Preparation, characterization, and structural systematics of diphosphane and diarsane complexes of gallium(III) halides

The diphosphane o-C6H4(PMe2)2 reacts with GaX3 (X = Cl, Br, or I) in a 1:1 molar ratio in dry toluene to give trans-[GaX2{o-C6H4(PMe2)2}2][GaX4], the cations of which contain the first examples of six-coordinate gallium in a phosphane complex. The use of a 1:2 ligand/GaCl3 ratio produced [GaCl2{o-C6H4(PMe2)2}][GaCl4], containing a pseudotetrahedral cation, and similar pseudotetrahedral [GaX2{o-C6H4(PPh2)2}][GaX4] complexes are the only products isolated with the bulkier o-C6H4(PPh2)2. On the other hand, Et2P(CH2)2PEt2, which has a flexible aliphatic backbone, formed [(X3Ga)2{mu-Et2P(CH2)2PEt2}], in which the ligand bridges two pseudotetrahedral gallium centers. The diarsane, o-C6H4(AsMe2)2, formed [GaX2{o-C6H4(AsMe2)2}][GaX4], also containing pseudotetrahedral cations, and in marked contrast to the diphosphane analogue, no six-coordinate complexes form; a very rare example where these two much studied ligands behave differently towards a common metal acceptor. The complexes [(I3Ga)2{mu-Ph2As(CH2)2AsPh2}] and [GaX3(AsMe3)] are also described. The X-ray structures of trans-[GaX2{o-C6H4(PMe2)2}2][GaX4] (X = Cl, Br or I), [GaCl2{o-C6H4(PPh2)2}][GaCl4], [GaX2{o-C6H4(AsMe2)2}][GaX4] (X = Cl or I), [(I3Ga)2{mu-Ph2As(CH2)2AsPh2}], and [GaX3(AsMe3)] (X = Cl, Br or I) are reported, and the structural trends are discussed. The solution behavior of the complexes has been explored using a combination of 31P{1H} and 71Ga NMR spectroscopy.     

Four-component relativistic theory for nuclear magnetic shielding constants: critical assessments of different approaches

Both formal and numerical analyses have been carried out on various exact and approximate variants of the four-component relativistic theory for nuclear magnetic shielding constants. These include the standard linear response theory (LRT), the full or external field-dependent unitary transformations of the Dirac operator, as well as the orbital decomposition approach. In contrast with LRT, the latter schemes take explicitly into account both the kinetic and magnetic balances between the large and small components of the Dirac spinors, and are therefore much less demanding on the basis sets. In addition, the diamagnetic contributions, which are otherwise "missing" in LRT, appear naturally in the latter schemes. Nevertheless, the definitions of paramagnetic and diamagnetic terms are not the same in the different schemes, but the difference is only of O(c(-2)) and thus vanishes in the nonrelativistic limit. It is shown that, as an operator theory, the full field-dependent unitary transformation approach cannot be applied to singular magnetic fields such as that due to the magnetic point dipole moment of a nucleus. However, the inherent singularities can be avoided by the corresponding matrix formulation (with a partial closed summation). All the schemes are combined with the Dirac-Kohn-Sham ansatz for ground state calculations, and by using virtually complete basis sets a new and more accurate set of absolute nuclear magnetic resonance shielding scales for the rare gases He-Rn have been established.     

The alkoxide sol–gel process in the calcium phosphate system and its applications†

A single calcium glycolate was synthesized. The alkoxide was stable under ambient atmosphere. The calcium glycolate, phosphoric acid and P(OH) _x (OEt)_{3− x} were used as the precursors. Acetic acid was used as a reagent to modify the calcium glycolate and to change the acidity of the mixtures of the precursors. Mixtures of the calcium glycolate and phosphoric acid in a Ca/P ratio of 1.67 showed unusual sol–gel behavior. A transparent gel could be formed depending on the content of acetic acid and the extent of stirring. The behavior is attributed to a high viscosity and a large molecular size of the ethylene glycol solvent, leading to a strong dependence of the reactions in the mixtures on the diffusion process, greatly affected by stirring. When the mixtures of the calcium glycolate and PO(OH) _x (OEt) _{3− x} contained acetic acid at an acetic acid/Ca ratio of 3, stable alkoxide solutions with Ca/P ratios of 1.0, 1.5 and 1.67 could be formed. Different calcium phosphate compounds and hydroxyapatite coatings on alumina substrates could easily be formed from the alkoxide solutions. The chemical homogeneity provided by the alkoxide route leads to easy formation of the required products. Copyright © 1999 John Wiley & Sons, Ltd.     

Modeling and characterizing the typical under-ice acoustic channel for the Arctic

The properties of arctic underwater acoustic channel were researched using BurkeTwersky(BT) model and ray theory.In the BT model,sea ice ridge is assumed as a set of semi-elliptical cylinder randomly distributed on a stress-free surface.By approximation of low frequency and high frequency of the BT model,the reflection coefficients were calculated at different frequencies.On the basis of ray theory,the acoustic field was calculated and the properties of underwater acoustic channel was analyzed.Compared to underwater acoustic channel properties when the boundary is air,the results show that under the ice surface some sound rays disappear during transmission,because the ice surface reflection coefficients is less than absolute soft surface.Especially,the higher the frequency,the higher the under-ice transmission loss.As a result,under-ice condition is unfavourable for acoustic signals to travel far.Besides,as to the channel structure,the reflection coefficient of ice layer is smaller,the channel multi-path structure is not significant compared to water-air interface without ice.The research results are valuable for our understanding of hydroacoustic channel and the prediction of the sonar system working in the polar region.     

海洋真菌对苯和甲苯的降解诱导黄烷酮的羟基化转化

真菌在各种氧化酶的作用下能将苯环类化合物转化降解,但转化降解过程中诱发的高活性酶的应用仍未见报道。本文研究海洋真菌Pseudallescheria boydii和Trichoderma erinaceum在添加苯和甲苯的培养条件下,诱导黄烷酮向4'-羟基黄烷酮的转化。结果表明,2种真菌对苯和甲苯有强耐受力,其降解过程中诱导的氧化酶对黄烷酮的羟基化具有高度的区域选择性,即发生4'-羟基化反应,而且转化率最高可达到82%,在酶促进的反应领域具有潜在的应用价值。     

掺铒光纤激光器反相位混沌同步及其编码

针对单模双环掺铒光纤激光器具有光耦合相互作用的非线性动力学特点,应用“交叉注入反相位双环对两环主动—被动”混沌同步方法,数值模拟实现了两组相互独立的单模单环掺铒光纤激光器激光分别和单模双环掺铒光纤激光器对应环激光混沌同步;提出并数值模拟了具有调制频率1kHz和15kHz的正弦信号的双环—两环的两路混沌隐藏编码保密通信系统,它们解码质量好,保密性能强,可以很好地应用在混沌多路保密通信中。     

Synthesis,characterization and performance of nanosized Bi<Subscript>0.1</Subscript>Sn<Subscript>0.9</Subscript>O<Subscript>2</Subscript>–WPU organic–inorganic hybrid coatings

A series of organic–inorganic hybrid coatings consisting of organic waterborne polyurethane (WPU) and inorganic nanosized bismuth-doped tin dioxide were successfully synthesized by the in situ polymerization approach. Bi_0.1Sn_0.9O₂ nano-powders were prepared via a new route of sol–gel combustion hybrid method using acetylene black as the fuel. The formed nano-powders were characterized by transmission electron microscopy and X-ray diffraction (XRD). Bi_0.1Sn_0.9O₂–WPU was then fabricated with isophorone diisocyanate, 2,2-bis(hydroxymethyl) propionic acid and nano-Bi_0.1Sn_0.9O₂-poly(ε-caprolactone) (PCL) as the starting materials. Organic–inorganic hybrid coatings are always achieved with adjustable contents of Bi_0.1Sn_0.9O₂. The hybrid coatings with Bi_0.1Sn_0.9O₂ loading on the glass substrate exhibited good heat insulation efficiency. The tensile strength and breaking extensibility of nanocomposite film containing 1.0% of the nano-Bi_0.1Sn_0.9O₂ were measured as 9.35 MPa and 248%, respectively. The transmittance of visible light was above 80%. The heat insulation of glass coated with nano-Bi_0.1Sn_0.9O₂–WPU hybrid was over 60 °C in contrast to the commercial blank glass.     

Comprehensive theoretical studies on the low-lying electronic states of NiF, NiCl, NiBr, and NiI

The low-lying electronic states of the nickel monohalides, i.e., NiF, NiCl, NiBr, and NiI, are investigated by using multireference second-order perturbation theory with relativistic effects taken into account. For the energetically lowest 11 lambda-S states and 26 omega states there into, the potential energy curves and corresponding spectroscopic constants (vertical and adiabatic excitation energies, equilibrium bond lengths, vibrational frequencies, and rotational constants) are reported. The calculated results are grossly in very good agreement with those solid experimental data. In particular, the ground state of NiI is shown to be different from those of NiF, NiCl, and NiBr, being in line with the recent experimental observation. Detailed analyses are provided on those states that either have not been assigned or have been incorrectly assigned by previous experiments.     

High-performance liquid chromatographic separation of imidazolinone herbicide enantiomers and their methyl derivatives on polysaccharide-coated chiral stationary phases

Many chiral pesticides exhibit enantioselectivity in biotransformation and ecotoxicity in the environment. A significant class of chiral pesticides is imidazolinone herbicides, of which enantioselectivity has not been well studied. Development of efficient chiral separation methods is the first step for allowing characterization of enantioselectivity in environmental processes. In this study, we attempted to resolve enantiomers of imidazolinone herbicides using reversed-phase and normal-phase high-performance liquid chromatography with polysaccharide-type chiral columns. Enantiomers of imazethapyr, imazaquin, and imazamox were separated on a Chiralcel OD-R column using 50mM phosphate buffer-acetonitrile as mobile phase. Enantiomers of imazapyr, imazapic, imazethapyr, imazamox and imazaquin were resolved on a Chiralcel OJ column using n-hexane (0.1% trifluoroacetic acid)-alcohol as mobile phase. The enantiomers of five methyl derivatives of imidazolinone herbicides were also resolved on the Chiralcel OJ column. The Deltak' values revealed a structure-enantioselectivity relationship for the separation behaviors of the enantiomers on the OJ column. The described method was successfully applied for chiral analysis of two imidazolinone herbicides (imazapyr and imazaquin) in spiked soil samples.     

计算水下凹面目标散射声场的声束弹跳法

为了解决含有多次散射时水下目标声散射场的计算问题,提出了一种声束弹跳方法。把入射声波划分为若干声束,根据几何声学方法计算每条声束在目标表面的反射方向和能量损失,利用物理声学方法计算最后一次反射的声束所对应的面元的散射场,通过计算所有声束产生的散射场的叠加得到整个目标的散射场。计算了直角凹面圆锥体的散射声场,并对具体模型进行了水池测量实验,理论计算和实验测量结果一致。表明该方法作为一种高频近似的数值计算方法,可以计算存在多次散射时水下目标的散射声场。