四磺酸基酞菁锌在水和非水溶剂中的电化学性质研究

在非水溶剂（二甲基亚砜（ＤＭＳＯ）及Ｎ,Ｎ＿二甲基甲酰胺（ＤＭＦ））中的伏安曲线．呈现三对电流峰,表明存在三个可逆或准可逆酞菁配体的单电子转移过程,而在水溶液中则不呈现准可逆行为,且波形改变很大．此外,还比较了四磺酸基酞菁锌的水溶液在自然光和红光（６００～７００ｎｍ）照射下的循环伏安曲线,其氧化还原峰的数目和峰电位基本不变,但在红光照射下比自然光照射下的峰电流明显增大．     

Resonance enhanced three-photon absorption of molecular iodine

D ← X resonance enhanced three-photon excitation spectrum of iodine was observed by a cw intracavity absorption technique. Vibrational quantum numbers of D ← X transitions are given for every major spectral feature. The corresponding one-photon enhancement from the B state is evident from the one-photon vibrational assignment. The spectroscopic constants for the D state are v₀₀ = 40 998 cm^?1 ω′₀ = 113 cm^?1 and ω′₀χ′₀ = 0.045 cm^?.     

Alkylation of ethylenethiourea with alcohols: a convenient synthesis of S-alkyl-isothioureas without toxic alkylating agents

The alkylation of ethylenethiourea with alcohols and aqueous acids (HCl, HBr, and HI) allows the synthesis of the respective S-alkyl-isothioureas in high yield and purity. Consistently high yields (91-98%) were obtained with 56% HI, the yields for 48% HBr (48-93%) and 37% HCl (36-85%) were lower and varied with the type of alcohol. The method is a convenient low-cost alternative to the use of alkyl iodides and an easy access to the S-tert-butyl isothiourea.     

Mass spectrometry analysis of synthetically myristoylated peptides

Myristoylpeptides were synthesized in order to determine if a neutral loss of 210 Da, C14H26O (the mass of the myristoyl moiety), was universal and observable by both liquid chromatography electrospray ionization quadrupole ion trap (LC-ESI-QIT) and matrix-assisted laser desorption/ionization time-of-flight time-of-flight (MALDI-ToF/ToF) mass spectrometry. Myristoylation was successfully introduced on the N-terminus, internally on the amino group of lysine and arginine. Larger peptides and the arginine compounds needed elevated temperatures for myristoylation. To our knowledge, this is the first report of a chemically-synthesized myristoylated arginine in a peptide. Collision energy studies for the LC-ESI-QIT instrument showed that modified peptides and a loss of 210 Da could be detected under commonly used conditions (energy level between 30 and 42%) with picomole amounts of sample. The loss of myristoyl moiety is observed on the MALDI-Tof/Tof mass spectrometer as well. Due to the hydrophobic properties of the myristoyl moiety, it is not surprising that the modified peptides all formed at least dimers, and in some cases trimers. We were also able to distinguish a mixture of two mono-myristoylated peptides. MS3 data from the LC-ESI-QIT instrument on a di-myristoylated peptide indicates the loss of 210 Da at either the N-terminus or lysine. We were also able to analyze a mixture of modified and unmodified peptides on the MALDI-ToF/ToF instrument. The data presented in this paper demonstrates the constant neutral loss of the 210 Da, C14H26O, from both N-terminally and internally myristoylated peptides can be identified unambiguously using LC-ESI-QIT or MALDI-ToF/ToF mass spectrometers. This will be a useful tool in determining the myristoylation status of candidate proteins after enzyme digestion, and in elucidating the modification sites of internal myristoyl proteins.     

Simultaneous determination of cefazolin in rat blood and brain by microdialysis and microbore liquid chromatography

A sensitive microbore liquid chromatographic method combined with the minimally invasive technique of microdialysis was devised for simultaneously and continuously monitoring the levels of unbound blood and brain cefazolin in rats. Microdialysis probes were inserted into the jugular vein and brain striatum for blood and brain sampling, respectively. Chromatographic conditions consisted of a mobile phase of methanol-acetonitrile-100 mM monosodium phosphoric acid (20:10:70, v/v, pH 4.5) pumped through a microbore reversed-phase column at a flow rate of 0.05 mL/min. The ultraviolet detection wavelength was set at 270 nm. An on-line design allowed direct and continuous analysis of protein-free samples in the dialysate. Microdialysis probes, being home-made, were screened for acceptable in vivo recovery. Chromatographic resolution and detection were validated for response linearity as well as intra-day and inter-day variabilities. This method was then applied to pharmacokinetic profiling of protein unbound cefazolin in both the blood and brain following intravenous administration (10 mg/kg, i.v., n = 6). Rapid appearance of cefazolin in the rat brain striatal dialysate following drug injection suggested good blood-brain barrier penetration. According to a non-compartmental pharmacokinetics model, the area under the concentration (AUC) vs time ratio of cefazolin in rat brain and blood was 6%.     

A novel route for waste water treatment: photo-assisted Fenton degradation of dye pollutants accumulated in natural polyelectrolyte microshells

The efficient accumulation of dyes in constructed natural polyelectrolyte microshells under moderate conditions, combined with the photo-assisted Fenton reagent, opens a new route for the effective elimination of dye pollutants from waste water.     

Studies into the Diels-Alder reactions of 5-trimethylsilylthebaine

The introduction of a 5-trimethylsilyl group on the least hindered face of the diene thebaine was anticipated to favor attack by dienophiles from the alternate face, but only gave rise to a rearrangement product when treated with 3-butene-2-one at 110 °C. Reaction with the more reactive benzoquinone at lower temperature gave rise to a very slow reaction from the same face as the silyl group, indicating that a trimethylsilyl group does not sufficiently hinder this face to achieve reaction at the other face.     

深圳市1408例儿童发中钙,铁,镁含量调查与分析

用火焰原子吸收法检测了深圳市１４０８例１３岁以下儿童发中钙，铁，镁的元素含量，并探讨了元素含量与年龄，性别的关系，结果显示，性别差异有显著意义，钙，镁含量随年龄增长有相似变化。     

Structures, stabilities, and electronic and optical properties of c(58) fullerene isomers, ions, and metallofullerenes.

The 1205 classical isomers of fullerene C58, as well as one quasi-fullerene C58 isomer with a heptagonal ring (labeled as Cs:hept) have been investigated by the quantum chemical methods PM3, HCTH/3-21G, and B3LYP/6-31G(d). Isomer C3v:0001, which has the lowest number of adjacent pentagons, is predicted to be the most stable isomer, but the quasi-fullerene isomer Cs:hept is only 2.50 kcal mol-1 higher in energy. Systematic investigations of the electronic properties of C3v:0001 and Cs:hept find that the C3v:0001 isomer has high vertical electron affinity (3.19 eV). The nucleus-independent chemical shifts (NICS) value at the center of Cs:hept (-5.1 ppm) is more negative than that of C60 (-2.8 ppm). The NICS value at the center of the heptagonal ring in Cs:hept (-2.5 ppm) indicates weakly aromatic character. In contrast, the C58(6-) and C58(8-) ions of the C3v:0001 and Cs:hept geometries possess large aromatic character, with NICS values between -14.0 and -26.2 ppm. To clarify the thermodynamic stabilities of C58 isomers at different temperatures, the entropy contributions are taken into account on the basis of the Gibbs energy at the B3LYP/6-31G(d) level. The C3v:0001 isomer prevails in a wide range of temperatures, and the Cs:hept isomer is also an important component around 2800 K. The IR spectra of C58 isomers are simulated to facilitate experimental identification of different isomers. In addition, the electronic spectra and the second-order hyperpolarizabilities are predicted by ZINDO and the sum-over-states model. The static second-order hyperpolarizability of the C3v:0001 isomer is 96.5 % larger than that of C60, and its second-order hyperpolarizabilities at external field frequencies are at least nine times larger than those of C60.