Self-adaptive control of infrared emissivity in a solution-processed plasmonic structure.

Active control of optical properties, particularly in the infrared (IR) regime, is critical for the regulation of thermal emission. However, most photonic structures and devices are based on a sophisticated design, making the dynamic control of their IR properties challenging. Here, we demonstrate self-adaptive control of IR absorptivity/emissivity in a simple stacked structure that consists of an oxide plasmonic nanocrystal layer and a phase change material (VO2) layer, both fabricated via a solution process. The resonance wavelength and emission intensity for this structure depend on the phase of the VO2. This has potential applications for thermal emission structures (e.g., self-adaptive radiative cooling and IR camouflage). The proposed structure is a candidate low-cost and scalable active photonic platform.

On-tissue polysulfide visualization by surface-enhanced Raman spectroscopy benefits patients with ovarian cancer to predict post-operative chemosensitivity.

Chemosensitivity to cisplatin derivatives varies among individual patients with intractable malignancies including ovarian cancer, while how to unlock the resistance remain unknown. Ovarian cancer tissues were collected the debulking surgery in discovery- (n = 135) and validation- (n = 47) cohorts, to be analyzed with high-throughput automated immunohistochemistry which identified cystathionine γ-lyase (CSE) as an independent marker distinguishing non-responders from responders to post-operative platinum-based chemotherapy. We aimed to identify CSE-derived metabolites responsible for chemoresistant mechanisms: gold-nanoparticle (AuN)-based surface-enhanced Raman spectroscopy (SERS) was used to enhance electromagnetic fields which enabled to visualize multiple sulfur-containing metabolites through detecting scattering light from Au-S vibration two-dimensionally. Clear cell carcinoma (CCC) who turned out less sensitive to cisplatin than serous adenocarcinoma was classified into two groups by the intensities of SERS intensities at 480 cm-1; patients with greater intensities displayed the shorter overall survival after the debulking surgery. The SERS signals were eliminated by topically applied monobromobimane that breaks sulfane-sulfur bonds of polysulfides to result in formation of sulfodibimane which was detected at 580 cm-1, manifesting the presence of polysulfides in cancer tissues. CCC-derived cancer cell lines in culture were resistant against cisplatin, but treatment with ambroxol, an expectorant degrading polysulfides, renders the cells CDDP-susceptible. Co-administration of ambroxol with cisplatin significantly suppressed growth of cancer xenografts in nude mice. Furthermore, polysulfides, but neither glutathione nor hypotaurine, attenuated cisplatin-induced disturbance of DNA supercoiling. Polysulfide detection by on-tissue SERS thus enables to predict prognosis of cisplatin-based chemotherapy. The current findings suggest polysulfide degradation as a stratagem unlocking cisplatin chemoresistance.

Correction to "DNA Brush-Directed Vertical Alignment of Extensive Gold Nanorod Arrays with Controlled Density".

[This corrects the article DOI: 10.1021/acsomega.7b00303.].

Nanoscale uniformity in the active tuning of a plasmonic array by polymer gel volume change.

Active plasmonic tuning is an attractive but challenging research subject, leading to various promising applications. As one of the approaches, nanostructures are placed in or on soft matter, such as elastomers and gels, and their gap distances are tuned by the mechanical extension or volume change of the supporting matrices. As hydrogels possess various types of stimuli-responsiveness with large volume change and biocompatibility, they are good candidates as supporting materials for active nanostructure tuning. However, it remains unclear how accurately we can control their nanogap distance changes using polymer gels with a low deviation due to major difficulties in the precise observation of nanostructures on the gels. Here, we prepared gold arrays with sub-100 nm dots on silicon substrates by electron beam lithography and transferred them onto the hydrogel surface. Then, their nanopattern was actively tuned by the changes in gel size in water and their structural changes were confirmed by optical microscopy, microspectroscopy, and atomic force microscopy (AFM). Further, we successfully prepared ionic liquid (IL) gels with various degrees of swelling via solvent exchange. Scanning electron microscopy (SEM) observation of the IL gels provided clear pictures at nanoscale resolution. Finally, we calculated the plasmonic spectra using a finite difference time domain (FDTD) simulation based on the SEM images and compared them with the measured spectra. The results in this study totally support the notion that active changes in plasmonic nanodot patterns via volume changes in the hydrogel are quite homogenous on a several nanometer scale, making them ideal for precise active surface plasmon tuning.

Size-Defined Cracked Vesicle Formation via Self-Assembly of Gold Nanoparticles Covered with Carboxylic Acid-Terminated Surface Ligands.

The self-assembly of gold nanoparticles (GNPs) into a defined structure, particularly hollow capsule structures, provides great potential for applications in materials science and medicine. However, the complexity of the parameters for the preparation of those structures through self-assembly has limited access to critical mechanistic questions. With this in mind, we have studied GNP vesicle (GNV) formation through self-assembly by the surface modification of GNPs with low-molecular-weight ligands. Here, we successfully prepared GNVs composed of GNPs with a diameter of 30 nm by surface modification with carboxylic acid-terminated fluorinated oligo(ethylene glycol) ligands (CFLs). As the carboxylic acid has two states (protonated and deprotonated), the balance of the attraction and repulsion between GNPs covered with CFLs is tunable. Sodium carboxylate-terminated fluorinated oligo(ethylene glycol) ligands (SCFLs) provided smaller GNVs than did CFLs at 0.8 × 1011 NPs/mL. Time-course study revealed that CFL-covered GNPs quickly form small aggregates and gradually grow to larger GNVs (ca. 200 nm), but no gradual growth was observed for SCFL-covered GNPs. This result indicated that the electrostatic repulsion inhibits fusion of the small GNVs. The size of the GNVs formed with the aid of CFLs was independent of the initial GNP concentration, but the extinction spectra were concentration-dependent. Electron microscopy imaging and simulations supported the defect formation in the assemblies. These results provided new insights into the vesicle formation mechanism.

Gold-nanofève surface-enhanced Raman spectroscopy visualizes hypotaurine as a robust anti-oxidant consumed in cancer survival.

Gold deposition with diagonal angle towards boehmite-based nanostructure creates random arrays of horse-bean-shaped nanostructures named gold-nanofève (GNF). GNF generates many electromagnetic hotspots as surface-enhanced Raman spectroscopy (SERS) excitation sources, and enables large-area visualization of molecular vibration fingerprints of metabolites in human cancer xenografts in livers of immunodeficient mice with sufficient sensitivity and uniformity. Differential screening of GNF-SERS signals in tumours and those in parenchyma demarcated tumour boundaries in liver tissues. Furthermore, GNF-SERS combined with quantum chemical calculation identified cysteine-derived glutathione and hypotaurine (HT) as tumour-dominant and parenchyma-dominant metabolites, respectively. CD44 knockdown in cancer diminished glutathione, but not HT in tumours. Mechanisms whereby tumours sustained HT under CD44-knockdown conditions include upregulation of PHGDH, PSAT1 and PSPH that drove glycolysis-dependent activation of serine/glycine-cleavage systems to provide one-methyl group for HT synthesis. HT was rapidly converted into taurine in cancer cells, suggesting that HT is a robust anti-oxidant for their survival under glutathione-suppressed conditions.

DNA Brush-Directed Vertical Alignment of Extensive Gold Nanorod Arrays with Controlled Density.

Control over the orientation of metal nanorods is important for both fundamental and applied research. We show that gold nanorods (GNRs) can be aligned in a single direction by adsorbing positively charged GNRs onto a double-strand DNA-grafted substrate through electrostatic interaction. The ordered structure can be optimized by controlling the density of the positive charges on the surface of the GNRs. We found, in agreement with the results of theoretical simulation, that the resultant structure exhibits plasmonic properties that are dependent on the GNR orientation relative to the direction of an oscillating electric field. Our approach provides new insights into the polymer-assisted self-assembly of rod-shaped nanoparticles utilizing electrostatic interactions.

Randomness in highly reflective silver nanoparticles and their localized optical fields.

Reflection of near-infrared light is important for preventing heat transfer in energy saving applications. A large-area, mass-producible reflector that contains randomly distributed disk-shaped silver nanoparticles and that exhibits high reflection at near-infrared wavelengths was demonstrated. Although resonant coupling between incident light and the nanostructure of the reflector plays some role, what is more important is the geometrical randomness of the nanoparticles, which serves as the origin of a particle-dependent localization and hierarchical distribution of optical near-fields in the vicinity of the nanostructure. Here we show and clarified the unique optical near-field processes associated with the randomness seen in experimentally fabricated silver nanostructures by adapting a rigorous theory of optical near-fields based on an angular spectrum and detailed electromagnetic calculations.

Large-area surface-enhanced Raman spectroscopy imaging of brain ischemia by gold nanoparticles grown on random nanoarrays of transparent boehmite.

Although SERS spectroscopy, which is sensitive to molecular vibration states, offers label-free visualization of molecules, identification of molecules and their reliable large-area imaging remains to be developed. Limitation comes from difficulties in fabricating a SERS-active substrate with homogeneity over a large area. Here, we overcome this hurdle by utilizing a self-assembled nanostructure of boehmite that is easily achieved by a hydrothermal preparation of aluminum as a template for subsequent gold (Au) deposition. This approach brought about random arrays of Au-nanostructures with a diameter of ∼125 nm and a spacing of <10 nm, ideal for the hot-spots formation. The substrate, which we named "gold nanocoral" (GNC) after its coral reef-like shape, exhibited a small variability of signal intensities (coefficient value <11.2%) in detecting rhodamine 6G molecule when 121 spots were measured over an area of 10 × 10 mm(2), confirming high uniformity. The transparent nature of boehmite enabled us to conduct the measurement from the back-side of the substrate as efficiently as that from the front-side. We then conducted tissue imaging using the mouse ischemic brain adhered on the GNC substrate. Through nontargeted construction of two-dimensional-Raman-intensity map using differential bands from two metabolically distinct regions, that is, ischemic core and contralateral-control areas, we found that mapping using the adenine ring vibration band at 736 cm(-1) clearly demarcated ischemic core where high-energy adenine phosphonucleotides were degraded as judged by imaging mass spectrometry. Such a detection capability makes the GNC-based SERS technology especially promising for revealing acute energy derangement of tissues.

Transparent near-infrared reflector metasurface with randomly dispersed silver nanodisks.

We present large-area ultrathin metasurfaces that transmit visible light and reflect near-infrared (NIR) wavelengths. These visible-transparent metasurfaces consist of 10 nm-thick monolayer of randomly dispersed silver nanodisks, that is only λ/90 thickness at the reflection peak wavelength. Calculated optical properties of the structure show that the reflectance for NIR wavelengths increases monotonically as a function of increasing nanodisk density, while the absorption saturates and scattering of visible light decreases. We demonstrate that the proposed structure is easy to fabricate with chemically synthesized silver particles using the bottom-up method and has industrially applications.

TOF-SIMS imaging of halide/thiocyanate anions and hydrogen sulfide in mouse kidney sections using silver-deposited plates.

In vivo imaging of reactive small molecule metabolites with high spatial resolution and specificity could give clues to understanding pathophysiology of various diseases. We herein applied time of flight-secondary ion mass spectrometry (TOF-SIMS) to newly developed silver-deposited plates that were stamped on mouse tissues, and succeeded in visualization of halide (Cl(-), Br(-), and I(-)) and pseudohalide thiocyanate (SCN(-)) anions, a class of substrates for neutrophils/eosinophil peroxidases to produce hypohalous acids (HOX/OX(-) mixture; X: (pseudo)halides), as well as hydrogen sulfide (H(2)S). Forty-micrometer frozen mouse kidney sections on cover glasses were attached to 37 °C preheated silver-deposited plates and incubated at -10 °C for 1 h. After sputter cleaning to remove surface contaminants, the plates were analyzed by TOF-SIMS to identify distribution of Br(-), AgBr(2)(-), I(-), AgI(2)(-), SCN(-), as well as S(2-) and AgS(-) as products of tissue-derived H(2)S. Br(-), AgBr(2)(-), I(-), and SCN(-) anions were mainly distributed in core regions including the inner medulla and inner stripe of the outer medulla (except for I(-)), rather than outer regions such as the cortex and outer stripe of the outer medulla. AgI(2)(-) anion was spread over the whole kidney, although its levels were relatively low. In contrast, S(2-) and AgS(-) anions were mainly present in the outer regions. To our knowledge, this is the first imaging study to reveal the distribution of (pseudo)halides and H(2)S in animal tissue sections.

Recognition of human emotions from cerebral blood flow changes in the frontal region: a study with event-related near-infrared spectroscopy.

BACKGROUNDS AND PURPOSE: The aim of this study is to develop a near-infrared spectroscopy (NIRS)-based system that recognizes pleasant and unpleasant human emotions based on cerebral blood flow (CBF) in order to understand the minds of patients whose brain function is severely impaired. The forehead region is easily accessible to NIRS measurements, whereas the role of the anterior prefrontal cortex (PFC) in the processing of emotion remains to be elucidated. METHODS: Initially, using event-related NIRS we examined changes in oxygenated hemoglobin (oxy-Hb) as an indicator of regional CBF changes, which reflect brain activity directly related to emotions, but not to cognitive operations in the anterior frontal regions, during viewing affective pictures. The event-related potentials (ERPs), systemic blood pressure, and pulse rate were also measured simultaneously. RESULTS: The event-related analysis of changes in oxy-Hb for a 6 s-picture presentation period showed that very unpleasant emotion was accompanied by an increase in oxy-Hb in the bilateral ventrolateral PFCs, while very pleasant emotion was accompanied by a decrease in oxy-Hb in the left dorsolateral PFC. There were no significant differences in either ERPs or autonomic nervous system activities between the two emotional states. CONCLUSION: These findings suggest the possibility of recognizing patients' emotions from CBF changes.