Itosides A – I,New Phenolic Glycosides from Itoa orientalis

Eight new benzoylated gentisyl alcohol (=2‐(hydroxymethyl)benzene‐1,4‐diol) glucosides, itosides A–H ( 1 – 8 ), together with the new pyrocatechol (=benzene‐1,2‐diol) glycoside itoside I ( 9 ) were isolated from the bark and twigs of Itoa orientalis (Flacourtiaceae). In itosides B–D ( 2 – 4 ), the gentisyl alcohol moiety was esterified by 1‐hydroxy‐6‐oxocyclohex‐2‐ene‐1‐carboxylic acid, while itosides E–H ( 5 – 8 ) contained instead an additional 2‐hydroxybenzoic acid moiety. The compounds were accompanied by the known derivatives 4‐hydroxytremulacin ( 10 ), poliothyrsoside ( 11 ), poliothyrsin ( 12 ), homaloside D ( 13 ), tremulacin, and pyrocatechol β‐D ‐glucopyranoside. The structures of the new compounds were elucidated by spectral and chemical methods.     

Improved method for the determination of sulfur components in natural gas

Determination of trace concentrations of sulfur components in natural gas is a true analytical challenge. Only analytical procedures based on gas chromatography can meet the sensitivity and accuracy requirements dictated by environmental regulation institutions and modern chemical industry. In the present contribution the sample pretreatment and chromatographic separation steps have been evaluated and optimized based on the use of a flamebased sulfur chemiluminescence detector (SCD) for target compound detection. The proposed instrument consists of a programmed temperature vaporizing (PTV) injector employing a liner packed with Chromosorb 104, a 4 μm thick film apolar column and a flame-based SCD. Using a 13 mL sample loop the detection limit achievable with the new method is 3 μg S/m³. The precision of replicate measure. ments is generally in the range of 5–15% relative standard deviation. Lower detection limits can be achieved by preconcentrating larger sample volumes, e.g. 100 mL.     

Atom-surface elastic scattering in the presence of laser radiation

A qualitative discussion on atom-surface elastic scattering taking place in the presence of laser radiation is given. It is suggested that appreciable effects of laser radiation on diffraction patterns may be expected if the laser radiation is capable of inducing electronic transitions in atoms with a large probability.Research sponsored by the Air Force Office of Scientific Research (AFSC), United States Air Force, under Contract No. F49620-78-C-0005, and the National Science Foundation under Grant No. CHE77-27826. The United States Government is authorized to reproduce and distribute reprints for governmental purposes notwithstanding any copyright notation hereon.Alfred P. Sloan Research Fellow, 1976–1980; Camille and Henry Dreyfus Teacher-Scholar, 1975–1980.     

Using three major criteria to evaluate aromaticity of five-member C-containing rings and their Si-, N-, and P-substituted aromatic heterocyclics

In this paper, we used bond-length equalization, aromatic stabilization energies (ASE) and nucleus-independent chemical shifts (NICS), calculated with (density functional theory) B3LYP levels at the 6-311+G^** basis set, to evaluate the aromaticity of a set of 38 five-member planar π-electron aromatic systems: sila-, aza- and phospha- derivatives and their parent systems. The result revealed statistically significant correlations among the above three criteria, and the order of aromaticity of the whole set was: Aza- derivatives rings > Phospha- derivatives rings > Sila- derivatives rings > Carbon-containing rings; NICS(0.6) and NICS(0.8) had the same results in evaluating the order of aromaticity in our case.     

Synthesis,structure, and thermal decomposition of a novel one-dimensional chain complex of manganese(II) with 2,2-diphenic acid and 1,10-phenanthroline

A novel one-dimensional (1D) chain coordination polymer [Mn₂(2,2′-dipha)₂(phen)]_n has been synthesized by hydrothermal reaction, and characterized by elemental analysis, IR spectroscopy, TGA, and X-ray diffraction. Orange crystals crystallized in the monoclinic system, space group C2/c with a = 19.393(7) Å, b = 19.183(7) Å, c = 19.729(7) Å, β = 90.826(6)°, V = 7338(5) ų, Z = 8. In the crystal structure, one manganese atom is six-coordinated with four carboxylate oxygen atoms from one pentadentate 2,2′-dipha ligand and two tetradentate 2,2′-dipha ligands, and with two nitrogen atoms of one phen ligand, giving a slightly distorted octahedral geometry. The other manganese atom is five-coordinated with five oxygen atoms from two tetradentate 2,2′-dipha ligands and two pentadentate 2,2′-dipha ligands and has a trigonal bipyramidal environment. The TGA curve shows that the compound is stable below 310°.     

Potential-energy surface for the electronic ground state of NH3 up to 20,000 cm-1 above equilibrium

Ab initio coupled cluster calculations with single and double substitutions and a perturbative treatment of connected triple excitations [CCSD(T)] with the augmented correlation-consistent polarized valence triple-zeta aug-cc-pVTZ basis at 51 816 geometries provide a six-dimensional potential-energy surface for the electronic ground state of NH3. At 3814 selected geometries, CBS+ energies are obtained by extrapolating the CCSD(T) results for the aug-cc-pVXZ(X=T,Q,5) basis sets to the complete basis set (CBS) limit and adding corrections for core-valence correlation and relativistic effects. CBS** ab initio energies are generated at 51,816 geometries by an empirical extrapolation of the CCSD(T)/aug-cc-pVTZ results to the CBS+ limit. They cover the energy region up to 20,000 cm-1 above equilibrium. Parametrized analytical functions are fitted through the ab initio points. For these analytical surfaces, vibrational term values and transition moments are calculated by means of a variational program employing a kinetic-energy operator expressed in the Eckart-Sayvetz frame. Comparisons against experiment are used to assess the quality of the generated potential-energy surfaces. A "spectroscopic" potential-energy surface of NH3 is determined by a slight empirical adjustment of the ab initio potential to the experimental vibrational term values. Variational calculations on this refined surface yield rms deviations from experiment of 0.8 cm-1 for 24 inversion splittings and 0.4 (3.0) cm-1 for 34 (51) vibrational term values up to 6100 (10,300) cm-1.     

电感耦合等离子体原子发射光谱专家系统中谱线激发模型

阐述了ＩＣＰ－ＡＥＳ专家系统中ＡＥＳ电离和激发模型的基本原理，研究了模拟中应用ｎｏｎ－ＬＴＥ理论的正确性以及所需的支持数据库。利用Ｂｏｌｔｚｍａｎｎ曲线，讨论了Ｂｏｌｔｚｍａｎｎ温度的测量值随能级激发能变化的现象，并与类似条件下的经验Ｂｏｌｔｚｍａｎｎ曲线进行对比，证明了专家系统中ＡＥＳ电脑和激发模型可靠性。     

Synthesis and heterocyclizations of 3‐alkynyl‐6,8‐dimethylpyrimido‐[4,5‐c]pyridazine‐5,7(6H,8H)‐diones and their lumazine analogues

Synthesis of some condensed pyrrolo‐, thieno‐, furo‐, pyrido‐ and pyranopteridines as well as isomeric pyrrolo‐ and thienopyrimido[4,5‐c]pyridazines from alkynyl derivatives of 6,8‐dimethylpyrimido[4,5‐c]pyridazine‐5,7(6H,8H)‐dione and 1,3‐dimethyllumazine is represented.     

纳米尺寸团簇NinZrn(n=3～5)的几何结构与成键规律研究

根据化学键理论与拓扑原理，设计了团簇NinZrn(n=3-5)的可能几何构型，并用从头算方法进行构型优化，结果表明，由NiZr组成的团簇原子间的Zr-Zr和Zr-Ni键明显较强，而Ni-Ni的成键较弱，并发与NinZrn(n=3-5)团簇电子性质与有机烯烃分子等瓣相似，原子之间的成键按照强弱相间的规则分布。     

New Dammarane Monodesmosides from the Acidic Deglycosylation of Notoginseng‐Leaf Saponins

Three new dammarane monodesmosides, named notoginsenosides Ft₁ ( 1 ), Ft₂ ( 2 ), and Ft₃ ( 3 ), together with three known ginsenosides, were obtained from a mild acidic hydrolysis of the saponins from notoginseng (Panax notoginseng (Burk .) F. H. Chen ) leaves. Their structures were elucidated to be (3β,12β,20R)‐12,20‐dihydroxydammar‐24‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 1 ), (3β,12β)‐12,20,25‐trihydroxydammaran‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 2 ), and (3β,12β,24ξ)‐12,20,24‐trihydroxydammar‐25‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1 → 2)‐O‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranoside ( 3 ), by means of spectroscopic evidences. The known ginsenosides Rh₂ and Rg₃ 4 – 6 were obtained as the major products from this acidic deglycosylation.