Determination of cell asymmetry in temperature-modulated DSC

The quality of measurement of heat capacity by differential scanning calorimetry (DSC) is based on the symmetry of the twin calorimeters. This symmetry is of particular importance for the temperature-modulated DSC (TMDSC) since positive and negative deviations from symmetry cannot be distinguished in the most popular analysis methods. Three different DSC instruments capable of modulation have been calibrated for asymmetry using standard non-modulated measurements and a simple method is described that avoids potentially large errors when using the reversing heat capacity as the measured quantity. It consists of overcompensating the temperature-dependent asymmetry by increasing the mass of the sample pan.On leave from Toray Industries, Inc., Otsu, Shiga 520, JapanOn leave from Toray Research Center, Inc., Otsu, Shiga 520, JapanThis work was supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, U. S. Department of Energy at Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the U. S. Department of Energy, under contract number DE-AC0S-96OR22464. Support for instrumentation came from TA Instruments, Inc. and Mettler-Toledo, Research support was also given by ICI Painls, and Toray Industries, Inc.     

Cell asymmetry correction for temperature modulated differential scanning calorimetry

The quality of measurement of heat capacity by differential scanning calorimetry (DSC) is based on strict symmetry of the twin calorimeter. This symmetry is of particular importance for temperature-modulated DSC (TMDSC) since positive and negative deviations from symmetry cannot be distinguished in the most popular analysis methods. The heat capacities for sapphire-filled and empty aluminum calorimeters (pans) under designed cell imbalance caused by different pan-masses were measured. In addition, the positive and negative signs of asymmetry have been explored by analyzing the phase-shift between temperature and heat flow for sapphire and empty runs. The phase shifts change by more than 180° depending on the sign of the asymmetry. Once the sign of asymmetry is determined, the asymmetry correction for temperature-modulated DSC can be made.On leave from Toray Research Center, Inc., Otsu, Shiga 520, JapanThis work was supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy at Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the U.S. Department of Energy, under contract number DE-AC05-960R22464.     

Interactive microcomputer conformation-analysis suite

Bogatskii Physicochemical Institute, Ukrainian Academy of Sciences. Division of the All-Union Research and Development Institute for Electrical Insulating Materials and Foil-Coated Dielectrics. Translated from Zhurnal Strukturnoi Khimii, Vol. 29, No. 1, pp. 172–174, January–February, 1988.     

Thiol derivatives of arylnaphthylmethane as novel anti-osteoporotic agents

(Mercaptophenyl)naphthylmethane derivatives were synthesized as novel estrogen receptor binding ligands. [4-(Methylsulfonyl)phenyl](naphth-1-yl)ketone shows a very promising activity towards osteoporosis. Correspondence: Sangita, Medicinal and Process Chemistry Division, Central Drug Research Institute, Lucknow 226001, India.     

A sequential multielement separation scheme for determination of As,Mn, Mo,Cu and Zn in human milk by neutron activation analysis

A simple separation scheme for the analysis of As, Mn, Mo, Cu and Zn using neutron activation is described. It has been checked using three standard reference materials, A-11 milk powder (IAEA) and bovine liver and orchard leaves (USNBS) and found to give acceptable results. This scheme was applied for determination of these trace elements in mature human milk samples. The concentrations of As, Mn, Mo, Cu in samples obtained from two socio-economic groups—low and middle incomes—were not significantly different. However, Zn levels in samples obtained from the poor income group were significantly lower than in those obtained from the other group. Work carried out under Research Contract No. 2598/RB of International Atomic Energy, Vienna. Health Physics Division. Analytical Chemistry Division.     

Modulated differential scanning calorimetry in the glass transition region

Temperature-modulated calorimetry (TMC) allows the experimental evaluation of the kinetic parameters of the glass transition from quasi-isothermal experiments. In this paper, model calculations based on experimental data are presented for the total and reversing apparent heat capacities on heating and cooling through the glass transition region as a function of heating rate and modulation frequency for the modulated differential scanning calorimeter (MDSC). Amorphous poly(ethylene terephthalate) (PET) is used as the example polymer and a simple first-order kinetics is fitted to the data. The total heat flow carries the hysteresis information (enthalpy relaxation, thermal history) and indications of changes in modulation frequency due to the glass transition. The reversing heat flow permits the assessment of the first and higher harmonics of the apparent heat capacities. The computations are carried out by numerical integrations with up to 5000 steps. Comparisons of the calculations with experiments are possible. As one moves further from equilibrium, i.e. the liquid state, cooperative kinetics must be used to match model and experiment.On leave from Toray Industries, Inc., Otsu, Shiga 520, Japan.This work was supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, U. S. Department of Energy at Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the U. S. Department of Energy, under contract number DE-AC05-96OR22464. Support for instrumentation came from TA Instruments, Inc. Research support was also given by ICI Paints, and Toray Industries, Inc.     

Synthesis of benzoxazole sulfanilamide derivatives

A number of hitherto undescribed 2-(p-aminobenzenesulfamide) benzoxazoles are prepared by treating 2-aminobenzoxazole or its 6-substituted compounds with p-carbomethoxyaminobenzenesulfochloride or p-acetylaminobenzenesulfochloride, followed by alkaline hydrolysis. A similar reaction with 6-amino-2-hydroxy- and 2-mercaptobenzoxazoles gives 6-(p-aminobenzenesulfamido)-2-hydroxy- and 2-mercaptobenzoxazoles.The work was done by E. N. Padeiska of the Chemotherapy Division of VNIKhFI (All-Union Pharmaceutical Chemistry Research Institute).     

Melting of indium by temperature-modulated differential scanning calorimetry

The melting and crystallization of a sharply melting standard has been explored for the calibration of temperature-modulated differential scanning calorimetry, TMDSC. Modulated temperature and heat flow have been followed during melting and crystallization of indium. It is observed that indium does not supercool as long as crystal nuclei remain in the sample when analyzing quasi-isothermally with a small modulation amplitude. For standard differential scanning calorimetry, DSC, the melting and crystallization temperatures of indium are sufficiently different not to permit its use for calibration on cooling, unless special analysis modes are applied. For TMDSC with an underlying heating rate of 0.2 K min^–1 and a modulation amplitude of 0.5–1.5 K at periods of 30–90 s, the extrapolated onsets of melting and freezing were within 0.1 K of the known melting temperature of indium. Further work is needed to separate the effects originating from loss of steady state between sample and sensor on the one hand and from supercooling on the other.On leave from Toray Research Center, Inc., Otsu, Shiga 520, Japan.This work was supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy at Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the U.S. Department of Energy, under contract number DEACOS-960R22464. Support for instrumentation came from TA Instruments, Inc. and Mettler-Toledo Inc. Research support was also given by ICI Paints.     

Triton-B catalyzed,efficient one-pot synthesis of dithiocarbazates

A quick and efficient, one-pot synthesis of dithiocarbazates was accomplished in high yields by the reaction of various primary, secondary, and tert. alkyl halides with a variety of substituted hydrazines using the benzyl-trimethylammonium hydroxide (Triton-B)/CS₂ system. The reaction conditions are mild with simpler work-up procedures than the reported methods. Correspondence: Devdutt Chaturvedi, Medicinal and Process Chemistry Division, Central Drug Research Institute, Lucknow-226001, U.P., India.     

Multiple melting peak analysis with gel-spun ultra-high molar mass polyethylene

The multiple melting peaks observed on differential scanning calorimetry (DSC) of ultrahigh molar-mass polyethylene fibers (UHMMPE) are analyzed as a function of sample mass. Using modern DSC capable of recognizing single fibers of microgram size, it is shown that the multiple peaks are in part or completely due to sample packing. Loosely packed fibers fill the entire volume of the pan with rather large thermal resistance to heat flow. On melting, the fibers contract and flow to collect ultimately at the bottom of the pan. This process seems to be able to cause an artifact of multistage melting dependent on the properties of the fibers. A method is proposed to greatly reduce, or even eliminate, errors of this type. The crucial elements of the analysis of melting behavior and melting temperature are decreasing the sample size and packing the individual fibers in a proper geometry, or to introduce inert media to enhance heat transport.This work was supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, US Department of Energy at Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the US Department of Energy, under contract number DE-ACOS-96OR22464. Support for instrumentation came from TA Instruments, Inc. and Mettler-Toledo, research support was also given by ICI Paints.     

A neutron induced prompt gamma-ray spectroscopy system using a 252Cf neutron source for quantitative analysis of aqueous samples

A neutron induced prompt γ -ray spectrometry (NIPS) facility has been developed at the Nuclear Chemistry Research Division, of the Korea Atomic Energy Research Institute (KAERI) with the aim of analyzing the major components of various elements in aqueous samples. The facility is equipped with a ²⁵²Cf neutron source and a γ-γ coincidence setup with two n-type coaxial HPGe detectors based on NIM spectrometric modules in association with data acquisition and spectral analysis systems. The development of the system, its set-up and the calibration of detection efficiency up to 8 MeV using a set of radionuclides and the (n,γ) reactions of chlorine are described in the paper. This revised version was published online in July 2006 with corrections to the Cover Date.     

Techno-commercial aspects of food irradiation in India

Research and development work has been carried out at Food Technology Division of Bhabha Atomic Research Center for more than past fifty years. After establishing potential commercial applications, a lot of time and efforts were spent on proving the wholesomeness and nutritional adequacy of irradiated foods. The first approval from health authorities came in 1994 for processing potato, onion and spices. Additional commodities were approved in 1998 and 2001, bringing the list of commodities to more than 20. Two technology demonstration plants were set up by the government, one for high dose applications like microbial decontamination of spices and dry vegetables in 2000, and another for low dose applications, like sprout inhibition and insect disinfestation, in 2003. In 2004, irradiation was approved as a quarantine measure. This enabled export of mango to USA after a gap of 18 years in 2007. More than a dozen plants have now been set up by private entrepreneurs in the country.     

An efficient method for the synthesis of spiro and fused N-heterocyclic phosphor esters. Reactions of triketoindan-2-oxime with α-phosphonyl carbanions

Treatment of triketoindan-2-oxime with α-phosphonyl carbanions in sodium ethanolate solution at reflux temperature led to a number of the corresponding substituted spiroisooxazole-, fused 1,3-oxazole, and 1,4-oxazine phosphor esters in moderate to high yields. Mechanisms for the formation of five- and six-membered rings are provided. A comparison of Wittig-Horner and Wittig reagent counterparts in reactions with the oxime is discussed. The various biological properties of selected examples of the synthesized products were studied. Correspondence: Wafaa M. Abdou, Chemical Industries Division, National Research Center, Elbohouth St., D-12622 Dokki, Cairo, Egypt.     

Single run heat capacity measurements

An outline for the data analysis of single-run heat capacity measurments by dual sample DSC is presented with the following features: 1. Heat flow correction by subtracting the contribution due to the sample pan, including correction for mismatched pan masses. 2. Heat flow and temperature correction with a nonlinear temperature calibration, temperature lag correction, and heating rate correction. 3. Calculation of the cell constants for both cell positions and evaluation of the asymmetry factor between cell positions A and B. 4. Heat capacity calibration and calculation with slope and asymmetry correction. 5. Calculation of heat capacity for multiple runs. 6. Data curve fitting for heat capacity.This work was supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 8818412 and the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy, under Contract DE-AC05-84OR21400 with Martin Marietta Energy Systems, Inc. Thanks are given to TA Instruments, Inc. (New Castle, DE) for providing the commercial heat capacity software and helping with the acquisition of the calorimeter.     

Stabilization of divalent californium in crystalline strontium tetraborate

The divalent oxidation state of californium (Cf) has been stabilized in crystalline SrB₄O₇. The ability to generate this less-stable oxidation state in an oxide matrix is significant. Factors promoting this stabilization have been determined. Access to this divalent state and those of many other lanthanide and actinide elements via a rather straightforward laboratory procedure now facilitates their study and characterization.Research sponsored by the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department of Energy under grant DE-FG05-88ER13865 to the University of Tennessee, Knoxville and contract DE-AC05-84OR21400 with Martin Marietta Energy Systems, Inc.     

On the contribution of A. C. Hurley to theoretical chemistry

Andrew Crowther Hurley was born in Melbourne, Australia, on 11 July 1926 and received his early education at Melbourne Church of England Grammar School. He graduated from the University of Melbourne with high honors in mathematics and natural philosophy and, in 1949, was awarded his M.A. with first class honors in the school of mathematics for his thesis “The Irreducible Crystal Classes in Four Dimensions,” his supervisor being Dr. Hans Schwerdtfeger. From 1950–1952 he was a member of Trinity College, Cambridge, and was awarded a Ph.D. for his research in theoretical chemistry under Sir John Lennard-Jones. In 1953 he returned to Melbourne and joined what was to become the Division of Chemical Physics of the Commonwealth Scientific and Industrial Research Organization (CSIRO). The award of a fellowship by Trinity College enabled him to spend two more years, 1954–1956, in the Theoretical Chemistry Department of the University of Cambridge, and this was followed by a year with Professor J.C. Slater's solid state and molecular theory group at the Massachusetts Institute of Technology. In 1957 Andrew again returned to the Division of Chemical Physics in Melbourne, where he has remained, except for the academic year 1962–1963, when he was Visiting Professor in Theoretical Chemistry at Iowa State University.     

Glossar von Begriffen der Kombinatorischen Chemie

Die Übersetzung basiert auf dem „Glossary of Terms used in Combinatorial Chemistry“ der Commission on Nomenclature and Terminology der Medicinal Chemistry Section der Chemistry and Human Health Division der International Union of Pure and Applied Chemistry, veröffentlicht in Pure Appl. Chem. 1999 , 71, 2349–2365. Das Original wurde von D. Maclean (Affymax Research Institute, USA), J. J. Baldwin (Pharmacopeia, Inc., USA), V. T. Ivanov (Shemyakin und Ovchinnikov Institut für Bioorganische Chemie, Moskau, Russland), Y. Kato (Teijin Institute for Bio‐Medical Research, Tokio, Japan), A. Shaw (Astra‐Zeneca Ltd., Großbritannien), P. Schneider (Novartis, Basel, Schweiz) und E. M. Gordon (Sunesis, Inc., USA) für die Veröffentlichung vorbereitet.     

Application of ternary and multicomponent complexes to spectrophotometric and spectrofluorimetric analysis of inorganics

The application of ternary and multicomponent complexes in spectrophotometric and spectrofluorimetric determination of trace elements is reviewed. Newer types of colour systems employing mixed ligand, surfactant sensitized, ion-association, flotation, derivative and FIA systems are described. Separate sections are devoted to advances in both spectrophotometric and spectrofluorimetric determination of individual elements. Future trends in spectrophotometric and spectrofluorimetric analysis are discussed.     

光度分析

本文是《分析试验室》定期评述中“光度分析”的第六篇文章，评述了１９９４．７～１９９６．６期间我国光度分析的概况，内容包括：学术会议，专著，标准，综述，新试业色体系，动力学光度法，萃取，浮选和离心光度法，双波长光度法，其他新光度法，以及这两年我国学者在国际杂志上发表的有关光度分析论文目录，引用文献１３７１篇。     

红外分光测油仪性能评价方法的探讨

针对非色散式红外测油仪和红外分光测油仪定性分析、定量分析的区别,阐述了制定我国红外分光测油仪性能评价方法标准的必要性,并提出了一套完整的红外分光测油仪性能评价方法。