A novel heteroseneous reaction for generating gaseous nitrous acid

The short-lived reactive specimen nitrous acid HONO was generated in the gas phase by the heterogeneous reaction of gaseous HCl with AgNO2 which can generate higher concentration of HONO than other methods. We investigated the process from generation to dissociation in the gas phase under different controlled temperatures, and discussed the ionization and reaction on the solid surface by combination of the photoelectron spectroscopy and photoionization mass spectroscopy （PES-PIMS） and in situ diffuse reflectance infrared Fourier transform spectroscopy （DRIFTS）.     

Styrene polymerization catalyzed by nickel complexes bearing hydroxyindanone-iminate ligands

Activated by methylaluminoxane, mononuclear bis（hydroxyindanone-iminate）nickel complexes Ni[ArN=CC2H3（CH3）C6H2（R）O]2 （Ar = 2,6-i-Pr2C6H3, R=Me（1）, R=CI（2）, and R=H（3）） showed good activity for the styrene polymerization. The effect of many reaction parameters including the AI/Ni ratio, temperature, and reaction time on catalytic activities of catalytic systems and the molecular weights of the obrained polystyrene was ascertained. The highest activity of 1.34×10^5g（PS）·mol^-1（Ni）·h^-1 was obtained under the optimum reaction condition. The ^13C NMR spectra of the polymers revealed that the polymer was isotactic-rich atactic polystyrene. And the coordination mechanism was confirmed by the analyses of the polymer chain end-groups.     

Modification of TiO2 nanotubes arrays by CdS and their photoelectrocatalytic hydrogen generation properties

In order to realize hydrogen generation under visible light, novel CdS/TiO2 nanotubes arrays are developed by electrochemical anodizaUon of Ti in 0.15 mol/L NHTF ＋ 0.08 mol/L H2C2O4 electrolyte. The diameter of the nanotube is 80-100 nm and the length is approximately 550 nm. The CdS nano-particles are deposited on the TiO2 nanotubes arrays by chemical bath deposition （CBD） in the ammonia-thiourea system. A 300 W Xe lamp is used as the light source, CdS/TiO2 nanotube arrays are used as the photoanode with the application of 1.0 V bath voltage, and 0.1 mol/L Na2S ＋ 0.04 mol/L Na2SO3 solution is used as the electrolyte, then the rate of photoelectrocatalytic hydrogen generation is 245.4 μL/（h·cm^2）. This opens new perspectives for photoelectrocatalytic hydrogen generation by using CdS/TiO2 nanotubes arrays.     

The uptake of ethyl iodide on black carbon surface

The importance of the iodine chemistry in the atmosphere has been demonstrated by recent obserations. The uptake of ethyl iodine on black carbon surface was inestigated at 298 K for the first time. Degussa FW2 （an amorphous black carbon comprising medium oxides） was used as black carbon sample. Black carbon surface was found to be deactiated in reaction with C2H51, and the uptake coefficient （r） was dependent on the time of exposure. The alue of （2.3±0.9）×10^-2 was determined for the initial uptake coefficient （No）. The result suggests that the heterogeneous loss of C2H51 on carbonaceous aerosols may be important under the atmospheric conditions.     

Visible light-induced degradation of organic pollutants using Fe（ll） supported on silica gel as an effective catalyst

Silica gel-supported Fe（ll） （SiOFe） was prepared and used for heterogeneous degradation of sulforhodamine B （SRB） and 2,4-dichlorophenol （DCP） under visible irradiation （λ 〉 420 nm） as an effective catalyst. UV-visible spectra, and infrared Spectrophotometry （IR）, fluorescence, total organic carbon （TOC） and electron spin resonance （ESR） measurements were employed to analyze the photoreaction products. The results showed that SRB could be efficiently degraded by SiOFe/H2O2 system under visible irradiation with 100% decolorization and 72.3% TOC removal after 180 min illumination. The results of ESR and fluorescence measurements indicated that the oxidative process was predominated mainly by the hydroxyl radical （.OH） generated in the system.     

Simulation experiments on the reaction system of CH4-MgSO4-H2O

H2S-rich gas in carbonate reservoirs is usually attributed to thermochemical sulfate reduction （TSR）. In this paper, thermal simulation experiments on the reaction system of CH4-MgSO4-H2O were carried out using autoclave at 425℃--525℃. The threshold temperature for initiating TSR is much lower than our previous studies （550℃）. Properties of the reaction products were analyzed by microcoulometry, gas-chromatography （GC）, Fourier transform-infrared spectrometry （FT-IR） and X-ray diffraction （XRD） methods. Thermodynamics and reaction kinetics of TSR processes were investigated on the basis of the experimental data. The results show that thermochemical reduction of magnesium sulfate with methane can proceed spontaneously to produce magnesium oxide, hydrogen sulfur, and carbon dioxide as the main products, and high temperature is thermodynamically favorable to the reaction. Ac- cording to the reaction model, the calculated activation energy of TSR is 101.894 kJ/mol, which is lower than that by most previous studies. Mg^2＋ may have played a role of catalytic action in the process of TSR. The elementary steps of TSR and reaction mechanism were discussed tentatively. The study can provide important information on the explanation of geochemical depth limit for natural gas and on the generation of high H2S gas in deep carbonates reservoirs.     

Investigation on the key factors in the hydrothermal synthesis of BN： The way of introducing sodium azide

The way of introducing sodium azide (NaN_3) into the reaction solution played an important role in the preparation of cBN by hydrothermal synthesis method. The results showed that both cBN content and crystalline perfection of the samples improved with increasing R_N value, and pure cBN could be obtained at 300℃ and 10 MPa when R_N increased to 3:1. Here R_N is defined as R_N =NaN_3(I)/NaN_3(II), wherNaN_3(I) denotes the amount of NaN_3 (in molar) that is added into the autoclave at the beginning of threaction process, and NaN_3(II) is the amount of NaN_3 (also in molar) introduced into the autoclave ahigh temperature and high pressure (i.e. 300℃ and 10 MPa). In order to explain the experimental results, a preliminary model was proposed in this paper.     

A novel Pd/silicalite-1 composite membrane for hydrogen separation

A novel Pd/silicalite-1 composite membrane supported on the macroporous tubular stainless steel substrate was successfully fabricated by electroless plating at 303 K. The structure, morphology and gaseous permeability of the membrane were detected by X-ray diffractiometry （XRD）, scanning electron microscopy （SEM） and single-gas permeation test, respectively. Results confirm the formation of a thin, smooth, and continuous Pd/silicalite-1 composite membrane. The obtained composite membrane shows a high H2 permeance of 1.15×10^-6 mol. m^-2. s^-1. Pa^-1 with moderate H2 selectivity of 250 for H2/N2 at 773 K, at 0.1 MPa pressure drop, suggesting the potential application for H2 separation.     

State of water and its implications for supersaturated structures in Mg(NO3)2 aerosols

One technique based on the difference spectra was developed to study the state of water in supersaturated Mg(NO₃)₂ aerosols. The technique could be derived from the observation that the Raman scattering and infrared absorbance cross sections of molecular vibrations of interest remain practically constant from diluted solutions to supersaturated aerosols. The spectra of solvated water were obtained and primarily related to the first hydration layers of solute molecules in supersaturated Mg(NO₃)₂ aerosols. Based on this investigation, a chain structure was proposed to occur in the supersaturated Mg(NO₃)₂ aerosols at low relative humidities (RHs). Supported by National Natural Science Foundation of China (Grant Nos. 20673010 and 20640420450), “111” Project (Grant No. B07012), and China Postdoctoral Science Foundation (Grant No. 20070410466)     

Detection of infrared photons with a superconductor

A superconductor single photon detector based on NbN nanowire was fabricated using electron beam lithography （EBL） and reactive ion etching （RIE） for infrared photon detection. When biased well below its critical current at 4.2 K, NbN nanowire is very sensitive to the incident photons. Typical telecommunication photons with a wavelength of 1550 nm were detected by this detector. Data analysis indicates the repeating rate of the device with 200 nm NbN nanowire may be up to 100 MHz, and the quantum efficiency is about 0,01% when biased at 0.95/c.     

A new type of longitudinally driven GMI effect of FeCo-based alloy

On investigating the longitudinally driven GMI effect of the DC annealed Fe36Co36Nb4Si4.8B19.2 alloy ribbon, the current density was 3.2×10^7 A/m^2, the GMI effect responds sensitively （the sensitivity is as high as 2440.2%/（A-m^-1）） to weak magnetic field after a 600-second annealing. The experimental result shows that the sensitivity is closely related to annealing current density, driven current frequency and eroded thickness. GMI effect, current annealing, sensitivity, magnetic domain structure     

Flow characteristics and reaction properties of carbon dioxide in microtubules and porous media

Carbon dioxide reacts with porous media while flowing through them enhancing their permeability. Its flow behavior as well as the permeability enhancement effects were studied in synthetic cores, natural cores and microtubes with an inner diameter of 5 μm. The results show that the permeability of H2O-saturated cores （containing carbonate ingredients） was enhanced by increasing the injection volume of a CO2-H2O solution. This enhancement is attributable to carbon dioxide＇s corrosion, which is justified by SEM scanning. The same phenomenon occurs with a CO2-H2O solution in microtubes, but for a different reason. The gas flow velocity of carbon dioxide in microtubes was approximately 100% faster than that of nitrogen because of the scale and the squeezing effects. Carbon dioxide molecules dissolved in water accelerate the diffusion rate of water molecules within the boundary layer, which in turn diminishes the thickness of the water film and enlarges the effective pore size. This flow behavior facilitates the injection of carbon dioxide into low-permeability reservoirs for oil-displacement and formation energy buildup purposes. This behavior also increases the potential for carbon dioxide channeling or release from the formation.     

Excitatory effect of histamine on neuronal activity of rat cerebellar fastigial nucleus Jn vitro

The cerebellar fastigial nucleus （FN） holds an important role in motor control and body balance. Previous studies have revealed that the nucleus is innervated by direct hypothalamocerebellar hletaminergic fibers. However, the functional role of histaminergic projection in cerebellar FN has never been established. In this study, we investigated the effect of histamine on neuronal firing of cerebellar FN by using slice preparations. Sixty-five FN cells were recorded from 47 cerebellar slices, and a vast majority of the cells responded to histamine stimulation with an excitatory response （58/65, 89.2%）. Perfusing slices with low-Ca^2＋/high-Mg^2＋ medium did not block the histamine-induced excitation （n=10）, supporting a direct postsynaptic action of histamine on the cells. Furthermore, the excitatory effect of histamine on FN neurons was not blocked by selective histamine H1 receptor antagonist triprolidine （n=15） or chlorpheniramine （n=10）, but was effectively suppressed by ranitidine （n=15）, a highly selective histamine H2 receptor antagonist. On the other hand, highly selective histamine H2 receptor agonist dimaprit （n=20） instead of histamine HI receptor agonist 2-pyridylethylamine （n=16） mimicked the excitatory effect of histamine on FN neurons. The dimaprit-induced FN neuronal excitation was effectively antagonized by selective histamine H2 receptor antagonist ranitidine （n=13） but not influenced by selective histamine H1 receptor antagonist triprolidine （n=15）. These results demonstrate that histamine excites cerebellar FN cells via the histamine H2 receptor mechanism and suggest that the hypothalamocerebellar histaminergic fibers may modulate cerebellar FN-mediated sensorimotor integration through their excitatory innervations on FN neurons.     

C-H···Pd(II) interaction-driven homochiral M helix formation of neutral (R,R)-bis(pyrrol-2-ylmethyl- eneamino) cyclohexane palladium(II) complex

A chiral complex of (R,R)-Pd was prepared by reaction of optically pure (R,R)-bis(pyrrol-2-ylmethyl-eneamino) cyclohexane ligand with Pd(OAc)2·2H2O under the base condition at room temperature. The weak intermolecular C-H···Pd interaction was found to be responsible for the homochiral M helix for-mation of the neutral,chiral,mononuclear (R,R)-Pd in the crystal packing.     

Density functional study on mechanism of CO oxidation with activated water on O/Au （1 1 1 ） surface

With density functional theory, the mechanism of water-enhanced CO oxidation on oxygen pre-covered Au （111） surface is theoretically studied. First, water is activated by the pre-covered oxygen atom and dissociates to OHads group. Then, OHads reacts with COads to form chemisorbed HOCOads, Finally, with the aid of water, HOCOads dissociates to CO2. The whole process can be described as 1/2H2Oads ＋ H2Oads ＋ 1/2Oads＋ COads→H3Osds ＋ CO2, gas. One CO2 is formed with only 1/2 pre-covered oxygen atom. That is why more CO2 is observed when water is present on oxygen pre-covered Au （111） surface. Activation energy of each elementary step is low enough to allow the reaction to proceed at low temperature.     

Synthesis and optical properties of poly[(4-(benzoxazole-2-yl)phenyl)methyl methacrylate] with 1,8-naphthalimide end group

A series of homopolymers, poly[(4-(benzoxazole-2-yl)phenyl)methyl methacrylate] (NAPH-PMABEs) containing benzoxazole side chain and 1,8-naphthalimide end group, were prepared by atom transfer radical polymerization (ATRP) and end-group modification. The structure of NAPH-PMABE was characterized by GPC, ¹H-NMR and UV-vis spectra. The polymer has good solubility in common organic solvents, such as dichloromethane (CH₂Cl₂), tetrahydrofuran (THF), N,N-dimethylformamide (DMF), chloroform (CHCl₃), acetone and toluene. The optical properties of NAPH-PMABE were investigated. Results show that NAPH-PMABE has a composite emission spectrum comprising an ultraviolet component originating from benzoxazole side chains and a green component originating from 1,8-naphthalimide end group in both solution and film. The intensity of the two emission bands can be easily tuned by changing molecular weight. Supported by National Natural Science Foundation of China (Grant Nos. 20476066 and 20571054), Science and Technology Project in Suzhou, China (Grant No. SG0718), and Project of High Technology of Jiangsu Province, China (Grant No. BG2005021)     

Relaxor behavior of (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 ceramics

n the present work, the phase transitions and relaxor behavior of (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMN-PT, x = 0.2―0.4) ferroelectric ceramics have been investigated by means of X-ray diffraction, di-electric spectroscopy, the P-E hysteresis loop measurements and Raman scattering techniques. Structural analysis revealed that with the increase of PbTiO₃ content, PMN-PT ceramics experienced a gradual phase transition process from rhombohedral to tetragonal. It is usually believed that such kinds of phase transitions resulted in the linear decrease of relaxation degree. Surprisingly, our analy-sis of the dielectric spectra revealed that the indicator of the degree of diffuseness γ reached the maximum value near morphotropic phase boundary (MPB) (x = 0.32), then decreased with the further increase of PbTiO₃ content. The large dielectric relaxor feature near MPB may be attributed to the for-mation of ordered nanodomains, resulting from complex coexisting nanostructures. Further, the P-E hysteresis loop measurements and Raman analysis of the B-site cation order correlated well with the dielectric measurement results. It was found that the hysteresis loop squareness R_sq received the minimum value while the inverse of the value of full wide of half maximum (FWHM) of A_1g mode reached the maximum value at MPB composition, which showed similar trends to γ.     

Low temperature thermodynamic study of the stable and metastable phases of vanadium

The low temperature thermodynamics of the stable phase of vanadium has been assessed by the polynomial and Debye models from the experimental data available in literature. By means of the con-strained nonlinear least squares curve fitting arithmetic,two sets of parameter values have been de-termined. Expressions of the thermodynamic functions Cp(T) and G(T)-H(298.15 K) at 0―298.15 K are presented. The low temperature thermodynamics of the metastable phase of vanadium can only be extrapolated by the Debye model. The expression of the thermodynamic function Cp(T) at 0―298.15 K is presented.     

Enhanced hydrosen production by insertional inactivation of adhE gene in Klebsiella oxytoca HP1

Ethanol is the main byproduct of anaerobic H2-producing fermentation in Klebsiella oxytoca HP1. Two moles of NAD（P）H are consumed to yield one mole of ethanol that may decrease bacterial hydrogen production. In this article the adhE gene that codes for acetaldehyde dehydrogenase was disrupted for the first time. A homologous recombination vector pTA-Str was constructed in which the adhE gene was disrupted by inserting an aminoglycoside-3＇-adenyltransferase （aadA） gene. As expected, the vector includes the insertion 5＇-adhE-aadA-adhE-3＇. The amplified DNA fragment 5＇-adhE-aadA-adhE-3＇ from pTA-Str was transformed into K. oxytoca HP1 and one recombinant was obtained. PCR analysis of the resulting genomic DNA indicated the appropriate deletion and insertion. Compared with the H2-production of wild type K. oxytoca HP1, the hydrogen yield of the mutant increased by 16.07% and ethanol concentration decreased by 77.47%, suggesting that inactivation of the adhE gene in K. oxytoca HP1 is a potential method for enhancing bacterial H2-production.     

Crystallization dynamics of supersaturated NaClO4 aerosols studied by high-speed photography

Single supersaturated NaClO4 aerosol droplets on a quartz substrate were observed by a high-speed video camera for their morphologic changes with decreasing relative humidity （RH）. The supersaturated droplets were found to form anhydrous NaClO4 at -10% RH. Three stages were roughly observed in this process, i.e., the main stem appearance, primary and secondary branches growth, and the deep dehydration. The main stem grew steadily and finished in 120 ms. Affected by both crystal precipitation and water evaporation, primary branches grew for 1200 ms, accompanied by a slower growth of secondary branches. The deep dehydration was more complicated, and lasted for a longer time.