光照下meso-四(4-磺基苯基)卟啉(H_2TPPS)形成锌配合物的光-极谱研究

在氨性溶液中,光照射对ZnTPPS的形成影响很大。光-极谱试验表明:光电流(i_p)与浓度(c)间有以下的关系:对Zn(NH_3)_4^(2+),i_p∝C_((Zn)(NH_3)_4)^(2+)_^(1/2),对H_2TPPS,i_p∝C_(H_2TPPS),ZnTPPS络合物还原波的i_p不明显。本文对其差异性和光电流产生的原因做了初步探讨。

White organic light-emitting diodes based on emission from DPVBi-doped 4,48-bis (2,28-diphenylvinyl)-1,18-biphenyl

White organic light-emitting diodes were fabricated by using 4,48-bis （2,28-diphenylvinyl） -1,18-bi- phenyl （DPVBi） as a dopant with a structure of ITO/4,4＂-bisEN-（1-naphthyl-1-）-N-phenyl-amino]-bi- phenyl （NPB,50 nm）/NPB：DPVBi （molecular weight ratio 10 ; 1,30 nm）/tris-（8-hydroxyquinoline）a- luminum（AIq：, ,20 nm）/LiF（1 nm）/Al. A broad emissive band with four major peaks of 438,464,496 and 520 nm was obtained by electroluminescence spectra,of which 438 nm-,464 nm- and 520 nm-peak come from emission of NPB, DPVBi and AIq3, respectively,and 496 nm-one resulted from the emissive superposition of three materials above. The emission from DPVBi was attributed to the charge trapping from NPB. The emission region was transferred partly from AIq3 to DPVBi-doped NPB by introducing the dopant DPVBi,which leads to emission of DPVBi and an enhanced emission from NPB. The maxi- mum luminance and current efficiency were 4721 cd/m^2 at 22 V and 0.80 cd/A at 5V,respectively.

Solvent-Induced Symmetry-Breaking Charge Transfer in an Octupolar Triphenylamine Derivative Resolved with Transient Fluorescence Spectroscopy

The excited-state symmetry-breaking charge transfer (SBCT) dynamics in quadrupolar or octupolar molecules without clear infrared markers is usually hard to be tracked directly. In this work, on the basis of the evolution of instantaneous emission dipole moment obtained by femtosecond transient fluorescence spectroscopy, we presented a real-time characterization of the solvent-induced SBCT dynamics in an octupolar triphenylamine derivative. While the emission dipole moment of the octupolar trimer in weakly polar toluene changes little during the excited-state relaxation, it exhibits a fast reduction in a few picoseconds in strongly polar tetrahydrofuran. In comparison with the uorescence dynamics of dipolar monomer, we deduced that the emitting state of the octupolar trimer in strongly polar solvent, which undergoes solvent-induced structural uctuation, changes from exciton-coupled octupolar to excitation localized dipolar symmetry. In weakly polar solvent, the octupolar symmetry of the trimer is largely preserved during the solvation stabilization.

In-situ electrochemical surface-enhanced Raman spectroscopy in metal/polyelectrolyte interfaces

Polyelectrolyte becomes more and more popular in electrocatalysis.The understanding of electrode/polyelectrolyte interfaces at the molecular level is important for guiding further the polyelectrolyte-based electrocatalysis.Herein,we demonstrate an in-situ surface-enhanced Raman spectroscopic method by using a three-electrode spectroelectrochemical cell towards characterizing the electrode/polyelectrolyte interfaces.The Ag/AgCl and Ag/Ag_(2)O electrodes are used as the reference electrode in the acidic and the alkaline systems,respectively.The working electrode is made of a transparent carbon thin film which loads the electrocatalysts.The applications of this method are demonstrated through the in-situ characterizations of the p-methylthiophenol adsorbed on the Au and Pt and the electrochemical oxidation of Au on polyelectrolyte membranes.The potential-dependent spectral features of these two systems show that this method is a powerful tool for investigating the electrode/polyelectrolyte interfaces in electrocatalysis.

Nonlinear Absorption and Dispersion Response in Optically Dense Media Driven by a Single-Mode Laser

Taking the density-dependent near dipole-dipole （NDD） interaction into consideration, we theoretically investigate the response of nonlinear absorption and dispersion in optically dense media of three-level atoms driven by a single-mode probe laser. The influence of the NDD effects on the absorption and dispersion spectra of the probe field is predicted via numerical calculations. It is shown that the NDD effects reduce gradually to transient absorption and amplification with the increase of the strengths of the NDD interaction, but do not change the steady-state behavior. Due to the presence of the NDD effects, steady-state absorption spectra exhibit asymmetric double-peak structure and overall shifts when a continuous-wave （cw） probe field is applied. However, frequency dispersion spectra are insensitive to them near the zero detuning.

Negative Corona Discharge Ion Source Under Ambient Conditions with Mini Line-cylinder Electrodes

A novel ambient negative corona discharge ion source with mini line-cylinder electrodes is designed. The diameters of inner and outer electrode are 0.16 and 4 mm respectively. With a special assembly method, a perfect coaxiality of the two electrodes is obtained. An injection system utilizing a temperature control technique, achieves a constant and stable concentration of the sample, which is critical to the experiment. The formulas of the corona onset voltage of line-cylinder electrodes are also introduced. The experiment results show that negative substances such as formic acid and acetic acid can be ionized under ambient conditions. When combined with micro electrical mechanical system fabricationprocess, the volume of the ion source can be reduced dramatically, but there is an undesirable surface discharge. To solve the surface discharge problem, an improved structure was designed and tested. The simplicity of the interface of the ion source makes it suitable for mass spectrometer, micro mass spectrometer, ion mobility spectrometer, and high-field asymmetric waveform ion mobility spectrometer applications.

Ab Initio Calculation on Spectroscopic Properties and Radiative Lifetimes of Low-Lying Excited States of NaK

We performed high-level ab initio calculations on electronic structure of Na K. The potential energy curves (PECs) of 10 Λ-S states correlated with the three lowest dissociation limits have been calculated. On the basis of the calculated PECs, the spectroscopic constants of the boundΛ-S states are obtained, which are in good agreement with experimental results. The maximum vibrational quantum numbers of the singlet ground state X^1Σ^+ and the triplet ground state a^3Σ^+ have been analyzed with the semiclassical scattering theory. Transition properties including transition dipole moments, Franck-Condon factors, and radiative lifetimes have been investigated. The research results indicate that such calculations can provide fairly reliable estimation of parameters for the ultracold alkali diatomic molecular experiment.

Capacitance-frequency Spectrum Characterization of Organics/Metal Schottky Diodes

An organics/metal Schottky diode is fabricated using 3, 4： 9, 10-perylenetetracarboxylic- dianhydride（PTCDA） thin film sandwiched between ITO and Au by simple thermal evaporation technique. The current-voltage（I-V） characteristics are investigated at room temperature in open air. The results show the rectification ratio is in excess of 100. From the capacitance-frequency（C-f） and capacitance-voltage（C-V） measurements, the Schottky barrier height between 0.2-0.3 eV is obtained according to standard Schottky theory.

Vacuum Ultraviolet Free-Electron Laser Photoionization Mass Spectrometry of Alpha-pinene Ozonolysis

α-pinene is the most abundant monoterpene that represents an important family of volatile organic compounds.Molecular identification of key transient compounds during theα-pinene ozonolysis has been proven to be a challenging experimental target because of a large number of intermediates and products involved.Here we exploit the recently developed hybrid instruments that integrate aerosol mass spectrometry with a vacuum ultraviolet free-electron laser to study theα-pinene ozonolysis.The experiments ofα-pinene ozonolysis are performed in an indoor smog chamber,with reactor having a volume of 2 m^(3) which is made of fluorinated ethylene propylene film.Distinct mass spectral peaks provide direct experimental signatures of previously unseen compounds produced from the reaction ofα-pinene with O_(3).With the aid of quantum chemical calculations,plausible mechanisms for the formation of these new compounds are proposed.These findings provide crucial information on fundamental understanding of the initial steps ofα-pinene oxidation and the subsequent processes of new particle formation.

DFT Study of the Solvent Effects on the Structure, UV-Vis Spectra and the Antioxidant Activity of Caffeic Acid Phenethyl Ester and Some of Its Derivatives

In this study, the antioxidative （3-methyl-2-butenyl caffeate）, BC efficiency of CAPE （caffeic acid phenethyl ester） and four of its derivatives （MBC （benzoic caffeate）, P3HC （phenethyl-3-hydroxy-cinnamate） and P4HC （phenethyl-4-hydroxy-cinnamate）） are compared in vacuum and in seven solvents. It turned out that the AA （antioxidant activity） in increasing order was P3HC 〈 P4HC 〈 CAPE 〈 MBC. Effects of solvents on the structure and the antioxidant activity of P3HC, P4HC, BC, MBC and CAPE, were studied at 133LYP/6-31G （d, p） then B3LYP/6-3 I＋G （d, p） level of theory using the conductor polarized continuum model methods. Thermodynamically, the authors showed that solvent effects on bond dissociation enthalpy are very weak （within 25 kJ/mol）, but sufficient to influence hydrogen bonds, O-H bond lengths and showed the preferential sites of hydrogen atom cleavage. In addition, solvent notably influences and changes the nature of the scavenging process of ROS （reactive oxygen species）, favouring by this way the HHAT （homolytic hydrogen atom transfer） in non polar solvents, the SPLET （sequential proton loss electron transfer） in polar solvents. Moreover, in chloroform and for the five molecules studied the SET-PT （sequential electron transfer proton transfer） mechanism is preferred compared to the HHAT, because in this solvent the IP is lower than the BDE. TD-DFT calculations revealed that solvent induce a bathochromic effect （red-shift of the wavelengths） coupled to hyperchromic or hypochromic effects.

Effect of Solvent Polarity on Excited-State Double Proton Transfer Process of 1,5-Dihydroxyanthraquinone

The excited-state double proton transfer(ESDPT)properties of 1,5-dihydroxyanthraquinone(1,5-DHAQ)in various solvents were investigated using femtosecond transient absorption spectroscopy and the DFT/TDDFT method.The steady-state fluorescence spectra in toluene,tetrahydrofuran(THF)and acetonitrile(ACN)solvents presented that the solvent polarity has an effect on the position of the ESDPT fluorescence emission peak for the 1,5-DHAQ system.Transient absorption spectra show that the increasing polarity of the solvent accelerates the rate of excited state dynamics.Calculated potential energy curves analysis further verified the experimental results.The ESDPT barrier decreases gradually with the increase of solvent polarity from toluene,THF to ACN solvent.It is convinced that the increase of solvent polarity can promote the occurrence of the ESDPT dynamic processes for the 1,5-DHAQ system.This work clarifies the mechanism of the influence of solvent polarity on the ESDPT process of 1,5-DHAQ,which provides novel ideas for design and synthesis of new hydroxyanthraquinone derivatives.

Nonlinear Absorption-Gain Response and Population Dynamics in a Laser-Driven Four-Level Dense Atomic System

We theoretically investigate the response of nonlinear absorption and population dynamics in optically dense media of four-level atoms driven by a single-mode probe laser, via taking the density-dependent near dipoledipole （NDD） interactions into consideration. The influence of the NDD effects on the absorption of the probe field and population dynamics is predicted via numerical calculations. It is shown that the NDD effects can reduce gradually to transient absorption with the increase of the strengths of the NDD interactions, and transient amplification can be achieved. In the steady-state limit, the probe field exhibits transparency for strong NDD interactions. Alternatively, the population entirely remains at the ground state due to the NDD effects.

Spectral Characteristics of White Organic Light-emitting Diodes Based on Novel Phosphorescent Sensitizer

White organic light-emitting diodes were fabricated by using a novel phosphorescence bis（1,2-diphenyl-1H-benzoimidazole）iridium（acetylacetonate）[（pbi）2Ir（acac）] as sensitizer and a fluorescent dye of 4- （dicyanomethylene）-2-t-butyl-6-（1,1,7,7-tetramethyljulolidyl-9-enyl）-4H-pyran （DCJTB） codoped into a carbazole polymer of poly（N-vinylcarbazole） （PVK）. Through characterizing the UV-Vis absorption spectra, the photoluminescence spectra of （pbi）2Ir（acac） and DCJTB, and the electroluminescence spectral properties of the WOLEDs, the energy transfer mechanisms of the codoped polymer system were deduced. The results demonstrate that the luminescent spectra with different intensity of （pbi）2Ir（acac） and DCJTB were co-existent in the EL spectra of the blended system, which is ascribed to an incomplete energy transfer process in the EL process. The efficient Forster and Dexter energy transfer between the host and the guests enabled a strong yellow emission from （pbi）2Ir（acac） and DCJTB, where （pbi）2Ir（acac） plays an important role as a phosphorescent sensitizer for DCJTB. With the blue emitting-layer of N,N＇-diphenyl-N,N＇-bis（1- naphthyl）（1,1＇-biphenyl）-4,4＇-diamine, the codoped system device achieved white emission. The codoped system showed that its Commissions Internationale de 1＇Eclairage coordinates were more independent of the variation of bias voltage than those of phosphorescent doped PVK systems.

A new kind of wavelet-based method for spectrum deconvolution

To subtract the slit function from the measured spectrum, a wavelet-based deconvolution method is proposed to obtain a regularized solution of the problem. The method includes reconstructing the signal from the wavelet modulus maxima. For the purpose of maxima selection, the spatially selective noise filtration technique was used to distinguish modulus maxima produced by signal from the one created by noise. To test the method, sodium spectrum measured at a wide slit was deconvolved. He-Ne spectrum measured at the corresponding slit width was used as slit function. Sodium measured at a narrow slit was used as the reference spectrum. The deconvolutton result shows that this method can enhance the resolution of the degraded spectrum greatly.

Conversion of CO2 by non-Thermal Inductively-Coupled Plasma Catalysis

CO2 decomposition is a very strongly endothermic reaction where very high temperatures are required to thermally dissociate CO2.Radio frequency inductively-coupled plasma enables to selectively activate and dissociate CO2 at room temperature.Tuning the flow rate and the frequency of the radio frequency inductively-coupled plasma gives high yields of CO under mild conditions.Finally the discovery of a plasma catalytic effect has been demonstrated for CO2 dissociation that shows a significant increase of the CO yield by metallic meshes.The metallic meshes become catalysts under exposure to plasma to activate the recombination reaction of atomic O to yield O2,thereby reducing the reaction to convert CO back to CO2.Inductively-coupled hybrid plasma catalysis allows access to study and to utilize high CO2 conversion in a non-thermal plasma regime.This advance offers opportunities to investigate the possibility to use radio frequency inductively-coupled plasma to store superfluous renewable electricity into high-valuable CO in time where the price of renewable electricity is plunging.

Electrochemical Tuning by Polarized UV Light Induced Molecular Orientation of Chiral Salen-type Mn（II） and Co（II） Complexes in an Albumin Matrix

The authors have prepared supramolecular systems as artificial metalloproteins composed of several chiral salen-type Mn（II） and Co（II） complexes in a HSA （human serum albumin） matrix. The docking was discussed by UV-vis spectral changes and a ligand-protein docking simulation program. After linearly polarized UV light irradiation, that anisotropy of molecular orientation of the complexes increased was confirmed by polarized IR spectra. The authors have observed that the electrochemical behavior of the aligned complexes incorporating diphenyl groups in HSA can be tuned without UV radiation damage of HSA higher structures.

Research on Preparation of the Composite Materials LiFePO4-Li3V2（PO4）3

The article developed a lithium iron phosphate - composite cathode material of lithium vanadium phosphate. Using X-ray diffraction （XRD）, electronic scanning electron microscopy surface （SEM）, laser particle size analyzer, carbon and sulfur analyzer, and X-ray photoelectron spectroscopy, etc. for the prepared composites were characterized and found the material is mainly crystalline structure of lithium iron phosphate, and lithium vanadium, wherein a small amount of impurities; finer particle size of the material, the particle size distribution is narrow and uniform, smooth particle surface, wrapping in good carbon composite with other materials prepared in comparison the case has a carbon content of about optimum conductivity. To assemble the material into a cell after the 0.1C, IC, 2C when and 5C, the first discharge capacity were 160,145,127 and 109 mA·h·g^-1, after 50 cycles, the discharge capacity of 162, respectively, 144,126 and 106 mA·h·g^-1, which showed good rate characteristics and cycle characteristics.

Structural and Optical Performance of GaN Thick Film Grown by HVPE

Thick GaN films were grown on GaN/sapphire template in a vertical HVPE reactor. Various material characterization techniques,including AFM, SEM, XRD, RBS/Channeling, CL, PL, and XPS, were used to characterize these GaN epitaxial films. It was found that stepped/terraced structures appeared on the film surface,which were indicative of a nearly step-flow mode of growth for the HVPE GaN despite the high growth rate. A few hexagonal pits appeared on the surface, which have strong light emission. After being etched in molten KOH, the wavy steps disappeared and hexagonal pits with {1010} facets appeared on the surface. An EPD of only 8 ×10^6cm^-2 shows that the GaN film has few dislocations. Both XRD and RBS channeling indicate the high quality of the GaN thick films. Sharp band-edge emission with a full width at half maximum（FWHM）of 67meV was observed, while the yellow and infrared emissions were also found. These emissions are likely caused by native defects and C and O impurities.

RTD’s Relaxation Oscillation Characteristics with Applied Pressure

The relaxation oscillation characteristics of a resonant tunneling diode （RTD） with applied pressure are reported. The oscillation circuit is simulated and designed by Pspice 8. 0, and the measured oscillation frequency is up to 200kHz. Using molecular beam epitaxy （MBE） ,AIAs/lnx Ga1-x As/GaAs double barrier resonant tunneling structures （DBRTS） are grown on （100） semi-insulated （SI） GaAs substrate,and the RTD is processed by Au/Ge/Ni/Au metallization and an airbridge structure. Because of the piezoresistive effect of RTD,with Raman spectrum to measure the applied pressure, the relaxation oscillation characteristics have been studied, which show that the relaxation oscillation frequency has approxi- mately a - 17.9kHz/MPa change.

Study on Methanol Oxidation at Pt and PtRu Electrodes by Combining in situ Infrared Spectroscopy and Differential Electrochemical Mass Spectrometry

Methanol oxidation reaction （MOR） at Pt and Pt electrode surface deposited with various amounts of Ru （denoted as PtxRuy, nominal coverage y is 0.17, 0.27, and 0.44 ML） in 0.1 mol/L HClO4＋0.5 mol/L MeOH has been studied under potentiostatic conditions by in situ FTIR spectroscopy in attenuated-total-reflection con guration and di erential electro-chemical mass spectrometry under controlled flow conditions. Results reveal that （i） CO is the only methanol-related adsorbate observed by IR spectroscopy at all the Pt and PtRu electrodes examined at potentials from 0.3 V to 0.6 V （vs. RHE）; （ii） at Pt0.56Ru0.44, two IR bands, one from CO adsorbed at Ru islands and the other from COL at Pt substrate are detected, while at other electrodes, only a single band for COL adsorbed at Pt is observed; （iii） MOR activity decreases in the order of Pt0.73Ru0.27〉Pt0.56Ru0.44〉Pt0.83Ru0.17〉Pt; （iv） at 0.5 V, MOR at Pt0.73Ru0.27 reaches a current e ciency of 50% for CO2 production, the turn-over frequency from CH3OH to CO2 is ca. 0.1 molecule/（site sec）. Suggestions for further improving of PtRu catalysts for MOR are provided.