M. S. Tswett and the discovery of chromatography II: Completion of the development of chromatography (1903–1910)

Summary In this, the second part of our review we continue the discussion of the activities of M. S. Tswett related to the development of chromatography. We shall deal here with his activities in Warsaw from 1903 onwards, resulting in his fundamental twin papers of 1906 and his book of 1910, summarizing all his activities related to the investigation of plant pigments and to the development of chromatography. Finally, a few special questions related to Tswett's work shall be discussed.For Part I, seeChromatographia 35, 223 (1993). References are numbered through.     

Asymmetric synthesis of heteroorganic analogs of natural products. 6. (S)-α-amino-ω-phosphonocarboxylic acids

Alkylation, by -haloalkylphosphonates, of the Ni(II) complex of the Schiff base formed from glycine and (S)-2-N-(N¹-benzylprolyl)-o-aminobenzophenone has been used for the asymmetric synthesis of (S)-2-amino-4-phosphonobutyric and (S)-2-amino-5-phosphonovaleric acids.Institute of Bioorganic Chemistry and Oil Chemistry, Ukrainian Academy of Sciences, 250800 Kiev. A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 397–402, February, 1992.     

On the study by D.S.C. of the unexpected ice melting at 0°C of emulsified aqueous saline solutions

Firstly, the behavior of droplets (Φ ≈ 1μm) of aqueous saline solutions dispersed within an emulsifying medium and subjected to steady cooling and heating is described. Droplets undergo freezing around a temperature T¹(x) and partial ice melting and total salt melting at the eutectic temperature T_E. This melting is followed by progressive melting of the remaining ice which ceases when the equilibrium temperature (T_e(x)) ice ⇆ solution is reached. Between T_e and T¹ the droplets are undercooled. Secondly, the results obtained when water crystallization occurs versus time at a fixed temperature _C, such as T¹(x) < > _C < T_e(x) are reported. During heating following crystallization at Θ_C, an unusual ice melting at 0° and/or ice melting ending at T & >; T_e(x) is noticed on the thermogram obtained by differential scanning calorimetry of the emulsion. This shows that pure ice or at all events less concentrated solutions must be present within the emulsion. A possible mechanism of crystallization at Θ_C is proposed.     

SAR—The U.S. Regulatory Perspective

Abstract

Structure-Activity Relationships (SAR) have been used for over a decade by the U.S. EPA's Office of Pollution Prevention and Toxics (OPPT) in their new chemicals program. The development and use of SAR resulted from the need to make rapid risk-based decisions on thousands of new chemicals per year while seldom receiving data on chemical properties, potential exposures, or hazards to humans or organisms in the environment. Qualitative SAR and quantitative SAR methods (QSAR) have been used to fill some of these data gaps by estimating the potential properties and hazards of such chemicals. SAR has been used to assess chemical hazards, identify testing needs, and set priorities. Validation of these SAR assessment tools is an ongoing process.     

C–S Targeted Biodegradation of Dibenzothiophene by Stenotrophomonas sp. NISOC-04

Crude oil-contaminated soil samples were gathered across Khuzestan oilfields (National Iranian South Oil Company, NISOC) consequently experienced a screening procedure for isolating C-S targeted dibenzothiophene-biodegrading microorganisms with previously optimized techniques. Among the isolates, a bacterial strain was selected due to its capability of biodegrading dibenzothiophene in a C-S targeted manner in aqueous phases and medium mostly consisting of separately biphasic water-gasoline. The 16S rDNA of the isolate was amplified using eubacterial-specific primers and then sequenced. Based on sequence data analysis, the microorganism, designated NISOC-04, clustered most closely with the members of the genus Stenotrophomonas. Gas chromatography indicated that Stenotrophomonas sp. NISOC-04 utilizes 82% of starting 0.8 mM dibenzothiophene within a 48-h-long exponential growth phase. Growth curve analysis revealed the inability of Stenotrophomonas sp. NISOC-04 to utilize dibenzothiophene (DBT) as the exclusive carbon or carbon/sulfur source. Gibbs' assay showed no 2-hydroxy biphenyl accumulation, but HPLC confirmed the presence of 2-hydroxy biphenyl as the final product of DBT desulfurization. Under sulfur starvation, Stenotrophomonas sp. NISOC-04 produced a huge biomass with untraceable sulfur and utilized atmospheric insignificant sulfur levels.     

Synthesis of chiral ferrocenylazines. Negishi cross-coupling or S N H reactions?

Preparation of new hetaryl-containing planar chiral ferrocene by a nucleophilic substitution of hydrogen in azines was performed using a lithium derivative of (S)-ferrocenyl-p-tolylsulfoxide as s nucleophilic reagent     

A review of: “Handbook of Derivatives for Chromatography. K. Blau and G. S. King (editors). Heyden Publishers,London, Bellmawr,N.J., Rheine, 1977. xvi f 576 pages. Price £24.00: U.S.A. $48.0: DM 154.00.”

Abstract

Urban particulate matter, collected from Washington, DC and certified by the National Institute of Standards and Technology (NIST) as Standard Reference Material 1649, was extracted and fractionated into acid, base and neutral fractions. Each fraction was tested for biological activity using a microbial mutagenesis assay system. The organic acid fraction showed unexpectedly high mutagenic activity, and was subjected to chemical characterization studies. Following derivatization, analysis by GC/MS showed the presence of fatty acids, aromatic acids (including phenolic compounds), and a significant number of compounds that could not be identified from mass spectral compendia. Spectroscopic and elemental analysis data supported the characterization of the fraction as predominantly aromatic. Mass spectra from both GC/MS and direct probe analysis showed the presence of a chlorinated substance, subsequently identified as the fungicide Dichlorophen. The compound was shown to comprise over 50% of the mass of the organic acid fraction. A reference standard of Dichlorophen was not mutagenic. The presence of the fungicide in the NIST certified urban aerosol is, in all probability, due to artifactual processes. Attempts to concentrate the observed mutagenic activity by preparative chromatography and acid/base partition experiments were not successful.     

M. S. Tswett and the discovery of chromatography I: Early work (1899–1903)

Summary On the occasion of the 90th anniversary of the Warsaw lecture of M. S. Tswett representing the first report on the chromatographic technique, this two-part article outlines the evolution of the method. This part deals with Tswett's early work in 1899–1901 and his research in 1901–1903 leading to the lecture at Warsaw. The second part will deal with the fundamental twin papers of 1906, with his book of 1910, summarizing all his activities related to the investigation of plant pigments and to the development of chromatography, and with a few special questions related to Tswett's scientific activities in this field.Part II of this article will be published in the next month's issue ofChromatographia.     

N. S. Kurnakov’s contribution to coordination chemistry

N.S. Kurnakov’s most important works in coordination chemistry are overviewed. Special attention is given to Kurnakov’s dissertation “On Complex Metal Bases,” to his understanding of the structure of coordination compounds, to the mutual effects of ligands, and to the key ideas in coordination chemistry developed by Chugaev and Chernyaev’s school. Kurnakov’s role in the foundation of the Soviet platinum industry is pointed out.     

配位化学的先驱S.M. Jφrgensen

配位化学的先驱Ｓ．Ｍ．Ｊｒｇｅｎｓｅｎ大学化学化学史张清建（四川师范学院化学系南充６３７００２）今天的化学工作者，大都熟悉配位化学的奠基人ＡｌｆｒｅｄＷｅｒｎｅｒ的名字。然而，很少有人认识到，Ｗｅｒｎｅｒ崭新的具有革命意义的理论，是建立在Ｊｒｇｅ...     

Quality (r)evolution – guidelines and practical implementation of quality management: the U.S. perspective

 All clinical laboratories in the United States were required for the first time in 1992 to comply with universal minimum regulations: the Clinical Laboratory Improvement Amendments of 1988 (CLIA'88). The CLIA'88 regulations precipitated revolutionary and evolutionary changes based in both total quality management and continuous quality improvement principles. The regulations specify minimum requirements for personnel, quality control, and proficiency testing. Under quality assurance, the requirements are more individualized and allow laboratories to meet the needs of their customers while being in compliance with the regulations. Biannual inspection is integral to CLIA'88. However, laboratories can choose other federally approved, "deemed" professional organizations, with regulations equivalent to CLIA'88. Selection of one of these organizations allows for some flexibility in the application of the requirements, and eliminates having federal CLIA'88 inspectors perform the inspection. Since CLIA's inception in 1992, inspectors have noted a decline in the number of deficiencies cited. An improved level of proficiency testing performance also indicates that better quality test results are being provided to clinicians. The quality evolution and revolution will continue in the United States, and a major impetus will be health care reform's mandate to reduce cost. Received: 13 December 1995 Accepted: January 1996     

Synthesis of α-Oxoketene CyclicO,S and S,S Acetals

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Asymmetric synthesis of heteroorganic analogs of natural compounds. 3. General preparative method of diastereo- and enantioselective synthesis of fluorine-containing 2(R), 3(S)-Β-phenylserines

The diastereo- and enantioselective synthesis of the previously unknown 2(R), 3(S)--phenylserines containing fluorine atoms, the O-CHF₂-, O-CF₃-, and CF₃ groups in the benzene ring, was carried out by alkylation of a Ni(II) complex of a Schiff base of glycine with (S)-2-N-(N'-benzylprolyl)aminobenzophenone by fluorine-substituted benzaldehydes. The factors influencing the stereochemical result of the reactions studied are not the steric characteristics of the substituents in benzaldehydes, but their electronic nature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1166–1175, May, 1991.