New light on an old story: formation of melam during thermal condensation of melamine

We report on the existence and formation of the carbon nitride precursor melam (H(2)N)(2)(C(3)N(3))NH(C(3)N(3))(NH(2))(2), thereby clarifying one of the last unresolved issues posed by the complex thermal condensation of melamine C(3)N(3)(NH(2))(3). Experimental proof is put forward that melam is a direct condensation product of melamine, but can be detected only in small amounts under special reaction conditions owing to its rapid transformation into melem. The coexistence of melamine and melem during thermal condensation yields two adduct phases with distinct compositions [C(3)N(3)(NH(2))(3)](2)[C(6)N(7)(NH(2))(3)] and [C(3)N(3)(NH(2))(3)][C(6)N(7)(NH(2))(3)](2). They may be considered as co-crystallizates of melamine and melem and can be isolated as intermediates between 590 and 650 K prior to the formation of single-phase melem C(6)N(7)(NH(2))(3). Melam (C2/c, a=1811.0(4), b=1086.7(2), c=1398.4(3) pm, beta=96.31(3) degrees, V=2735.3(9)x10(6) pm(3), T=130 K) adopts a ditriazinylamine-type structure with a twisted conformation about the bridging NH moiety and transforms into melem around 640 K. Two compounds deriving from melam have been synthesized by solution and solid-state reactions. The salt melamium diperchlorate C(6)N(11)H(11)(ClO(4))(2).2H(2)O (C2/c, a=1747.8(4), b=1148.2(2), c=993.6(2) pm, beta=118.79(3) degrees, V=1747.4(6)x10(6) pm(3), T=130 K) crystallizes as a dihydrate and exhibits a doubly protonated, planar melam core. In the neutral complex Zn[C(6)N(11)H(9)]Cl(2) (P2(1)/c, a=743.00(15), b=2233.2(5), c=762.5(2) pm, beta=99.86(3) degrees, V=1246.5(4)x10(6) pm(3), T=200 K), melam acts as a symmetrically bent bidentate ligand, which is coordinated to the Lewis acid Zn-site through two ring nitrogen atoms.     

Phase equilibria in Pr0.7Cd0.3MnO3 and Pr0.7Bi0.3MnO3

A solid state synthesis and phase transitions of solid solutions Pr_0.7Cd_0.3MnO₃ (PCM) and Pr_0.7Bi_0.3MnO₃ (PBM) have been studied within 20–1150°C temperature range. At room temperature, PCM and PBM phases are rhombic within Pnma space group. At high temperatures, Mn-O bonds in PCM are highly anisotropic, the anisotropy becoming insignificant at low temperatures.     

Emanation Thermal Analysis: Ready to fulfill the future needs of materials characterization

The paper reviews the actual state of the development and use of emanation thermal analysis (ETA). Examples of its recent applications are presented. The advantages of ETA in the microstructure characterization of materials under in situ conditions of their heat treatment are outlined.This revised version was published online in November 2005 with corrections to the Cover Date.     

New developments in clinical analysis

Summary The revolutionary development of clinical chemistry finds expression in the fact, that the total number of analyses doubles nearly every five years. The only solution of this problem is automation. Some examples of new developments in the fields of enzyme, protein and amino-acid chemistry are given. These few examples can be extended almost ad infinitum. It is clear however, that analytical chemical technique development goes hand in hand with modern instrumentation development. A short survey of some of the major points concerning spectrophotometry, gas chromatography and radioactive isotopes is given. Attention is finally drawn to a very important aspect of these new developments, which may easily be overlooked, namely standardization. A survey is given of the Dutch work on the standardization of haemoglobinometry (HiCN-method).

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Zusammenfassung Die revolutionäre Entwicklung der klinischen Chemie wird schon dadurch klar ersichtlich, daß die Gesamtzahl der klinisch-chemischen Bestimmungen sich fast alle fünf Jahre auf das Zweifache steigert. Die einzige Lösung dieses Problems liegt in der Automatisierung. Einige Beispiele neuer Entwicklungen werden gegeben auf dem Gebiet der Enzym-, Eiweiß- und Aminosäurechemie. Diese wenigen Beispiele können ad infinitum ergänzt werden. Es ist jedoch klar, daß die Fortschritte in der analytischen Chemie unlöslich mit der Entwicklung neuer Apparaturen verbunden sind. Eine kurze Zusammenfassung dieser Entwicklung auf dem Gebiete der Spektrophotometrie, der Gaschromatographie und der radioaktiven Isotopenanalyse im klinisch-chemischen Laboratorium wird gegeben.Zum Schluß wird der Standardisierung klinisch-chemischer Bestimmungen Aufmerksamkeit gewidmet. Die Standardisierung nimmt im Rahmen der neuesten Entwicklungen eine hervorragende Stelle ein. Eine Übersicht der niederländischen Arbeit über die Standardisierung der Hämoglobinometrie, (HiCN-Methode), wird gegeben.

     

Preparative solid state chemistry. Recent developments

A survey of recent developments in preparative solid state chemistry shows that, with a knowledge of structural chemistry and reactivity patterns of solids, it is possible to synthesize a variety of new solids possessing novel structures. A distinction is made between synthesis ofnew solids and synthesis of solids bynew methods. Three new routes to solid state synthesis are recognized: the precursor method, and topochemical methods involving redox and ion-exchange reactions. The low-temperature topochemical methods enable synthesis of metastable phases that are inaccessible by the high temperature route. Several illustrative examples of solid state synthesis from the recent literature are presented.     

New trends in methodological developments in clinical chemistry

Many new techniques have been introduced in clinical chemistry. Three important new methodologies are dry chemistry, gen technology and biosensors. Solid-phase chemistry systems. The two most common solid-phase systems are the Kodak-Ektachem and the Boehringer Mannheim Reflotron. The first one is working with serum and the second one mainly with whole blood. The determination of urea and the determination of the activity of AST (GOT) will be described. The greatest problems of these systems are the quality control of the analysis and the interferences by endogenous and exogenous substances. Analysis with the aid of gen technology. The major diagnostic applications of gen technology in human disease is the detection of genetic disorders and the tumor diagnosis. The beta-thalassemia will be the example for genetic disorders and the chronic myeloid leukemia (CML) for diagnosis of a tumor. Thalassemias are a group of inherited disorders caused by the defective or absent outpout of one of the globin chains of the Hb tetramere. The CML is an example of a specific translocation of a small region of chromosome 9 bearing the abl-oncogene to chromosome 22. Biosensors in biochemical analysis. Biosensors are analytical devices that respond selectively to analytes in an appropriate sample and convert their concentration into an electrical signal. As examples an in-vivo ferrocene-mediated glucose sensor and the determination of the isoenzyme LDH5 based on an antigene-antibody reaction are described.     

New developments in the symmetry-adapted algorithm of the Polarizable Continuum Model

We present recent developments in the symmetry implementation of the Polarizable Continuum Model (PCM). The structure of the matrix, which defines the PCM solvent response, is examined, and we demonstrate how this matrix can be transformed to a block diagonal form where each block belongs to different irreducible representations of the molecular point group. This development is especially important at the Multi-configurational Self-Consistent Field (MCSCF) level where symmetry is needed to avoid problems with symmetry breaking in the wave function and facilitate the optimization of electronic excited states. Moreover, although only the totally symmetric part of the solvent interaction is needed for energy calculations, in response or perturbation theory calculations of molecular properties, other irreps play an important role and the classification of solvent interaction terms by irrep is, therefore, desirable. In addition, the use of symmetry reduces the computational cost. The implementation presented here is illustrated with a series of calculations of absorption and emission processes in solution on the diazines pyrazine, pyrimidine, and pyridazine. These calculations allow us to illustrate both formal aspects of the implementation such as the choice of active spaces based on orbital symmetry as well as practical aspects such as the speed-up of the calculation.     

固态有机反应新进展

总结了一些典型的固态有机反应。由于固态反应的特性，多数固态有机反应表现出较溶液中更高的反应效率和更好的选择性，在某些情况下，利用光活性主体与反应物形成包结物，可实现对映选择性的不对称固态合成。     

Crystal Structures and Phase‐Transition Dynamics of Cobaltocenium Salts with Bis(perfluoroalkylsulfonyl)amide Anions: Remarkable Odd–Even Effect of the Fluorocarbon Chains in the Anion

Crystal structures and thermal properties of cobaltocenium salts with bis(perfluoroalkylsulfonyl)amide (C_nF_2n+1SO₂)₂N anions [n=0 ( 1 ), 1 ( 1 a ), 2 ( 1 b ), 3 ( 1 c ), and 4 ( 1 d )] and the 1,1,2,2,3,3‐hexafluoropropane‐1,3‐disulfonylamide anion ( 2 ) were investigated. In these solids, the cations are surrounded by four anions around their C₅ axis, and stacking of these local structures forms two kinds of assembled structures. In the salts with even n ( 1 , 1 b , and 1 d ), the cation and anion are arranged alternately to form mixed‐stack columns in the crystal. In contrast, in the salts with odd n ( 1 a and 1 c ), the cations and anions independently form segregated‐stack columns. An odd–even effect was also observed in the sum of the phase‐change entropies from crystal to melt. All of the salts exhibited phase transitions in the solid state. The phase transitions to the lowest‐temperature phase in 1 , 1 a , and 2 are accompanied by order–disorder of the anions and symmetry lowering of the space group, which results in the formation of an ion pair. Solid‐state ¹³C NMR measurements on 1 a and 1 b revealed enhanced molecular motions of the cation in the higher‐temperature phases.     

New developments in the field of reactive acrylic adhesives and sealing materials

The influence of oligomeric base on the properties of acrylic adhesives and sealants cured by radical mechanism is studied. New anaerobic materials on the basis of oligourethane(meth)acrylates (OUMs) are developed. It is shown that, by adjusting the OUM nature, it is possible to increase the heat and moisture stability of adhesive compositions. As a result of these works, UV-cured adhesive compositions, heat-cured adhesive for bonding untreated aluminum, and two-part adhesive compounds cured at both positive and negative temperatures are developed.     

New Technology for Solid-state Polymerization of Polymers: Polyethylene terephthalate–Solid-state Polyaddition

This article introduces the new M&G technology for Solid state polyaddition (SSPA) of polyethylene terephthalate (PET). The new SSPA is characterized by the following: (1) It is based on a novel chemical process, SSPA. (2) It is suitable for high-performance polyesters. (3) It enables separate control of many different key properties of the polyester (molecular weight, rheology, crystallinity, etc.). This intrinsic flexibility has already been exploited to produce tailor-made polyesters suitable for most important applications in packaging and related fields. It is also a powerful tool for the upgrading of recycled PET. The SSPA reaction has a much faster kinetic than the standard solid-state upgrading process so that accordingly the intrinsic viscosity (I.V.) built up in the solid state is much faster than that of solid-state polycondensation. This raises the possibility of solid-state upgrading at lower temperatures, where standard solid-state polycondensation reactions are barely noticeable. The accelerating reactions used in this process could be utilized to de-bottleneck the existing production plants in order to attain greater productivity, more flexibility, lower costs and higher quality. © 1997 John Wiley & Sons, Ltd.     

A unified theory for the kinetic analysis of solid state reactions under any thermal pathway

The Ozawa concept of generalized time has been used for developing master plots for the different kinetic models describing solid state reactions. These plots can be indistinctly used for analysing isothermal or non-isothermal experimental data. It is demonstrated that it is not possible to discriminate the kinetic model from a single non-isothermal curve without a previous knowledge of the activation energy. However, it has been shown that the ln [(da/dt)/f(a)] data taken from a set of DTG curves obtained at different heating rates lie on a single straight line when represented as a function of 1/T only if the kinetic model really obeyed by the reaction is considered. Moreover, the true values of E and A are obtained from the slope and the intercept of this straight line. This revised version was published online in July 2006 with corrections to the Cover Date.     

New developments in trace element analysis in the life sciences

Summary In the analysis of trace elements in biological materials it has become more and more apparent that there is often a need not only to determine the levels of the elements in the whole sample but also to measure the element contents in fractions of the materials, such as certain types of cells, subcellular components and molecules. Furthermore, it is sometimes necessary to relate the elemental data to relevant biological and biochemical parameters as there is otherwise a danger that wrong conclusions may be drawn. In this paper these trends in trace element analysis are described with the help of examples and the problems which can occur in the various steps of sampling and sample preparation are discussed.

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Neue Entwicklungen bei der Spurenelementanalyse in den Biowissenschaften

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Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

New developments in theory of fast electron scattering in solids: Applications to microbeam analysis

The study of fast electron interaction with solids in the energy range from 100 eV to several tens of keV is prompted by quickly developing microbeam analysis techniques such as electron probe microanalysis, scanning electron microscopy, electron energy loss spectroscopy and so on. It turned out that for random solids the electron transport problem might be solved on the basis of the generalized radiative field similarity principle. The latter states that the exact differential elastic cross section in the kinetic equation may be replaced by an approximate one provided the conditions of radiative field similarity are fulfilled. Application of the generalized similarity principle to electron scattering in solids has revealed many interesting features of electron transport. Easy to use and effective formulae have been obtained for the angular and energy distribution of electrons leaving a target, total yields of characteristic photons and slow electrons escaping from a sample bombarded by fast primaries, escape probability of Auger electrons as a function of depth etc. The analytical results have been compared with Monte Carlo calculations and experiments in a broad range of electron energies and scattering properties of solids and good agreement has been observed.     

Solid State Analysis with the New Leipzig High-Energy Ion Nanoprobe

 The high-energy ion nanoprobe LIPSION at the University of Leipzig has been operational since October 1998. The ultrastable single ended 3.5 MV SINLETRON^TM accelerator supplies the H⁺ or He⁺ ion beam. A magnetic scanning system moves the focused beam across the sample. At present, a resolution of 150 nm in the low current mode and 300 nm at 5 pA could be achieved. The UHV grade experimental chamber is equipped with electron-, energy dispersive X-ray-, and particle detectors. They can be used simultaneously to analyse the sample by means of PIXE (particle induced X-ray emission), RBS (Rutherford backscattering) and in the case of thin samples STIM (scanning transmission ion microscopy). A goniometer allows the application of channeling measurements in single crystals in combination with these methods. The detection limits depend on the elements to be analysed and range from (1000⋯1) μg/g relative and (1⋯0.01) pg absolute. The analysis is nondestructive, but the sample has to be vacuum resistant. Applications of the nanoprobe in the field of semiconductor research, biomedicine, and archaeology will be described.     

Recent developments in the field of oxa-Michael reactions

Oxa-Michael reactions, i.e. addition reactions of oxygen nucleophiles to conjugated systems, have traditionally received much less attention from the scientific community compared to the addition of carbon nucleophiles to conjugate acceptor systems (Michael reaction). This was mainly due to lack of reactivity and selectivity of these reactions. Within the last few years however, there has been a remarkable increase in publications focussing on method development as well as applications to natural product synthesis. This tutorial review discusses instructive examples that have substantially broadened the scope of oxa-Michael reactions.