derive the existence of a low-lying dark state in their electronic structures. Our findings are highly relevant for the development and understanding of single-photon emitters in transition metal dichalcogenide materials.

Manipulating Immune Activation of Macrophages by Tuning the Oligonucleotide Composition of Gold Nanoparticles.

This paper describes how the ligand shell containing immunostimulatory oligonucleotides surrounding gold nanoparticles affects the in vitro activation of macrophages. Nanoconstructs with similar ligand densities but different oligonucleotide compositions (from 0% to 100% immune-active cytosine-phosphate-guanine, CpG) were compared. Maximum immunostimulation was achieved with CpG content as low as 5% (with total oligonucleotide surface coverage remaining constant), correlating to high levels of antitumor cytokine release and low levels of cancer-promoting ones. Independent of CpG content, gold nanoparticles with low oligonucleotide densities exhibit poor cellular uptake, leading to insignificant immunostimulation and cytokine release. By identifying effects of ligand shell composition on macrophage activation, we can inform the design rules of therapeutic nanoconstructs to achieve specific immune responses.

Nanoparticle Anisotropy Increases Targeting Interactions on Live-Cell Membranes.

This paper describes how branch lengths of anisotropic nanoparticles can affect interactions between grafted ligands and cell-membrane receptors. Using live-cell, single-particle tracking, we found that DNA aptamer-gold nanostar nanoconstructs with longer branches showed improved binding efficacy to human epidermal growth factor receptor 2 (HER2) on cancer cell membranes. Inhibiting nanoconstruct-HER2 binding promoted nonspecific interactions, which increased the rotational speed of long-branched nanoconstructs but did not affect that of short-branched constructs. Bivariate analysis of the rotational and translational dynamics showed that longer branch lengths increased the ratio of targeting to nontargeting interactions. We also found that longer branches increased the nanoconstruct-cell interaction times before internalization and decreased intracellular trafficking velocities. Differences in binding efficacy revealed by single-particle dynamics can be attributed to the distinct protein corona distributions on short- and long-branched nanoconstructs, as validated by transmission electron microscopy. Minimal protein adsorption at the high positive curvature tips of long-branched nanoconstructs facilitated binding of DNA aptamer ligands to HER2. Our study reveals the significance of nanoparticle branch length in regulating local chemical environment and interactions with live cells at the single-particle level.

Investigating Reaction Intermediates during the Seedless Growth of Gold Nanostars Using Electron Tomography.

Good's buffers can act both as nucleating and shape-directing agents during the synthesis of anisotropic gold nanostars (AuNS). Although different Good's buffers can produce AuNS shapes with branches that are oriented along specific crystallographic directions, the mechanism is not fully understood. This paper reports how an analysis of the intermediate structures during AuNS synthesis from HEPES, EPPS, and MOPS Good's buffers can provide insight into the formation of seedless AuNS. Electron tomography of AuNS structures quenched at early times (minutes) was used to characterize the morphology of the incipient seeds, and later times were used to construct the growth maps. Through this approach, we identified how the crystallinity and shape of the first structures synthesized with different Good's buffers determine the final AuNS morphologies.

Review of Evidence for the Usage of Antioxidants for Eye Aging.

Oxidative stress is one of the common factors leading to age-related eye diseases in older adults. Factors such as high oxygen consumption, high concentration of polyunsaturated fatty acids, and cumulative exposure to high-energy visible light in the eyes, lead to excessive generation of reactive oxygen species, hence triggering apoptosis of ocular cells and giving rise to ophthalmic diseases. Dietary supplements such as carotenoids, anthocyanins, and vitamins have antioxidant properties which may be of benefit in retaining better vision or reversing vision impairment; thus, studies have been conducted to understand the role of dietary supplements in the treatment or prevention of ophthalmic diseases. While high concentration of carotenoids such as lutein and zeaxanthin decrease the risk of developing age-related macular disease, anthocyanins and vitamins play a role in the treatment and prevention of other ophthalmic diseases: saffron extract reduced intraocular pressure in glaucoma patients; bilberry extract prevented impairments in lenses and retina, as well as alleviate symptoms of dry eye disease; high concentration of beta-carotene may reduce the risk of developing cataract. Further studies with clinical measurements are required to investigate the effectiveness of antioxidants on visual function and ophthalmic diseases.

Review of the management of sight-threatening diabetic retinopathy during pregnancy.

Diabetes mellitus (DM) is a noncommunicable disease reaching epidemic proportions around the world. It affects younger individuals, including women of childbearing age. Diabetes can cause diabetic retinopathy (DR), which is potentially sight threatening when severe nonproliferative DR (NPDR), proliferative DR (PDR), or sight-threatening diabetic macular oedema (STDME) develops. Pregnancy is an independent risk factor for the progression of DR. Baseline DR at the onset of pregnancy is an important indicator of progression, with up to 10% of women with baseline NPDR progressing to PDR. Progression to sight-threatening DR (STDR) during pregnancy causes distress to the patient and often necessitates ocular treatment, which may have a systemic effect. Management includes prepregnancy counselling and, when possible, conventional treatment prior to pregnancy. During pregnancy, closer follow-up is required for those with a long duration of DM, poor baseline control of blood sugar and blood pressure, and worse DR, as these are risk factors for progression to STDR. Conventional treatment with anti-vascular endothelial growth factor agents for STDME can potentially lead to foetal loss. Treatment with laser photocoagulation may be preferred, and surgery under general anaesthesia should be avoided. This review provides a management plan for STDR from the perspective of practising ophthalmologists. A review of strategies for maintaining the eyesight of diabetic women with STDR with emphasis on prepregnancy counselling and planning, monitoring and safe treatment during pregnancy, and management of complications is presented.

Plasmonic nanostar photocathodes for optically-controlled directional currents.

Plasmonic nanocathodes offer unique opportunities for optically driving, switching, and steering femtosecond photocurrents in nanoelectronic devices and pulsed electron sources. However, angular photocurrent distributions in nanoplasmonic systems remain poorly understood and are therefore difficult to anticipate and control. Here, we provide a direct momentum-space characterization of multiphoton photoemission from plasmonic gold nanostars and demonstrate all-optical control over these currents. Versatile angular control is achieved by selectively exciting different tips on single nanostars via laser frequency or linear polarization, thereby rotating the tip-aligned directional photoemission as observed with angle-resolved 2D velocity mapping and 3D reconstruction. Classical plasmonic field simulations combined with quantum photoemission theory elucidate the role of surface-mediated nonlinear excitation for plasmonic field enhancements highly concentrated at the sharp tips (Rtip = 3.4 nm). We thus establish a simple mechanism for femtosecond spatiotemporal current control in designer nanosystems.

Single-Nanoparticle Orientation Sensing by Deep Learning.

This paper describes a computational imaging platform to determine the orientation of anisotropic optical probes under differential interference contrast (DIC) microscopy. We established a deep-learning model based on data sets of DIC images collected from metal nanoparticle optical probes at different orientations. This model predicted the in-plane angle of gold nanorods with an error below 20°, the inherent limit of the DIC method. Using low-symmetry gold nanostars as optical probes, we demonstrated the detection of in-plane particle orientation in the full 0-360° range. We also showed that orientation predictions of the same particle were consistent even with variations in the imaging background. Finally, the deep-learning model was extended to enable simultaneous prediction of in-plane and out-of-plane rotation angles for a multibranched nanostar by concurrent analysis of DIC images measured at multiple wavelengths.

Wavelength-Dependent Differential Interference Contrast Inversion of Anisotropic Gold Nanoparticles.

Gold nanorods are promising nanoparticle-orientation sensors because they exhibit wavelength and angle-dependent optical patterns in their differential interference contrast (DIC) microscopy images. In this paper, we report a finite-difference time-domain method to simulate DIC images using nanorods as model probes. First, we created a DIC image library of nanorods as a function of imaging wavelength and rotation angle that showed good agreement with experimental results. Second, we used this simulation tool to explain why the patterns inverted from bright to dark when the imaging wavelength increased from below to above the plasmon resonance of the nanorod. We found that this intensity inversion resulted from reversal in electric field direction depending on wavelength relative to the nanorod plasmon resonance. Finally, we showed that this DIC contrast inversion is a general phenomenon by measuring and simulating DIC images from gold nanorods of different sizes and gold nanostars.

A SERS-based lateral flow assay biosensor for highly sensitive detection of HIV-1 DNA.

User-friendly lateral flow (LF) strips have been extensively used for point-of-care (POC) self-diagnostics, but they have some limitations in their detection sensitivity and quantitative analysis because they only identify the high cut-off value of a biomarker by utilizing color changes that are detected with the naked eye. To resolve these problems associated with LF strips, we developed a novel surface-enhanced Raman scattering (SERS)-based LF assay for the quantitative analysis of a specific biomarker in the low concentration range. Herein, human immunodeficiency virus type 1 (HIV-1) DNA was chosen as the specific biomarker. Raman reporter-labeled gold nanoparticles (AuNPs) were employed as SERS nano tags for targeting and detecting the HIV-1 DNA marker, as opposed to using bare AuNPs in LF strips. It was possible to quantitatively analyze HIV-1 DNA with high sensitivity by monitoring the characteristic Raman peak intensity of the DNA-conjugated AuNPs. Under optimized conditions, the detection limit of our SERS-based lateral flow assay was 0.24 pg/mL, which was at least 1000 times more sensitive compared to colorimetric or fluorescent detection methods. These results demonstrate the potential feasibility of the proposed SERS-based lateral flow assay to quantitatively detect a broad range of genetic diseases with high sensitivity.