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.

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.

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.

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.

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.

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.

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.

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.

Cellular effects of magnetic nanoparticles explored by atomic force microscopy.

The investigation of subtle change of cells exposed to nanomaterials is extremely essential but also challenging for nanomaterial-based biological applications. In this study, atomic force microscopy (AFM) was employed to investigate the effects of iron-iron oxide core-shell magnetic nanoparticles on the mechanical properties of bovine articular chondrocytes (BACs). After being exposed to the nanoparticles even at a high nanoparticle-concentration (50 µg mL(-1)), no obvious difference was observed by using conventional methods, including the WST-1 assay and live/dead staining. However a significant difference of Young's modulus of the cells was detected by AFM even when the concentration of nanoparticles applied in the cell culture medium was low (10 µg mL(-1)). The difference of cellular Young's modulus increased with the increase of nanoparticle concentration. AFM was demonstrated to be a useful tool to identify the subtle change of cells when they were exposed to nanomaterials even at a low concentration.

Fluorescent carbon nanowires made by pyrolysis of DNA nanofibers and plasmon-assisted emission enhancement of their fluorescence.

We report on a facile method for preparing fluorescent carbon nanowires (CNWs) with pyrolysis of highly aligned DNA nanofibers as carbon sources. Silver nanoparticle (AgNP)-doped CNWs were also produced using pyrolysis of DNA nanofibers with well-attached AgNPs, indicating emission enhancement assisted by localized plasmon resonances.

Direct observation of one-dimensional plasmon coupling in metallic nanofibers prepared by evaporation-induced self-assembly with DNA.

Here we report a simple method for the preparation of highly aligned metallic nanofibers with anisotropic aggregates of silver nanoparticles (AgNPs) as well as a direct observation of localized plasmon field and its coupling in the prepared metallic nanofibers. Metallic nanofibers of several tens of nanometers wide and millimeters long were prepared. The preparation method, which is based on the process of evaporation-induced self-assembly with DNA and drying front movement, eliminates the need for lithography and an external field, and it is fast, cheap and easy. Dark-field scattering spectroscopy was used to study the strong plasmon coupling of AgNPs in the metallic nanofibers. We observed strong near-field coupling between neighboring nanoparticles, which results in red-shifted multipolar plasmon modes that are highly polarized along the fiber axis. The polarization dependence of plasmon coupling in the metallic nanofibers observed in this study was satisfactorily explained by the morphology of the metallic nanofibers, which was characterized by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Furthermore, Raman spectra imaging of the metallic nanofibers revealed the existence of intense hot spots localized along their axes, which played a significant role in the intensity of surface enhanced Raman scattering (SERS) signals from DNA bases in the metallic nanofiber. Our results demonstrate the use of evaporation-induced self-assembly with DNA as a straightforward method to produce one-dimensional coupling of localized plasmons with a longer scale.

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.

Sequences in PSF/SFPQ mediate radioresistance and recruitment of PSF/SFPQ-containing complexes to DNA damage sites in human cells.

PSF (gene name SFPQ) is a member of a small family of proteins with dual functions in RNA biogenesis and DNA repair. PSF and PSF-containing complexes stimulate double-strand break repair in cell free systems, most likely via direct interaction with the repair substrate. Prior in vitro studies are, however, insufficient to demonstrate whether PSF contributes to DNA repair in living cells. Here, we investigate the effect of miRNA-mediated PSF knockdown in human (HeLa) cells. We find that PSF is essential for reproductive viability. To circumvent this and investigate the DNA damage sensitivity phenotype, we established a genetic rescue assay based on co-transfection of PSF miRNA and mutant PSF expression constructs. Mutational analysis suggests that sequences required for viability and radioresistance are partially separable, and that the latter requires a unique N-terminal PSF domain. As an independent means to investigate PSF sequences involved in DNA repair, we established an assay based on real-time relocalization of PSF-containing complexes to sites of dense, laser-induced DNA damage in living cells. We show that relocalization is driven by sequences in PSF, rather than its dimerization partner, p54(nrb)/NONO, and that sequences required for relocalization reside in the same N-terminal domain that contributes to radioresistance. Further evidence for the importance of PSF sequences in mediating relocalization is provided by observations that PSF promotes relocalization of a third protein, PSPC1, under conditions where p54(nrb) is limiting. Together, these observations support the model derived from prior biochemical studies that PSF influences repair via direct, local, interaction with the DNA substrate.

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.