Random Lasing via Plasmon-Induced Cavitation of Microbubbles.

Numerous laboratories have observed random lasing from optically pumped solutions of plasmonic nanoparticles (NPs) suspended with organic dye molecules. The underlying mechanism is typically attributed to the formation of closed-loop optical cavities enabled by the large local field and scattering enhancements in the vicinity of plasmonic NPs. In this manuscript, we propose an alternative mechanism that does not directly require the plasmon resonance. We used high-speed confocal microspectroscopy to observe the photophysical dynamics of NPs in solution. Laser pulses induce the formation of microbubbles that surround and encapsulate the NPs, then sharp peaks <1.0 nm are observed that match the spectral signature of random lasing. Electromagnetic simulations indicate that ensembles of microbubbles may form optical corral containing standing wave patterns that are sufficient to sustain coherent optical feedback in a gain medium. Collectively, these results show that ensembles of plasmonic-induced bubbles can generate optical feedback and random lasing.

Plasmonic-induced self-assembly of WGM cavities via laser cavitation.

We show how photoexcitation of a single plasmonic nanoparticle (NP) in solution can create a whispering-gallery-mode (WGM) droplet resonator. Small nano/microbubbles are initially formed by laser-induced heating that is localized by the plasmon resonance. Fast imaging shows that the bubbles collect and condense around the NP and form a droplet in the interior of the bubble. Droplets containing dye generated lasing modes with wavelengths that depend on the size of the droplet, refractive index of the solvent, and surrounding environment, matching the behavior of a WGM. We demonstrated this phenomenon with two kinds of Au NPs in addition to TiN NPs and observed cavity diameters as small as 4.8 µm with a free spectral range (FSR) of 12 nm. These results indicate that optical pumping of plasmonic NPs in a gain medium can generate lasing modes that are not directly associated with the plasmon cavity but can arise from its photophysical processes. This process may serve as a method to generate plasmonic/photonic optical microcavities in solution on demand at any location in a solvent using free-space coupling in/out of the cavity.

Enhancement of the complex third-order nonlinear optical susceptibility in Au nanorods.

We experimentally determined the dispersion of the complex third-order nonlinear optical susceptibility χ(3) of Au nanorods over a wide bandwidth (370 - 800 nm). Compared to bulk Au, these nanorods exhibit greatly enhanced nonlinearities that can be manipulated by geometrical parameters. Accurately measuring the χ(3) values of nanostructured metals is challenging because χ(3) is strongly influenced by the local field effects. Hence the current published χ(3) values for Au nanorods have huge variations in both magnitude and sign because Z-scan measurements are used almost exclusively. This work combines pump-probe methods with spectroscopic ellipsometry to show that Au nanorods exhibit strong wavelength dependence and enhanced χ(3) in the vicinity of the longitudinal plasmon mode and explains where the regions of SA and RSA exist and how focusing and defocusing affects χ(3). In this context, the results highlight the importance of the dispersion of the quantity χ(3) to design plasmonic platforms for nanophotonics applications.

Relationship between advanced glycation end-product accumulation in the skin and pulmonary function.

. [Purpose] This study aimed to evaluate the relationship between advanced glycation end-product accumulation and pulmonary function in a general population with normal spirometry results. [Subjects and Methods] A total of 201 subjects (mean age, 56 ± 11 years; males, 58%) enrolled in this study. Subjects were classified into two groups (younger group [<65 years old] and elderly group [≥65 years old]). Skin autofluorescence was assessed as an estimate of advanced glycation end-product. Forced vital capacity and forced expiratory volume in one second were measured using a spirometer, and the forced expiratory volume in one second/forced vital capacity ratio (FEV1/FVC) was calculated. [Results] Skin autofluorescence was not an independent factor associated with FEV1/FVC in the younger group, but both skin autofluorescence and pack-years of smoking were significant independent factors associated with FEV1/FVC in the elderly group. [Conclusion] Advanced glycation end-product accumulation, assessed by skin autofluorescence, is an independent factor negatively associated with FEV1/FVC in elderly people with normal spirometry results.

Amplifying Photochromic Response in Tungsten Oxide Films with Titanium Oxide and Polyvinylpyrrolidone.

Tungsten oxide (WO3) is known for its photochromic properties, making it useful for smart windows, displays, and sensors. However, its small bandgap leads to rapid recombination of electron-hole pairs, resulting in poor photochromic performance. This study aims to enhance the photochromic properties of WO3 by synthesizing hexagonal tungsten oxide via hydrothermal synthesis, which increases surface area and internal hydrates. Titanium oxide (TiO2) was adsorbed onto the tungsten oxide to inject additional charges and reduce electron-hole recombination. Additionally, polyvinylpyrrolidone (PVP) was used to improve dispersion in organic solvents, allowing for the fabrication of high-quality films using the doctor blade method. Characterization confirmed the enhanced surface area, crystal structure, and dispersion stability. Reflectance and transmittance measurements demonstrated significant improvements in photochromic properties due to the composite structure. These findings suggest that the introduction of TiO2 and PVP to tungsten oxide effectively enhances its photochromic performance, broadening its applicability in various advanced photochromic applications.

Rapid and transient recruitment of DNMT1 to DNA double-strand breaks is mediated by its interaction with multiple components of the DNA damage response machinery.

DNA methylation is an epigenetic mark critical for regulating transcription, chromatin structure and genome stability. Although many studies have shed light on how methylation impacts transcription and interfaces with the histone code, far less is known about how it regulates genome stability. We and others have shown that DNA methyltransferase 1 (DNMT1), the maintenance methyltransferase, contributes to the cellular response to DNA damage, yet DNMT1's exact role in this process remains unclear. DNA damage, particularly in the form of double-strand breaks (DSBs), poses a major threat to genome integrity. Cells therefore possess a potent system to respond to and repair DSBs, or to initiate cell death. In the current study, we used a near-infrared laser microirradiation system to directly study the link between DNMT1 and DSBs. Our results demonstrate that DNMT1 is rapidly but transiently recruited to DSBs. DNMT1 recruitment is dependent on its ability to interact with both PCNA and the ATR effector kinase CHK1, but is independent of its catalytic activity. In addition, we show for the first time that DNMT1 interacts with the 9-1-1 PCNA-like sliding clamp and that this interaction also contributes to DNMT1 localization to DNA DSBs. Finally, we demonstrate that DNMT1 modulates the rate of DSB repair and is essential for suppressing abnormal activation of the DNA damage response in the absence of exogenous damage. Taken together, our studies provide compelling additional evidence for DNMT1 acting as a regulator of genome integrity and as an early responder to DNA DSBs.

Formation of Si-Rich Interfaces by Radiation-Induced Diffusion and Microsegregation in CrN/ZrN Nanolayer Coating.

A combination of coating deposition and consequent ion implantation could be beneficial in wear-resistant antifriction surface design and modification. In the present paper, the effects of low-energy 60 keV Si-ion implantation on multinanolayered CrN/ZrN grown on a stainless-steel substrate have been investigated. Complementary experimental (X-ray diffraction, high-resolution transmission electron microscopy, energy-dispersive spectroscopy, secondary ion mass spectrometry) and theoretical (first-principles) methods have been employed to investigate the structure, phase, and composition under a 1 × 10-17 cm-2 irradiation dose. This study has revealed a moderate radiation-tolerance of the CrN/ZrN system, with a 26 nm bilayer period, where the effective ion range after irradiation was below 110 nm. Within the ion range, a decrease in composition homogeneity and structure crystallinity has been found. Si negative ions have been distributed asymmetrically with peak concentrations (10 and 6%) occupying the interfaces between the CrN and ZrN layers. First-principles investigations of the CrN/ZrN(001) heterostructures were carried out to validate the experimental results, which showed that the alignment of Si-rich interfaces closer to chromium layers is a consequence of the lower substitution energy of CrN rather than ZrN. Thus, strong Si-Cr bindings and difference in displacement energies of ZrN and CrN have been attributed as the main factors in Si-rich interface formation. The pin-on-ball tribological test results have exposed the enhancement in wear resistance and the friction coefficient of nanoscale coating via amorphous Si particles descending from interfacial areas and acting as a third-body.

Spectral dependence of third-order susceptibility of Au triangular nanoplates.

We experimentally investigated the spectral dependence of the third-order susceptibility [Formula: see text] of Au triangular nanoplates in a broad wavelength region (400-1,000 nm). Complex shaped plasmonic nanoparticles provide a promising route to achieve control of their optical properties at the nanoscale. However, little is known about the effects of geometrical parameters to the optical nonlinearities and underlying mechanisms of the plasmon modes. Here, we obtained the [Formula: see text] of Au triangular nanoplates featuring a narrow plasmon resonance that is tunable in the visible and near-IR regions. This work demonstrates that the plasmonic triangular nanoplates simultaneously shows self-focusing and -defocusing, and saturable and reverse-saturable absorption properties at specific wavelength regions. Maximum amplitudes of real and imaginary components are - 6.8 × 10-18 m2/V2 at 668 nm and - 6.7 × 10-18 m2/V2 at 646 nm, respectively. Spectral dependence of the quantity [Formula: see text] enables comparison between different shaped plasmonic NPs to boost active plasmonic applications performance.

Antibacterial Effect of Au Implantation in Ductile Nanocomposite Multilayer (TiAlSiY)N/CrN Coatings.

A multilayered nanocomposite designed for biomedical applications based on (TiAlSiY)N/CrN coating implanted by heavy Au- ions is studied. Ion irradiation produced formation in the upper-surface of local amorphous clusters. The obtained composite system was characterized by SEM-EDS, RBS, SIMS, HRTEM, STEM, and nanoindentation mechanical tests, inspecting microstructure, phase state, elemental composition and surface defectiveness. The range of ion impact with correlation to TRIM simulations amounted to 23.5 nm with visible dislocations and interstitial loops indicating the nanopores' creation up/lengthways to the interface boundary. Mechanical parameters remain stable with a slight decrease (less than 2%) in hardness along with an increase in ductility. The antibacterial effect was evaluated in vitro by agar-diffusion and time-kill (72 h) assessments to define both cell-killing mechanisms: dry surface-contact and cytotoxic golden ions-release into moist environment. The identified antibacterial activity within implantation was 2-2.5 times higher due to inhibition zone diameter and antibacterial rate increase. The Au- implanted composite exhibits excellent defense against Gram-negative and Gram-positive bacteria without appreciable surface contamination. Possible biophysical and chemical mechanisms of microorganisms' disruption and annihilation were proposed and analyzed. The present study shows that produced composite has large potential for use in biomedical areas.

Wavelength dispersion of nonlinear dielectric function of Cu nanoparticle materials.

The wavelength dispersions of third-order nonlinear optical response for Cu nanoparticle materials have been experimentally evaluated from transient spectra measured with the pump-probe method. The evaluated dispersions were analyzed on hot electron contribution using the Maxwell-Garnett approximation with the Drude model for intraband transition and first principles calculation for interband transition. The wavelength dispersion didn't directly reflect the dispersion of a local electric field factor. The interband transition term in hot electron contribution strongly dominated the dispersion around the surface Plasmon resonance by Fermi smearing. Intrinsic interband contribution to the nonlinearity was suggested from the analysis. Particle-size and host-medium dependence of the nonlinearity were also simulated.

Immunoblotting conditions for human hemoglobin chains.

Immunoblotting to analyze low-molecular-weight proteins like calmodulin and metallothioneins is challenging and requires modifications for reproducible detection. Human globin chains are 17-kDa proteins and are not detectable by conventional immunoblotting using nitrocellulose membranes. Here we describe an immunoblotting method using nitrocellulose membranes that allows quantitative analyses of globin chains. Although previous studies have demonstrated that the fixation of blotted membranes with glutaraldehyde improves immunodetection of low-molecular-weight proteins, we found that the detection sensitivity for human globins is increased markedly by fixation with paraformaldehyde, but not glutaraldehyde. This immunoblotting procedure facilitates studies of posttranscriptional mechanisms for globin gene expression.

Dispersion of nonlinear dielectric function of Au nanoparticles in silica glass.

We have investigated wavelength dispersion of photo-induced nonlinear dielectric function of Au nanoparticle materials. Transient transmission and reflection spectra were sequentially measured by the pump-probe method with a femtosecond laser system. The dispersion of real and imaginary parts of the nonlinear dielectric function of Au:SiO(2) nanoparticle material in the vicinity of the surface plasmon resonance was evaluated from these transient spectra with total differential. A local electromagnetic field factor and interband transition in Au nanoparticles directly dominate the dispersion.

Relationship between advanced glycation end-product accumulation and low skeletal muscle mass in Japanese men and women.

AIM: The present study aimed to investigate the relationship between advanced glycation end-product accumulation and skeletal muscle mass among middle-aged and older Japanese men and women. METHODS: A total of 132 participants enrolled in this cross-sectional study. Skin autofluorescence was assessed as a measure of advanced glycation-end products. Appendicular skeletal muscle mass was measured using dual-energy X-ray absorptiometry, and skeletal muscle index was calculated by dividing appendicular skeletal muscle mass by height squared. Participants were divided into two groups (low skeletal muscle index and normal skeletal muscle index) using the Asian Working Group for Sarcopenia's skeletal muscle index criteria for diagnosing sarcopenia. Multivariate logistic regression analysis and the area under the receiver operating characteristic curve were used to determine significant factors associated with low skeletal muscle index. RESULTS: Participants consisted of 70 men (mean age 57 ± 10 years) and 62 women (mean age 60 ± 11 years). There were 31 and 101 participants in the low and normal skeletal muscle index groups, respectively. Skin autofluorescence was significantly higher in the low skeletal muscle index group compared with the normal skeletal muscle index group (P < 0.01). Skin autofluorescence was a significant independent factor associated with low skeletal muscle index based on multivariate logistic regression analysis (odds ratio 15.7, 95% confidence interval 1.85-133.01; P = 0.012). The cut-off for skin autofluorescence was 2.45 arbitrary units, with a sensitivity of 0.75 and specificity of 0.91. CONCLUSIONS: Skin autofluorescence was an independent factor associated with low skeletal muscle index among middle-aged and older Japanese men and women. Geriatr Gerontol Int 2017; 17: 785-790.

Modification of the ionizing radiation response in living cells by an scFv against the DNA-dependent protein kinase.

The non-homologous end joining pathway uses pre-existing proteins to repair DNA double-strand breaks induced by ionizing radiation. Here we describe manipulation of this pathway in living cells using a newly developed tool. We generated a single chain antibody variable fragment (scFv) that binds to the DNA-dependent protein kinase catalytic subunit (DNA-PKcs), a key enzyme in the pathway. In contrast to existing pharmacologic inhibitors, the scFv binds a newly defined regulatory site outside the kinase catalytic domain. Although the scFv inhibits kinase activity only modestly, it completely blocks DNA end joining in a cell-free system. Microinjection of the scFv sensitizes human cells to radiation, as measured by a reduction in efficiency of colony formation and induction of apoptosis at an otherwise sublethal dose of 1.5 Gy. The scFv blocks non-homologous end joining in situ at a step subsequent to histone gamma-H2AX focus formation but preceding gamma-H2AX dephosphorylation. Blockage occurs in cells exposed to as little as 0.1 Gy, indicating that DNA-PKcs is essential for double-strand break repair even at low radiation doses. The ability to modify the radiation response in situ in living cells provides a link between biochemical, genetic and cytologic approaches to the study of double-strand break repair intermediates.

Biochemical evidence for Ku-independent backup pathways of NHEJ.

Cells of higher eukaryotes process within minutes double strand breaks (DSBs) in their genome using a non-homologous end joining (NHEJ) apparatus that engages DNA-PKcs, Ku, DNA ligase IV, XRCC4 and other as of yet unidentified factors. Although chemical inhibition, or mutation, in any of these factors delays processing, cells ultimately remove the majority of DNA DSBs using an alternative pathway operating with an order of magnitude slower kinetics. This alternative pathway is active in mutants deficient in genes of the RAD52 epistasis group and frequently joins incorrect ends. We proposed, therefore, that it reflects an alternative form of NHEJ that operates as a backup (B-NHEJ) to the DNA-PK-dependent (D-NHEJ) pathway, rather than homology directed repair of DSBs. The present study investigates the role of Ku in the coordination of these pathways using as a model end joining of restriction endonuclease linearized plasmid DNA in whole cell extracts. Efficient, error-free, end joining observed in such in vitro reactions is strongly inhibited by anti-Ku antibodies. The inhibition requires DNA-PKcs, despite the fact that Ku efficiently binds DNA ends in the presence of antibodies, or in the absence of DNA-PKcs. Strong inhibition of DNA end joining is also mediated by wortmannin, an inhibitor of DNA-PKcs, in the presence but not in the absence of Ku, and this inhibition can be rescued by pre-incubating the reaction with double stranded oligonucleotides. The results are compatible with a role of Ku in directing end joining to a DNA-PK dependent pathway, mediated by efficient end binding and productive interactions with DNA-PKcs. On the other hand, efficient end joining is observed in extracts of cells lacking DNA-PKcs, as well as in Ku-depleted extracts in line with the operation of alternative pathways. Extracts depleted of Ku and DNA-PKcs rejoin blunt ends, as well as homologous ends with 3' or 5' protruding single strands with similar efficiency, but addition of Ku suppresses joining of blunt ends and homologous ends with 3' overhangs. We propose that the affinity of Ku for DNA ends, particularly when cooperating with DNA-PKcs, suppresses B-NHEJ by quickly and efficiently binding DNA ends and directing them to D-NHEJ for rapid joining. A chromatin-based model of DNA DSB rejoining accommodating biochemical and genetic results is presented and deviations between in vitro and in vivo results discussed.

Modifying the function of DNA repair nanomachines for therapeutic benefit.

This article, which is based on a presentation at the First Annual Meeting of the American Academy of Nanomedicine, is divided into three parts. First, we describe naturally occurring DNA repair nanomachines, using as an example the nanomachine that executes the nonhomologous end-joining (NHEJ) reaction for DNA double-strand break (DSB) repair. Second, we discuss therapeutic benefits that may be derived from the ability to modify the behavior of naturally occurring nanomachines, using as an example the concept of delaying DSB repair in rapidly dividing cancer cells to increase their natural sensitivity to radiation therapy. Third, we discuss similarities in the overall size, shape, and design of different nanomachines that manipulate DNA and RNA, and the possibility of developing nanomachines with new specificities not found in nature.

Time of flight-secondary ion mass spectrometry analysis of protein adsorption on a polyvinylidene difluoride surface modified by ion irradiation.

We investigated the effects of nanoscopic surface modification of polyvinylidene difluoride (PVDF) and low-density polyethylene (LDPE) by plasma-based ion implantation on protein adsorption with time of flight-secondary ion mass spectrometry (ToF-SIMS) analysis. The chemical composition of the LDPE and PVDF surfaces was changed by ion irradiation. In particular, irradiation substantially decreased the number of CH and CF bonds on the PVDF surface, but only slightly decreased that of CH bonds for LDPE. These decreases may reflect a higher hydrogen recombination rate of the LDPE than the PVDF surface. An increase in oxygen was observed on both the LDPE and PVDF surfaces following ion irradiation, but was saturated after irradiation of 1×1015cm-2 on the PVDF surface. The hydrophilicity of the ion-irradiated LDPE surface was promoted with an increase of the total ion fluence. Ion irradiation also changed the surface properties of PVDF to become more hydrophilic, but the variation did not correlate with the total ion fluence presumably due to the presence of fluorine atoms and the saturation of oxidation. Both bovine serum albumin (BSA) and collagen adsorption were suppressed on the LDPE surface by ion irradiation, which may have resulted from a decrease of the hydrophobic interaction. By contrast, ion irradiation increased protein adsorption on the PVDF surface, and BSA was adsorbed more than collagen, whereas there was no difference in the adsorption between BSA and collagen on the ion-irradiated LDPE surface. Moreover, the adsorption of BSA decreased on the oxygen- and fluorine-rich PVDF surface. These results indicate that the nanoscopic composition changes on the PVDF surface affect the adsorption behavior of BSA. Specifically, ferroelectric property on the PVDF surface was changed by ion irradiation and the nanoscopic change in polarity presumably affected the protein adsorption. Our findings suggest that selective adsorption control of protein can be achieved by ion irradiation to PVDF surface.

Direct Imaging of Carboxymethyl Cellulose-mediated Aggregation of Lactic Acid Bacteria Using Dark-field Microscopy.

The ecological functions of lactic acid bacteria (LAB) have been utilized in human life for food processing and probiotic therapy. Understanding the interaction mechanisms between LAB and food ingredients may help to clarify the fermentation process and physiological functions of LAB in the production of fermented foods made from plant materials and dairy products. However, the interaction mechanisms have yet to be fully clarified. Although laser diffraction was used for measuring the size changes of aggregates caused by the interaction between LAB and food ingredients, aggregate sizes could not be determined because of the precipitation of aggregates and its disruption from stirring. Therefore, a microscopy-based method for directly visualizing their interactions is required. We directly observed aggregation processes of LAB cells mediated by water-soluble polysaccharides, carboxymethyl cellulose (CMC), by dark-filed microscopy (DFM). DFM could visualize CMC-mediated cell aggregation with high contrast in real time, and revealed that the aggregates were formed by repeated collisions of LAB cells in a suspension. This suggests that our method can be used as a useful assay to directly visualize grain formation caused by interactions between LAB cells and various polysaccharides in food ingredients.