Preparation and characterization of nitrogen-doped TiO2 photocatalyst in different acid environments

Nitrogen-doped TiO₂ powders were successfully prepared by a wet method, i.e., a micro-emulsion-hydrothermal method, in different acid environments. Several characterization techniques, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance spectra, were combined to determine the crystal phase, concentration and chemical states of the nitrogen doped in TiO₂. The high photocatalytic activity of the nitrogen-doped TiO₂ was evaluated through the decomposition of rhodanmine B under visible light irradiation. It was suggested that the doped nitrogen formed oxynitride (NO) and produced impurity states at higher above the valence band of TiO₂. Therefore, the nitrogen doping could enhance the response of photocatalyst to the visible light and improve the photocatalytic activity because of the narrowing of band gap of TiO₂.     

重油催化裂化汽油中含氮化合物的分析

利用酸萃取技术浓缩分离重油催化裂化（RFCC）汽油中的氮化物，比较了两种萃取剂和两种油剂比对分离效果的影响，结果发现选用10％（体积分数）HCl作萃取剂，油剂比为10：1（体积比）时，碱性氮化物的提取率较高；浓缩分离出的氮化物用色谱－质谱联用方法对其进行了检测，结果表明RFCC汽油中的氮化物主要是C0－C2苯胺及少量吡啶类、喹啉类碱性氮化物。     

Force Constants and Bond Orders of Nitrogen Bonds

The force constants and the corresponding bond orders of nitrogen bonds have been calculated from the vibrational spectra (infrared and Raman spectra) of a great number of nitrogen compounds. Plotting the maximum bond order of stable nitrogen bonds against the sum of Pauling's electronegativities of the bonding partners (Σx) leads to one continuous curve for the N? X bonds where X represents elements of the first and the second short period of the periodic table. Furthermore, when the bonds formed between these elements are arranged in a coordinate system in such a way that the position of each bond is determined by the difference between the electronegativities of the bonding partners (Δx along the ordinate) and the sum of the electronegativities of the bonding partners (Σx along the abscissa), the bonding partners capable of forming multiple bonds all lie within a closed domain, where their position can be correlated with their polymerizability and other reactivities of the multiple bonds. Also discussed are the orders of bonds between nitrogen and some transition elements. In an appendix, the present methods used to calculate force constants and bond orders are surveyed.     

Optimization of a nitrogen analyser based on the Dumas method

The objectives of this work was to obtain a total nitrogen concentration in milk with the Dumas method for industrial and research applications. This method was faster than the Kjheldal method (5 min against 2 h or 3 h) but less precise. A three factor experimental design was performed to optimize the instrument, a FP-2000 supplied by LECO. The first interpretation of the experimental design was disappointing and no conclusion could be done. It was not a failure of experimental design but a lack of thinking on the physical and chemical aspect of the problem. Selection and construction of composite responses based on chemical and physical consideration were the keys to optimize the Dumas method. This method is now as precise as the Kjheldal method, but considerably faster.     

Synthesis and structural characterization of ferrocene-based bis(pyrazol-1-yl)borate ligands: FcB(Me)pz2K, Fc2Bpz2K, and 1,1′-fc[B(Me)pz2]2K2 (Fc: ferrocenyl, fc: ferrocenylene, pz: pyrazolyl)

Reaction of the ferrocenyl(dimethylamino)boranes FcB(Me)NMe₂, Fc₂BNMe₂, and 1,1′-fc[B(Me)NMe₂]₂ with 1:1 mixtures of pyrazole and potassium pyrazolide in refluxing THF gave the potassium salts of the ferrocene-based bis(pyrazol-1-yl)borate ligands FcB(Me)pz₂K, Fc₂Bpz₂K, and 1,1′-fc[B(Me)pz₂]₂K₂ in good yield (Fc: ferrocenyl, fc: ferrocenylene, pz: pyrazolyl). In the solid state, FcB(Me)pz₂K and Fc₂Bpz₂K form centrosymmetric dimers with short K?Cp contacts suggesting an η⁵ coordination mode of the potassium ion. The crystal lattice of the ditopic ligand 1,1′-fc[B(Me)pz₂]₂K₂ consists of coordination polymer strands featuring essentially the same structural motif that has been observed for the monotopic derivatives. All three scorpionate ligands are thus promising building blocks for the preparation of ferrocene-containing multiple-decker sandwich complexes.     

Structure and protonation of some indolizine derivatives studied by ab initio MO calculations

Some gauge invariant atomic orbitals-coupled-perturbed Hartree-Fock (GIAO-CPHF) calculations were performed for seven indolizine derivatives and their monoprotonated forms. Chemical shift, molecular geometry, and charge distribution data are reported for each molecule. The calculations support the results of nuclear magnetic resonance (NMR) spectroscopy measurements showing that protonation occurs preferentially at N1. The good agreement between the calculated and observed ¹³C and ¹⁵N chemical shifts show that such calculations can be used for chemical shift assignment purposes. Cation structures and probable sites for electrophilic reaction or second protonation are also discussed.     

Use of D–T-produced fast neutrons for in vivo body composition analysis: a reference method for nutritional assessment in the elderly

Body composition has become the main outcome of many nutritional intervention studies including osteoporosis, malnutrition, obesity, AIDS, and aging. Traditional indirect body composition methods developed with healthy young adults do not apply to the elderly or diseased. Fast neutron activation (for N and P) and neutron inelastic scattering (for C and O) are used to assess in vivo elements characteristic of specific body compartments. Non-bone phosphorus for muscle is measured by the ³¹P(n,)²⁸Al reaction, and nitrogen for protein via the ¹⁴N(n,2n)¹³N fast neutron reaction. Inelastic neutron scattering is used to measure total body carbon and oxygen. Body fat is derived from carbon after correcting for contributions from protein, bone, and glycogen. Carbon-to-oxygen ratio (C/O) is used to measure the distribution of fat and lean tissue in the body and to monitor small changes of lean mass. A sealed, D–T neutron generator is used for the production of fast neutrons. Carbon and oxygen mass and their ratio are measured in vivo at a radiation exposure of less than 0.06 mSv. Gamma-ray spectra are collected using large BGO detectors and analyzed for the 4.43 MeV state of carbon and 6.13 MeV state of oxygen, simultaneously with the irradiation. P and N analysis by delayed fast neutron activation is performed by transferring the patient to a shielded room equipped with an array of NaI(Tl) detectors. A combination of measurements makes possible the assessment of the quality of fat-free mass. The neutron generator system is used to evaluate the efficacy of new treatments, to study mechanisms of lean tissue depletion with aging, and to investigate methods for preserving function and quality of life in the elderly. It is also used as a reference method for the validation of portable instruments of nutritional assessment.     

Synthesis of β-tosylethylhydrazine and its use in preparation of N-protected pyrazoles and 5-aminopyrazoles

β-Tosylethylhydrazine (6) can be prepared efficiently in one step from commercially available p-tolyl vinyl sulfone (7) and hydrazine hydrate. This hydrazine reacts with both 1,3-diketones and conjugated ynones in glacial acetic acid to provide a variety of N-tosylethyl-protected (TSE) pyrazoles in good yields. The TSE group can be removed from the pyrazoles using potassium t-butoxide in THF at −30 °C-rt. In addition, hydrazine 6 condenses with β-ketonitriles and β-aminoacrylonitriles to afford 5-aminopyrazoles, which can be deprotected by brief treatment with NaOEt in EtOH/DMSO at 45 °C.     

Asymmetric synthesis of 1-substituted-1-(pyridin-2-yl)methylamines by diastereoselective reduction of enantiopure N-p-toluenesulfinyl ketimines

Reduction of enantiopure N-p-toluenesulfinyl ketimines derived from 2-pyridyl ketones affords N-p-toluenesulfinyl amines with good yields and diastereoselectivities.     

碳化树脂全孔结构分析

本文阐述了改良的MP法,对含中孔和微孔的碳化树脂,用改良的MP法计算其微孔分布;用模型法计算其中孔分布,两种方法分析的和表示其全部孔结构分析。