Photo-induced Alignment Behavior of Azobenzene-containing Polymer Films with Different Cross-linking Degree

Three series of amorphous copolymers containing azobenzene groups with various substituents and certain amounts of crosslinkable acrylic groups were prepared. The cross-linked polymer films were obtained by thermal polymerization of the acrylic groups in the copolymers, during which, by controlling the time of cross-linking reaction, the films can be made with different cross-linking degree （from 0 to 32%, which was monitored by FT-IR spectra measurement）. Photo-induced alignment process of the films was performed under irradiation with linearly polarized light at 442 nm, and the effect of cross-linking degree on the photo-induced alignment rate was investigated. The dynamics of the photo-induced alignment was analyzed with biexponential curve fitting. The photo-induced alignment rate and the maximum transmittance of the films decreased because of the cross-linking. Furthermore, for the cross-linked samples, it was found that their saturated value of transmittances keep constant after repeated ＂writing＂ and ＂erasing＂ cycles. The findings reveal that the cross-linking of the film can effectively restrain the phototactic mass transport of azopolymer during irradiation by polarized light. The relationship between the cross-linking degree and the photo-induced alignment behavior of azopolymer is discussed in detail.

Photo-induced intramolecular electron transfer and intramolecular vibrational relaxation of rhodamine 6G in DMSO revealed by multiplex transient grating spectroscopy

Photo-induced intramolecular electron transfer （PIET） and intramolecular vibrational relaxation （IVR） dynamics of the excited state of rhodamine 6G （Rh6G＋） in DMSO are investigated by multiplex transient grating. Two major compo- nents are resolved in the dynamics of Rh6G＋. The first component, with a lifetime τTPIET = 140 fs-260 fs, is attributed to PIET from the phenyl ring to the xanthene plane. The IVR process occurring in the range ZIVR = 3.3 ps-5.2 ps is much slower than the first component. The PIET and IVR processes occurring in the excited state of Rh6G＋ are quantitatively determined, and a better understanding of the relationship between these processes is obtained.

PHOTO-INDUCED DOPED POLYANILINE BY THE VINYLIDENE CHLORIDE AND METHYL ACRYLATE COPOLYMER AS PHOTO ACID GENERATOR

The emeraldine base form of polyaniline (PANI) can be doped by a photo-induced doping method. In this method a. copolymer of vinylidene chloride and methyl acrylate (VCMAC) was used as photo acid generator which can release proton when it is exposed to ultraviolet light (lambda = 254 nm). The structure of PANI-VCMAC system before and after irradiation was characterized by elemental analysis, IR, XTP, anti SEM images. Results obtained indicate that the photo-induced doping characteristics, such as doping position and type of charge carriers, are similar to that of PANI doped with HCl. The poor room-temperature conductivity (similar to 10-S-5/cm) of PANI-VCMAC system after irradiation may be due to low doping degree (similar to pH=3) and the difference in morphology as compared with PANI-HCl film.

Photo-induced absorption in the pump probe spectroscopy of single-walled carbon nanotubes

Femtosecond pump probe spectroscopy is employed to study the photo-induced absorption feature in the single-walled carbon nanotube transient spectrum. The two advantages of the experiment, a chirality enriched sample and tuning the pump wavelength to the resonance of a specific nanotube species, greatly facilitate the identification of the photo-induced absorption signal of one tube species. It is found that a photo-induced absorption feature is located at one radial breathing mode to the blue side of the E11 state. This finding prompts a new explanation for the origin of the photo-induced absorption： the transition from the ground state to a phonon coupled state near the E ii state. The explanation suggests a superposition mechanism of the photo-bleach and photo-induced absorption signals, which may serve as a key to the interpretation of the complex pump probe transient spectrum of carbon nanotubes. The finding sheds some light on the understanding of the complex non-radiative relaxation process and the electronic structure of single-walled carbon nanotubes.

Photo-induced Phenomena in GeS_4 Glasses

GeS4 bulk glasses were prepared by the melt-quench technique and the samples were irradiated by 532-nm linearly polarized light. After the laser treatment, the photo-induced changes of the samples were investigated by UV-1601 speetrophotometer and optical second-order nonlinear tester. The results show that the transmittance of the samples around 532 nm obviously decreases and Bragg reflector forms, which is due to the production of photon-generated carriers. With the increase of laser pulse energy or the extension of irradiation duration, the Bragg reflector increases and gradually tends to be stable. These can be ascribed to the excitation- capture process of the carriers. After irradiation, the relaxation phenomenon results from the release of part of the absorbed energy in the glass matrix. And the fitting equation of the relaxation process is consistent with a conventional Kohlrausch stretched exponential function. The origin of the second harmonic generation （SHG） is because of the dipole reorientation caused by the photo-induced anisotropy in the glass.

STUDY ON PHOTO-INDUCED ORIENTATION OF A NOVEL PHOTO-ALIGNMENT FILM WITH SURFACE ENHANCED RAMAN SCATTERING (SERS) SPECTROSCOPY

Surface enhanced Raman scattering (SERS) spectroscopy was first utilized to study the photo-orientation behaviour of the photoreactive groups on a novel photo-alignment film surface and elucidate the generation mechanism of pretilt angle. The novel photo-alignment film was prepared by spin-coating a solution of ladderlike polysiloxane (LPS) bearing dual photoreactive group on an ITO surface and by irradiation with linear-polarized ultraviolet (LPUV) light A Si—H terminal compound (M) containing an identical photosensitive part has been used to fabricate a model film for SERS investigation.

Time-dependent density functional theoretical studies on the photo-induced dynamics of an HCI molecule encapsulated in C60 under femtosecond laser pulses

By using first-principles simulations based on time-dependent density functional theory, the chemical reaction of an HCl molecule encapsulated in C60 induced by femtosecond laser pulses is observed. The H atom starts to leave the Cl atom and is reflected by the C60 wall. The coherent nuclear dynamic behaviors of bond breakage and recombination of the HCl molecule occurring in both polarized parallel and perpendicular to the H-Cl bond axis are investigated. The radial oscillation is also found in the two polarization directions of the laser pulse. The relaxation time of the H-Cl bond lengths in transverse polarization is slow in comparison with that in longitudinal polarization. Those results are important for studying the dynamics of the chemical bond at an atomic level.

CHARGE-TRANSFER AND ENERGY-TRANSFER IN THE PHOTO-INDUCED COPOLYMERIZATION OF 2-VINYLNAPHTHALENE WITH MALEIC ANHYDRIDE

The initiation mechanism of the copolymerization of 2-vinylnaphthalene with maleic anhydride was studied under irradiation of 365 nm. The excited complex was formed from (1) the local excitation of 2-vinylnaphthalene followed by the charge-transfer interaction with maleic anhydride and (2) the excitation of the ground state charge-transfer complex, and then it collapsed to 1,4-tetramethylene biradical for initiation. A1: 1 alternating copolymer was formed in different monomer feeds. Addition of benzophenone could greatly enhance the rate of copolymerization through energy-transfer mechanism.

Photo-induced Coupling Reaction of 1,1-Diphenyl-2,2-dicyanoethylene with 10-Methyl-9,10-dihydroacridine

Diphenyl-2, 2-dicyanoethylene reacts with 10-methyl-9, 10-dihydroacridine in deaerated acetonitrile under irradiation with l>320 nm to give the coupling product 1, 1-diphenyl-1-(10-methyl-9-acridinyl)-2, 2-dicyanoethane, which has been characterized by X-ray crystallographic, MS and NMR analyses.

Photo-Induced Thermally Stimulated Depolarization Current (TSDC) in Natural and Synthetic Alexandrite (BeAl2O4:Cr3+)

The investigation of electrical properties in alexandrite (BeAl2O4:Cr3+) in synthetic and natural forms is presented in this paper. Alexandrite is a rare and precious mineral that changes color according to the light incident on it. In the synthetic form, it is used technologically as an active laser medium. The electrical characterization was obtained using the Thermally Stimulated Depolarization Current (TSDC) technique, an interesting tool to study the behavior of impurities in insulators. Alexandrite presented the electric dipole relaxation phenomenon, both in natural and in synthetic samples. It was possible to observe TSDC bands for the synthetic sample at around 170 K, and at around 175 K for the natural sample. Besides, photo-induced TSDC measurements were performed through the excitement of the samples by using a continuous wave argon laser. In addition, photoluminescence measurements were performed to verify in advance whether the laser light would be absorbed by the sample, and in order to complement the photo-induced TSDC measurements analysis. The results of photo-induced TSDC experiments have contributed to the understanding of the TSDC bands behavior: the results obtained with the technique suggest that there is an effective participation of Cr3+ ions in the formation of TSDC bands because they were more intense when the sample was exposed to the argon laser beam.

Photo-induced grease/oil switched lubricant for friction regulation

Controllable friction regulation has drawn much interest in both scientific and industrial fields.And there have been many researches on friction regulation by many physical fields and chemical factors.Photo-sensitive materials are promising because it is relatively easy to change their properties compared with others.Here,a new kind of photo-induced grease/oil switched lubricant is designed and shows great reversibility under ultraviolet(UV)and visible(Vis)irradiation.Its viscosity can change more than 50 times under different irradiation,and the coefficients of friction(COFs)obviously increase under Vis irradiation and decrease under UV irradiation,which performs better than those of the common grease.According to the experimental results,the phenomena are contributed to the break and reconstruction of the three-dimensional network inside the lubricant.With a switchable grease/oil state under different irradiation,this work provides a new principle for designing a smart lubricant with controllable friction regulation.

Capturing the non-equilibrium state in light–matter–free-electron interactions through ultrafast transmission electron microscopy

Ultrafast transmission electron microscope(UTEM) with the multimodality of time-resolved diffraction, imaging,and spectroscopy provides a unique platform to reveal the fundamental features associated with the interaction between free electrons and matter. In this review, we summarize the principles, instrumentation, and recent developments of the UTEM and its applications in capturing dynamic processes and non-equilibrium transient states. The combination of the transmission electron microscope with a femtosecond laser via the pump–probe method guarantees the high spatiotemporal resolution, allowing the investigation of the transient process in real, reciprocal and energy spaces. Ultrafast structural dynamics can be studied by diffraction and imaging methods, revealing the coherent acoustic phonon generation and photoinduced phase transition process. In the energy dimension, time-resolved electron energy-loss spectroscopy enables the examination of the intrinsic electronic dynamics of materials, while the photon-induced near-field electron microscopy extends the application of the UTEM to the imaging of optical near fields with high real-space resolution. It is noted that light–free-electron interactions have the ability to shape electron wave packets in both longitudinal and transverse directions, showing the potential application in the generation of attosecond electron pulses and vortex electron beams.

Photo-induced Ag modulating carbon dots:Greatly improved fluorescent properties and derived sensing application

Carbon dots(CDs)have been attracted much attention and widely studied due to their excellent fluorescence(FL)properties,better biocompatibility and outstanding photo/chemical stability.However,the disadvantage of lower quantum yield(QY)still limits its wide application.Herein,we reported a novel and convenient strategy to prepare photo-induced Ag/CDs(p-Ag/CDs)by irradiating the mixed Ag+and hydrophobic CDs(h-CDs)acetone solution with ultraviolet(UV)light.The obtained p-Ag/CDs exhibit a greatly enhanced FL emission together with a blue shift(460 nm)than h-CDs(520 nm).The QY of p-Ag/CDs is measured to be 51.1%,which is 10.4 times higher than that of h-CDs(4.9%),indicating that photo-induced Ag modulation can effectively improve the optical properties of CDs.The mechanisms for the FL enhancement and blue shift of h-CDs are studied in detail.The results prove that the greatly enhanced FL emission is from the generated Ag nanoparticles(AgNPs)by UV light irradiation based on metal-enhanced fluorescence(MEF),and the increased oxygen-contained groups in this process lead to the blue shift in CDs fluorescence.Interestingly,the p-Ag/CDs exhibit higher sensitivity and selectivity for sulfide ions(S2-)detection than that of h-CDs,which have a lower response to S2-.This work not only offers a novel strategy to improve the FL properties of materials but also endows them with new functions and broadens their application fields.

Ferroelectrically modulate the Fermi level of graphene oxide to enhance SERS response

Surface-enhanced Raman scattering(SERS)substrates based on chemical mechanism(CM)have received widespread attentions for the stable and repeatable signal output due to their excellent chemical stability,uniform molecular adsorption and controllable molecular orientation.However,it remains huge challenges to achieve the optimal SERS signal for diverse molecules with different band structures on the same substrate.Herein,we demonstrate a graphene oxide(GO)energy band regulation strategy through ferroelectric polarization to facilitate the charge transfer process for improving SERS activity.The Fermi level(Ef)of GO can be flexibly manipulated by adjusting the ferroelectric polarization direction or the temperature of the ferroelectric substrate.Experimentally,kelvin probe force microscopy(KPFM)is employed to quantitatively analyze the Ef of GO.Theoretically,the density functional theory calculations are also performed to verify the proposed modulation mechanism.Consequently,the SERS response of probe molecules with different band structures(R6G,CV,MB,PNTP)can be improved through polarization direction or temperature changes without the necessity to redesign the SERS substrate.This work provides a novel insight into the SERS substrate design based on CM and is expected to be applied to other two-dimensional materials.

Research perspectives for catalytic valorization of biomass

Efficient utilization of biomass for the supply of energy and synthetic materials would mitigate the heavy reliance on fossil resources and the growing CO_(2) emission, thus contributing to establishing sustainable and carbon–neutral societies. Much effort has been devoted to catalytic transformations of lignocellulosic biomass, the most abundant and nonedible form of biomass.

Investigation on the photo-induced de-oxygenation process of myoglobin in aqueous solution by use of fluorescence spectroscopy

A photo-induced de-oxygenation process of myoglobin (Mb) in aqueous solution was investigated by use of fluorescence spectroscopy. The spectra are characterized by the fluorescence intensity declining gradually after each scan,and the decay of fluorescence intensity being significant in each scan,which is assigned to the release of oxygen from the opening of the heme-pockets induced by illumination. More illumination will cause more release of oxygen; if the temperature of an Mb solution is increased when it is illuminated,the rate of de-oxygenation will be higher. It was found that ligand-oxygen in Fe-porphyrin could be removed from Mb by nitrogen. This indicates that the interac-tion between oxy-Mb and other different gases can be tested by the method of fluorescence spectros-copy. In addition,fluorescence spectroscopy can be employed to probe the energy transfer between Fe-porphyrin and tryptophan or tyrosine in Mb molecules.

Ni60-SiC Coating Prepared by Plasma Spraying, Plasma Re-melting and Plasma Spray Welding on Surface of Hot Forging Die

In order to produce the hear-resistant inner layer of hot-forging die, plasma spraying and plasma re-melting and plasma spray welding were adopted. Substrate material was W6Mo5Cr4V2, including 10%, 20%, 30% SiC ceramic powder used as coating material to obtain different Ni-based SiC alloys coating. Micro-structure and micro-hardness analysis of the coating layer were followed, as well as thermophysical properties for the coating layer were measured. The experimental results show that the coating prepared with 70% Ni60, 30% SiC powder has best properties with plasma spray welding, in which the micro-hardness can achieve 1100 HV, meanwhile can improve the thermal property of hot-forging die dramatically.

MICROSTRUCTURAL STUDIES OF FRICTION STIR WELDED AZ31 MAGNESIUM ALLOY

Friction stir welding achieves the weld in solid phase by locally introducing frictional heating and plastic flow arising from rotation of the welding tool, which results in changes in the local microstructure of magnesium alloy. The purpose in the paper is to study the microstructures of friction stir welded AZ31 magnesium alloy. Residual microstructures, including dynamic re-crystallization zone and nugget structures have been systematically investigated utilizing optical microscopy (OM), scanning electric microscopy (SEM), transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and micro-hardness. AZ31 magnesium alloy has been successfully friction stir welded and exhibits the variations of microstructure including dynamically recrystallized, equaxied grains in the weld nugget. Residual hardness in the nugget was found slightly lower than the parent but not too obvious.

The advanced multi-functional carbon dots in photoelectrochemistry based energy conversion

Carbon dots(CDs),as a unique zero-dimensional member of carbon materials,have attracted numerous attentions for their potential applications in optoelectronic,biological,and energy related fields.Recently,CDs as catalysts for energy conversion reactions under multi-physical conditions such as light and/or electricity have grown into a research frontier due to their advantages of high visible light utilization,fast migration of charge carriers,efficient surface redox reactions and good electrical conductivity.In this review,we summarize the fabrication methods of CDs and corresponding CD nanocomposites,including the strategies of surface modification and heteroatom doping.The properties of CDs that concerned to the photo-and electro-catalysis are highlighted and detailed corresponding applications are listed.More importantly,as new non-contact detection technologies,transient photo-induced voltage/current have been developed to detect and study the charge transfer kinetics,which can sensitively reflect the complex electron separation and transfer behavior in photo-/electro-catalysts.The development and application of the techniques are reviewed.Finally,we discuss and outline the major challenges and opportunities for future CD-based catalysts,and the needs and expectations for the development of novel characterization technologies.

Photo-induced effect in the layered perovskite manganite La_(1.2)Sr_(1.8)Mn_(1.8)Co_(0.2)O_(7)

It is helpful to study the photo-induced effect in the perovskite manganites not only for elucidating the mechanism of colossal magnetoresistance (CMR) effect but also for potential applications in technology. The laser-induced effect in the Co doping layered perovskite manganites La1.2Sr1.8Mn1.8Co0.2O7 is studied in this paper and the obtained results are also compared with that gained in the Nd-doping manganites with cubic perovskite structure.