The synthesis of cypridina etioluciferamine and the proof of structure of cypridina luciferin

An unambiguous synthesis of Cypridina etioluciferamine was accomplished in order to prove the structure of this important bioluminescent natural product. Several 2-aminopyrazine 1-oxides were synthesized in order to establish a spectroscopic method for determining the placement of substituents on the pyrazine nucleus of Cypridina etioluciferamine. Titanium tetrachloride was used to improve the yields of these compounds; for example, the yield of 2-amino-3-methyl-5-phenylpyrazine 1-oxide (19) from reaction of phenylglyoxal 1-oxime and α-aminopropionitrile was raised from 3% to 51% by the use of titanium tetrachloride. The pyrazine ring proton is found at τ 1·37 (DMSO-d₆). The isomeric 2-amino-3-methyl-6-phenylpyrazine 1-oxide (22) was similarly prepared and its pyrazine ring proton is found at τ 2·18. This large difference (0·81 ppm) in chemical shift was used to determine whether a 2-aminopyrazine 1-oxide was 5- or 6- substituted. Prepared in an analogous fashion were 2-amino-5-(indol-3-yl)-3-methylpyrazine 1-oxide (23) and 2-amino-5-(indol-3-yl)-3-(3-phthalimidopropyl)pyrazine 1-oxide (16). The structures of these compounds were verified by NMR spectroscopy. By treatment with Raney nickel and hydrogen gas, then 100% hydrazine hydrate, 16 was converted to 2-amino-3-(3-aminopropyl)-5-indol-3-ylpyrazine (5), isolated as the dihydrochloride. This compound, with the indole moiety definitely placed at C-5, is identical with Cypridina etioluciferamine dihydrochloride (IR, UV, TLC). These results show that the structures of Cypridina etioluciferamine and luciferin are correct as published.     

Preparation of apolar glass capillary columns by the barium carbonate procedure

As an extension of previous reports, the barium carbonate procedure has been optimized in detail for the preparation of apolar columns. The aim was to produce optimum overall column characteristics, and to maintain them unchanged under the prolonged influence of the highest possible temperature. The main parameters under optimization were glass variety, leaching of glass surface with aqueous HCl, and amount of barium carbonate deposited, while deactivation and coating were kept constant. The basic column characteristics were adsorption properties and thermostability of deactivation, acid/base behaviour and separation efficiency. They were determined by a new, quantitative testing procedure. Intense leaching was able to eliminate almost totally the differences between glass varieties and to create a well-defined glass surface. While untreated glass, leached glass, and barium carbonate treated glass showed specific weak points in the respective column quality, the combination of leaching and barium carbonate treatment yielded the highest and most stable quality. Some technical modifications of the preparation procedure are described, including deactivation in the gas phase, and use of pentane as a solvent for static coating.     

Analytical applications of picolinealdehyde salicyloylhydrazone: Spectrophotometric determination of nickel and zinc

With a view to the use of picolinealdehyde salicyloylhydrazone as analytical reagent, a study of the physical properties and chemical reactions of this substance has been carried out. It reacts with nickel (λ_max = 375 nm, ? = 3.9 × 10⁴M^?1cm^?1) or zinc (λ_max = 365 nm, ? = 4.8 × 10⁴M^?1cm^?1) to produce a yellow 1:2 complex in both cases. Spectrophotometric determinations of trace amounts of nickel and zinc have been established.     

Correlation of the position of the bond functions in H-X with electronegativity

S type Gaussian bond functions are optimized for HF, H₂O, NH₃, and CH₄. The optimization is carried out with respect to the exponent and position in the H-X bond. The position is found to correlate well with the electronegativity of Pauling and Allred-Rochow.     

The composition of the evolved gases from the thermal decomposition of certain metal sulfates

By the use of TG—MS, the thermal dissociation of anhydrous CuSO₄ and Al₂(S0₄)₃ was found to proceed according to the reactions:

followed by the reactions:

No SO₃ was indicated in the dissociation of alunite. The sulfate ion appears to dissociate by at least two different mechanisms although the parameter which controls the mechanisms has not been elucidated.     

Multiparametric curve fitting-VII Determination of the number of complex species by factor analysis of potentiometric data

The number of complex species in solution may be determined by a computer-assisted factor analysis of a set of potentiometric titration curves, by finding the rank of the normalized data matrix. An application of the program SPECIES is demonstrated for some examples of titration data. The method is limited in that it can discriminate only between species with differing degrees of polymerization.     

“限时服务规则”下的复线船闸多目标调度优化

针对现有船舶过闸排队规则的欠缺,基于“限时服务规则”,构建复线船闸多目标双层优化调度模型:上层模型用于获得两个闸室安全区域的船舶排布可行方案;下层模型用于获得不同船舶排布可行方案的优化闸次数。下层模型分两个阶段完成:对符合“限时服务规则”的船舶,构建以闸次最少为目标的0-1规划模型,获得此类船舶安排的闸次;对其余船舶按照“先到先服务规则”,构建以闸次最少、闸室利用率最大为目标的多目标决策模型,获得不同船舶排布可行方案应该安排的频次。以位于江苏省干线航道上的某复线船闸某日24小时内过闸船舶的数据为例,计算结果表明:采用本文优化模型获得的优化方案与“经验编排方式”相比,两座船闸各节约2个闸次,两个船闸的平均闸室利用率分别提高了3.66和4.72个百分点。     

Polychloroprene rubbers used for adhesives: a small angle X-ray scattering preliminary investigation under stretching

Summary Three types of polychloroprene rubbers (Du Pont de Nemours Co. Neoprenes AD, WHV and W) used for adhesives and having different crystallization rates have been investigated.The mechanical properties of the Neoprenes samples were determined and the films were examined under stretching by SAXS for a preliminary investigation on their different superreticular order.

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Zusammenfassung Drei Typen von Polychloropren-Kautschuk mit verschiedener Kristallisationsgeschwindigkeit (Neoprene AD, WHV und W von Du Pont de Nemours), die als Klebemittel dienen, wurden als gedehnte Filme mechanisch und röntgenographisch (SAXS) untersucht. Sie zeigen Unterschiede in der Überstruktur.

     

On the configuration interaction method for singlet states

The direct CI method, which avoids explicit calculation of the Hamiltonian matrix, is presented in a new form. The method is linked with Davidson's algorithm for iterative evaluation of the ground state eigenvector. The viability of the method is indicated by the test calculations on water which are described.     

HPLC of antibiotics. 1. Streptolydigin and related compounds

Two new acyltetramic acids related to streptolydigin have been isolated from fermentations of Streptomyces lydicus. The principal members of this complex were resolved by TLC on silica gel. However, the methods of detection, permanganate spray or bioautography, were not suitable for both crude fermentation broths and purified extracts. Gas chromatography is unsuitable for the detection of either underivatized or silylated streptolydigins. High performance liquid chromatography (HPLC) particularly on triethylaminoethyl cellulose is rapid and sensitive and is the method of choice for the analysis of both crude and purified samples. Using high performance liquid chromatography, two components were detected in the complex, which are not observed using any of the other chromatographic procedures.