Preparation and characterization of finely dispersed drugs. 5. Ethyl 3,5-di(acetylamino)-2,4,6-triiodobenzoate

Controlled precipitation of the diagnostic imaging agent ethyl 3,5-di(acetylamino)-2,4,6-triiodobenzoate has been used to produce fine particles of various sizes, morphologies, and degrees of crystallinity, which depended on experimental conditions. In addition, two distinct polymorphic forms of the drug have been fully characterized by single crystal X-ray diffraction studies, and evidence for a third polymorph was also observed. Some of the so prepared dry particles were coated with a thin layer of silica.     

A nucleophilic substitution reaction in microemulsions based on either an alcohol ethoxylate or a sugar surfactant

A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.

¹²⁷I NMR studies, as well as quadrupole splitting experiments performed by ²H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.

The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles.     

用于激光推进的高功率激光器的选择

 从激光推进的要求出发，阐述了用于激光推进的高功率激光器的选择原则，即激光器必须满足：（1）高的平均功率和峰值功率；（2）高的单脉冲能量；（3）高的重复频率；（4）优良的大气传输特性。主要分析了目前YAG固体激光器、自由电子激光器和TEA脉冲CO₂激光器的特点，通过上述4个方面性能的比较，认为在目前水平下，TEA脉冲CO₂激光器是进行激光推进的首选强激光源，其优点表现在：功率可达10kW量级，单脉冲能量可达0.5~1kJ，重复频率为20~40Hz；激光波长处于大气传输窗口，对大气变化不敏感；工作物质快速流动，不存在热透镜效应和破坏阈值；相关光学元件易于制造；光束质量较好；运行成本低。     

Non-protein amino acids in peptide design

An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the useα-aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments and^DPro-Xxx segments for nucleating ofβ-hairpin structures.β- andγ-amino acid residues have been used to expand the range of designed polypeptide structures. Dedicated to Professor C N R Rao on his 70th birthday     

Three-dimensional structure of Saccharomyces cerevisiae inorganic pyrophosphatase complexed with cobalt and phosphate ions

Crystals of Saccharomyces cerevisiae inorganic pyrophosphatase suitable for X-ray diffraction study were grown by cocrystallization of the enzyme with cobalt chloride and imidodiphosphate. Saccharomyces cerevisiae is a metal-dependent enzyme which catalyzes hydrolysis of inorganic pyrophosphate to orthophosphate. The three-dimensional structure of this enzyme was solved by the molecular-replacement method and refined at 1.8 Å resolution to an R factor of 19.5%. Cobalt and phosphate ions were revealed in the active centers of both identical subunits (A and B) of the pyrophosphatase molecule. In subunit B, a water molecule was found between two cobalt ions. It is believed that this water molecule acts as an attacking nucleophile in the enzymatic cleavage of the pyrophosphate bond. It was demonstrated that cobalt ions and a phosphate group occupy only part of the potential binding sites (two chemically identical and crystallographically independent subunits have different binding sites). The arrangement of ligands and the structure of the nucleophile-binding site are discussed in relation to the mechanism of action of the enzyme and the nature of the metal activator.     

Shell effects in the symmetric-modal fission of pre-actinide nuclei

Mass distributions of fragments in the low-energy fission of nuclei from ¹⁸⁷Ir to ²¹³At have been analysed. This analysis has shown that shell effects in symmetric-mode fragment mass yields from the fission of pre-actinide nuclei could be described if one assumes the existence of two strongly deformed neutron shells in the arising fragments with neutron numbers N₁ ≈ 52 and N₂ ≈ 68. A new method has been proposed for quantitatively describing the mass distributions of the symmetric fission mode for pre-actinides with A ≈ 180–220.     

Electronic molecule-like spectrum of quantum wells in crossed fields

We show that an electron confined to a single finite parabolic quantum well in crossed electric and magnetic fields can behave as a double quantum well system. The magnetic field is parallel to the heterostructure layers and the electric field is perpendicular to those. For a suitable choice of both fields and quantum well width, the electron can be confined to a double quantum well effective potential that is very similar to the electronic potential model for diatomic molecules. The double quantum well spectrum is calculated using a numerical algorithm based on semiclassical methods. A physical interpretation of this quantum system is given based on the analogy to the electrons bound to diatomic molecules.     

Partial structure elucidation of the most abundant octa and nonachlorotoxaphene congeners in marine mammals by using conventional electron ionization mass spectrometry and mass spectrometry/mass spectrometry

Summary Conventional electron ionization (EI) mass spectrometry (MS) and MS/MS techniques were applied to the analysis of two abundant octa and nonachlorobornanes isolated from seals of the Baltic sea and originating from technical toxaphene. The exact sterical structures of the two compounds were previously determined using nuclear magnetic resonance (NMR) spectroscopy by two independent research groups. The MS and MS/MS data generated in this study allowed partial structure elucidation of these polychlorobornanes, in particular revealing the distribution of the Cl substituents between the six-membered carbon ring, the bridge and the bridgehead in the parent bornane structure. Fragmentation of the six-membered carbon ring and the bridge by retro-Diels-Alder (RDA) and related mechanisms was discovered by studying specific parent/daughter ion transitions. The detailed fragmentation pathways formulated may be applicable to the structure elucidation of other toxaphene congeners and the monitoring of strategic transitions is highly selective for the detection of these compounds in technical toxaphene and in environmental samples.