Theoretical study on photophysical property of C60M（CO）5 （M=Cr,Mo and W）

Configurations of three η2 models of transition-metal [60]fullerene derivatives C60M（CO）5（M=Cr, Mo and W） have been optimized at B3LYP/LanL2DZ level. On the basis of the optimized geometrical structures, their electronic spectra and the frequency dependence of third-order nonlinear optical polarizabilities γ in different optical processes of third-harmonic generation （THG）, electric-field-induced second-harmonic generation （EFISHG） and degenerate four-wave mixing （DFWM） are calculated by using TDB3LYP model based on LanL2DZ level coupled with the SOS （sum-over-state） method. The obtained results show that their electronic spectra have a red shift compared with that of [60]fullerene and different transition-metal functional groups added to C60 cage may result in different spectrum properties. For the three studied species, （η^2-C60）Mo（CO）5 has the largest third-order nonlinear optical polarizability.     

Chemical composition of decomposing stumps in successive rotation of Chinese fir （Cunninghamia lanceolata （Lamb.） Hook.） plantations

Decomposition of stumps in successive rotation of Chinese fir （Cunninghamia lanceolata （Lamb.） Hook.） plantations was studied using a chronosequenee approach. The results showed that decomposition rate constant of Chinese fir stump was 0.02695 as calculated from Olson＇s model. The N content of stump increased during the first two-year decomposition. When the dead stump C/N ratio was 463.2 ± 27.3, the stumps started to release N. The pattern of P release was similar to that for N. However, K content of stumps showed a consistent declining trend over time during the whole decomposition. ^13C nuclear magnetic resonance spectroscopy with cross polarization and magic-angle spinning （^13C CPMAS-NMR） was used to analyse organic carbon （C） components in decomposing stumps. The ^13C CPMAS-NMR spectra of stumps displayed that stump was dominated by cellulose and hemieellulose. The spectra also showed the accumulation of intensity in alkyl C, aromatic C, and earboxyl C spectral regions, which was expected as the labile cellulose and hemieellulose components in O-alkyl C spectral region were selectively decomposed first.     

An experiment on multibubble sonoluminescence spectra in sodium chloride solution

We investigated experimentally the spectra of MBSL in sodium chloride water solution with krypton as dissolved gas. We observed and compared the spectra of hydroxyl ion at 310 nm and that of sodium atom at 589 nm. It has been found that under the same experimental condition, the intensity of sodium atom spectra is obviously higher than that of the hydroxyl ion spectra, and is more sensitive to the experimental condition. The krypton content, the concentration of sodium chloride solution, and the driving sound pressure obviously affect the spectra intensity in certain range.     

Novel trichromatic phosphor Co-doped with Eu, Tb in SiO2 gel matrix

The Eu, Tb co-doped SiO2 matrix tricolor fluorescence system was prepared by sol-gel technique. Red emission at 618 nm, green emission at 543 nm and blue emission at 350-500 nm were observed in the PL spectra of the sample, indicating that Eu^3＋, Eu^2＋ and Tb^3＋ ions coexisted in the matrix. In the co-doped sample, the blue emission of Eu^2＋ was much stronger than that of the sample single doped with Eu, which implied that the electron transfer between Eu^3＋ and Tb^3＋ maybe happened in the SiO2 matrix. The influences of the annealing temperature and Tb concentration on the PL spectra of the samples were investigated. The optimal doped concentration of Tb was determined to be 0.2% and the optimal annealing temperature 850℃. Annealed at 600℃, Tb^3＋ had a sensitizing effect on Eu^3＋ in the SiO2 matrix, and the emission intensity of Eu^3＋ in the Eu, Tb co-doped sample was more than four times that of the single doped sample, which could be attributed to the energy transfer from Tb^3＋ to Eu^3＋.     

DIRECT ELECTROCHEMICAL SYNTHESIS AND CHARACTERIZATION OF NEODIMIUM （Ⅲ） COMPLEX WITH 2-HYDROXY-2,4,6-CYCLOHEPTATRIENONE（TROPOLONE）

Tris(tropolonato)neodimium(Ⅲ）has been prepared by the electrochemical oxidation of neodimium metal anode in acetonitrile solution of 2-hydroxy-2,4,6-cycloheptatrienone(tropolone).The unusual divalent neodimium complex was formed at the first step of electrosyn-thesis.The final product,Nd(C7H6O2)3,has been characterized by microanalysis and the studies of IR and ^1H,C3 NMR spectra.     

Photodissociation/photoionization processes of chlorobromomethane induced by femtosecond laser pulses with pump-probe scheme

The photodissociation/photoionization processes of chlorobromomethane （CH2BrCl） induced by femtosecond laser pulses have been investigated using pump-probe scheme combined with the time-of-flight mass spectra. The dominate photoproducts are observed at different delay time of the pump （400 nm） and probe （800 nm） pulses and the corresponding time-dependence of them is obtained. The results show that the decaying time of the molecule CH2BrCI in the A-band is in the 100 fs. The decaying tendencies of the fragment ions （CH2CI^＋ and CH2Br^＋） and the parent ion （CH2BrCI^＋） are almost the same and the relative ratios of the yields of them keep constant during the delay time of 0 to 150 fs. These facts suggest that the fragment ions come from the fragmentation of the parent ions in excited electronic states. The probabilities to form CH2CI^＋ and CH2Br^＋ are obtained from the relative ratio of the ion intensity and are about 71.6% and 14.2%, respectively.     

Up-conversion luminescence of Er^3＋ doped and Er^3＋/Yb^3＋ co-doped YTaO4

The synthesis and up-conversion luminescent properties of YTaO4：Er^3＋ and YTaO4：Er^3＋/Yb^3＋ are reported for the first time. According to the measurement results of up-conversion spectra, Yb^3＋ co-doping can remarkably enhance the green （^2H11/2/^4S3/2→^4I15/2） and red （^4F9/2→^4I15/2） emissions, but depress the infrared emission （^4I9/2→^4I15/2）. With the increase of the Yb^3＋ concentration, the intensity of green emission increases, after that, when the Yb^3＋ concentration increases continuously, the intensity of green emission decreases, while those of the red and infrared emissions increase and decrease alternately. In addition, the up-conversion mechanisms of Er^3＋ doped and Er^3＋/Yb^3＋ co-doped YTaO4 are also discussed. It is found that the transform of up-conversion mechanism from two-step energy transfer to cooperating sensitization takes place when Yb^3＋ concentration is increased up to 12 mol%. With the further increase of Yb^3＋ concentration, the energy-back-transfer gradually becomes the dominant up-conversion mechanism, which results in the quenching of the green emission and slight increasing of the red and infrared emissions.     

4-Formyl-2-（2H-benzotriazol-2-yl）-phenol： an ESIPT chromophore

In the present work, excited state intramolecular proton transfer （ESIPT） emission properties of a new benzotriazole derivative 4-formyl-2-（2H-benzotriazol-2-yl）- phenol （C1） were studied. 4-Formyl-2-（2H-benzotriazol-2- yl）-methoxy-benzene （C2）, 4-formyl-2-（2H-benzotriazol-2- yl）-phenyl acetate （C3） and 4-methyl-2-（2H-benzotriazol- 2-yl）-phenol （C4） were used as the reference molecules. ^1H NMR chemical shift of hydroxy group in C1 was located at more down field than that of C4 or p-hydroxy-benzaldehyde （C5）, respectively. C1 showed two absorption bands in the range of 260-400 nm zones in various solvents, while C2 and C3 exhibited single absorption band. The equal molar mixtures of C2/C5 or C3/C5 showed single absorption band. C2 and C3 displayed single fluorescence emission band in various solvents, while C1 exhibited dual emission bands in some strong polar solvents. Furthermore, the second emission band in these strong polar solvents showed the large Stokes shift. The results show that the second emission band of C1 was produced by ESIPT. C2 and C3 could not undergo ESIPT due to no hydroxy group. The geometry optimization calculation of enol and keto forms in the ground and excited states of C1 provided tough theoretical evidences of ESIPT.     

A theoretical study of the proton transfer process in the spin-forbidden reaction ^1HNO（^1A＇） ＋ OH^-→^ 3NO^-（^3∑^-） ＋ H2O

The spin-forbidden reaction 1HNO（^1A＋OH^-→3NO^-（^3∑^-）＋H2O has been extensively explored using vari- ous CASSCF active spaces with MP2 corrections in several basis sets. Natural bond orbital （NBO） analysis, together with the NBO energetic （deletion） analysis, indicates that the two isomers have nearly equal total energy and could compete with each other in the title reaction. More significantly, the singlet/triplet surface crossing regions have been examined and the spin-orbit coupling （SOC） and energetics have been computed. The computational results indicate that the SOC is very large at the crossing point T1/S0 trans （ca. 40.9 cm^-1）. Moreover, the T1/S0 trans has a low energy of 10.67 kcal/mol relative to that of trans-So. Therefore, the surface crossing to the triplet state seems much more efficient at the T1/S0 trans region along the minimum energy path （MEP）, However, The values of single （P1^ISC） and double （P2^ISC） passes estimated at T1/S0 trans show that the ISC occurs with a little probability.     

Raman scattering and photoluminescence of Fe-doped ZnO nanocantilever arrays

Single crystalline Fe-doped ZnO nanocantilever arrays have been synthesized by thermal evaporating amorphous Zn-Fe-C-O composite powder. The characterizations of composition, structure and phonon spectrum properties of the nanocantilevers have been performed. Arrays of uniform, perfectly aligned and single-crystal nanowires have been observed by electron microscopy. The results of the X-ray photo-electric spectra and the Raman spectrum provide the evidence that Fe is incorporated into the ZnO lattice at Zn site. Abnormally, the room temperature UV emission band of Fe-doped ZnO nanocantilevers disappears and the green one has a large red-shift, and the intensity of the green emission is strongly quenched because the Fe^3＋ enters the ZnO crystal lattice.     

Optical Properties of Ru(bipy)_2(dppx)~(2 ) in Different Environments

0Introduction Withtheincreasinginterestinginthestudyoftheinter actionbetweenpolypyridylruthenium(Ⅱ)complexesandDNA,ligandsderivedfromvariousmodificationof2,2′bipyridine(bipy)and1,10phenanthroline(phen)havebeen developed.Oneofthemostinterestingobservationsisthedis coveryofthemolecular“lightswitch”complexes[1].Theyarenotphotoluminescentinwaterbutdoemitinnonaqueoussol ventsorinthepresenceofDNA.Atfirst,thecomplexesRu(bipy)2(dppz)2 andRu(phen)2(dppz)2 (dppz=dipyrido[3,2a:2′,3′c]phena zine…     

Studies on the interaction of DNA and Ru (1,10-phenanthroline)2− (dipyrido[3,2−a:2′,3′−c]phenazine)2+

The interaction of Ru(phen)₂(dppz)²⁺(phen=1,10-phenanthroline,dppz=dipyrido[3,2−1:2′,3′−c]phenazine) and the calfthymus DNA were studied with fluorescence and ultraviolet visible absorption spectroscopy. The ultraviolet visible absorption spectrum of Ru(phen)₂(dppz)²⁺ calfthymus DNA, and their interaction demonstrated that Ru(phen)₂(dppz)²⁺ intercalated into the double helix of DNA via the ligand dppz. Fe(CN)₆ ⁴⁻ and NaCl can not quench the fluorescence of Ru(phen)₂(dppz)²⁺-DNA, which was in agreement with the intercalation mode. Foundation item: Supported by National Natural Science Foundation of China Biography: LING Lian-sheng (1972-), male, PhD, candidate.     

Chemiluminescence determination of tetracycline and oxytetracycline in pharmaceutical preparations using Ru (bipy)3 2+-cerium (IV) system

A new chemiluminescence (CL) method for the determination of tetracycline and oxytetracycline is developed, based on the CL reaction of tetracycline and oxytetracycline with Ru (bipy)₃ ²⁺ and Ce (IV). In sulfuric acid medium, the CL emission is generated upon continuous oxidtion of Ru(bipy)₃ ²⁺ by cerium (IV). The emission intensity is greatly enhanced when tetracycline and oxytetracycline are introduced into the reaction system after acid degradation. Under the optimum conditions, the calibration curves are linear over the range of 8.0×10⁻⁸∼4.0×10⁻⁶ mol/L for tetracycline and of 2.0×10⁻⁷∼4.0×10⁻⁵ mol/L for oxytetracycline, with the detection limits are 4.2×10⁻⁸ mol/L for tetracycline and 1.5×10⁻⁷ mol/L for oxytetracycline, respectively. The proposed method was used for the determination of tetracycline and oxytetracycline in pharmaceutical formulations with good results. Foundation item: Supported by the National Natural Science Foundation of China and the Natural Science Foundation of Hubei Province. Biography: HAH He-you (1962), male, Associate profeddor, Ph.D graduate candidate. Present address, Department of Chemistry, Huainan Teacher's College, Huainan.     

A Novel Degradation Pathway of Zn（dmid） （ phen）2 in Pyridine

The light-oxidation degradation processes of Zn(dmid)(phen)2(dmid = 4, 5-dimercapto-1,3-dithiole-2 one, phen = 1,10-phenanthroaline) in pyridine solvent has been monitored, h has been found under the light, dmid^2- of Zn(dmid)(phen)2 in pyridine solution could generate NCS^- and NCS^-replaces dmid^2- to form Zn(NCS)2 (phen)2 simultaneously. The crystal structure of Zn(NCS)2 (phen)2 has been determined. In the crystal of Zn(NCS)2 (phen)2. two NCS^- ligands are arranged in syn-configuration, and there is strong π-π interaction between the two adjacent parallel phen.     

Investigation of Ru （ phen ）3^2＋-Hydrazine-Ce（Ⅳ） Chemiluminescence System and Its Analytical Application

0 IntroductionThbiep ycroidmipnlee)xru ctahteinoinu mof(Ⅱ r)u t(he Rniuu(mbip,y m)3ai2n +ly) atrnids- t(r2is -,(21’ -,10-phenanthroline)ruthenium(Ⅱ) (Ru(phen)32 +) ,is a kindof sensitive analytical reagent for electrogenerated chemilumi-nescence(ECL) and chemiluminescence(CL) ,on which a par-ticular review has been presented[1]. The earliest publicationon the synthesis of Ru(bipy)32 +appeared in 1936[2], andduringthefollowing30 years ,theinvestigations relatedtothissubstance were only in…     

Preparation and luminescence characteristics of Sr3SiO5：Eu^2＋ phosphor for white LED

The Sr3SiO5：Eu^2＋ phosphor was synthesized by high temperature solid-state reaction. The emission spectrum of Sr3SiO5：Eu^2＋ shows two bands centered at 487 and 575 nm, which well agree with the theoretic values of emission spectrum. The excitation spectrum for 575 nm emission center has several excitation bands at 365, 418, 458 and 473 nm. And the results show that the emission spectrum of Sr3SiO5：Eu^2＋ is influenced by the Eu^2＋ concentration. The relative emission spectra of the white-emitting InGaN-based YAG：Ce^3＋ LED and Sr3SiO5：Eu^2＋ LED were investigated. The results show that the color development of InGaN-based Sr3SiO5：Eu^2＋ is better than that of InGaN-based YAG：Ce^3＋, and the CIE chromaticity of InGaN-based Sr3SiO5：Eu^2＋ is （x=0.348, y=0.326）.     

Determination of some carbonyl carboxylic acids using chemiluminescent reaction of Ru(bipy)3 2+−Ce(IV)

A coupled chemiluminescence method for the determination of some carboxylic acids was developed, based on their enhancement the chemiluminescence light emission of the reaction of tirs (2,2′-bipyridine) ruthenium(II) and Ce(IV) in sulfuric acid medium. The conditions for their determination were optimized. The following detection limits were obtained: oxalic acid, 2.67×10⁻⁸ mol/L; propandioic acid, 1.20×10⁻⁶ mol/L; pyruvic acid, 1.35×10⁻⁸ mol/L; citric acid, 5.10×10⁻⁸ mol/L; barbituric acid, 2.48×10⁻⁷ mol/L. The proposed method was successfully applied to determination of oxalic acid. The coupled chemiluminescent reaction mechanism and rate equation are proposed. Foundation item: Supported by the National Natural Science Foundation of China and the Natural Science Foundation of Hubei Province Biography: HAN He-you (1962-), male, Associate professor, phD, graduate candidate     

Photovoltaic properties of MEH-PPV/TiO2 nanocomposites

Photovoltaic properties of photodiodes based on nano-TiO2 and poly[2-methoxy,5-（2＇-ethlhexyloxy）-p-phenylenevinylene] （MEH-PPV） composites are investigated. By comparing composite devices with the same weight of TiO2 （nanoparticles and nanotubes）：MEH-PPV, it was found that the device with TiO2 nanotubes exhibited better performance. By further optimizing the weight radio of TiO2 nanotubes： MEH-PPV, we gained the device with a short circuit current density of 9.27μA/cm^2 with a light intensity of 16.7mW/cm^2 at the 500 nm wavelength, the highest open-circuit voltage of 1.1V, and a photosensitivity of 332 at reverse bias of -0.6V. The photosensitivity is improved by a factor of 33 compared with the undoped MEH-PPV device.     

Degradation of 2, 4-D acid using Mn2+ as catalyst under UV irradiation

In this paper, the oxidative degradation of 2, 4-dichlorophenoxyacetic acid (2, 4-D) using Mn²⁺/H₂O₂ reagent under UV irradiation was studied. The results show that 2, 4-D was degraded more completely in Mn²⁺/H₂O₂ solution than traditional Fenton solutions. The effects of the concentration of Mn²⁺, H₂O₂ and pH were also investigated. And under the optimal condition of 1.48×10⁻⁴ mol/L, 8.99×10⁻⁵ mol/L and pH 3.38, the formation of ·OH was the most, both the decomposition rate of H₂O₂ and the degradation rate of 2, 4-D were the fastest. In addition, the photoreaction process was monitored using spin-trapping electron paramagnetic resonance (EPR), and the results indicated that the oxidative process was predominated mainly by the hydroxyl radical (·OH) gennerated in the system. Biography: HUANG Yingping (1964–), Professor, Ph. D., research direction: pollution ecology and water pollution control.     

Preparation and performance of LiNi0. 8Co0.2O2 cathode material based on Co-substituted α-Ni（OH）2 precursor

Co-substituted α-Ni（OH）2 was synthesized by a novel microwave homogeneous precipitation method in the presence of urea. LiNi0.8Co0.2O2 cathode material was synthesized by calcining Co-substituted α-Ni（OH）2 precursor and LiOH·H2O at 900℃for 10 h in flowing oxygen. XRD, FTIR, FESEM and electrochemical tests were used to study the physical and the electrochemical performances of the materials. The results show that the prepared LiNi0.8Co0.2O2 compound has a good layered hexagonal structure. Moreover, the LiNi0.8Co0.2O2cathode material demonstrates stable cyclability with a high initial specific discharge capacity of 183.9 mAh/g. The good electrochemical performance could be attributed to the uniform distribution of Ni^2＋ and Co^2＋ ions in the crystal structure and a minimal cation mixing in LiNi0.8Co0.2O2 host structure.