Marks of permutation groups and isomer enumeration

The concept of the mark of a permutation group is at least eighty years old, but comparatively little use has been made of it until recently. Redfield rediscovered marks in the 1930's, but his work was not published until 1984. He used them to count group reduced distributions according to their symmetry groups. In this paper, the Mark Version of Redfield's Superposition Theorem is used to count isomers. The method is compared with a related method used by Hässelbarth, Mead and Fujita.     

Direct Synthesis of Carbamoyl Fluorides by CO2 Deoxyfluorination

Herein, a new concept for the direct synthesis of carbamoyl fluoride derivatives is disclosed. The developed method makes use of CO₂ as an inexpensive and abundant C₁ source; a variety of amines were successfully converted in the presence of a deoxyfluorinating reagent. The corresponding products were often obtained in excellent yields under mild reaction conditions (1 atm and room temperature). The reaction was easily scaled up, demonstrating the efficiency of the developed process.     

Chiral separation of racemic mandelic acids by use of an ionic liquid-mediated imprinted monolith with a metal ion as self-assembly pivot

A new chiral stationary phase based on molecularly imprinted polymers (MIP) was prepared in ionic liquid by use of the metal pivot concept. Imprinted monoliths were synthesized by use of a mixture of R-mandelic acid (template), 4-vinylpyridine, ethylene glycol dimethacrylate, and several metal ions as pivot between the template and functional monomer. A ternary mixture of dimethyl sulfoxide–dimethylformamide–[BMIM]BF₄ containing metal ions was used as the porogenic system. Separation of the enantiomers of rac-mandelic acid was successfully achieved on the MIP thus obtained, with resolution of 1.87, whereas no enantiomer separation was observed on the imprinted monolithic column in the absence of metal ions. The effects of polymerization conditions, including the nature of the metal ion and the ratios of template to metal ions and template to functional monomer, on the chiral separation of mandelic acid were investigated. The results reveal that use of metal ions as a pivot, in combination with ionic liquid, is an effective method for preparation of a highly efficient MIP stationary phase for chiral separation.

An alternative bioreactor concept for application of an isolated oxidoreductase for asymmetric ketone reduction

In this paper an isolated NADH dependent ketone reductase has been used to synthesise (S)-6-bromo-β-tetralol from 6-bromo-β-tetralone, together with commercially available formate dehydrogenase (FDH) as a recycle enzyme to produce preparative quantities of the product. Furthermore, initial experiments indicate potential for an alternative bioreactor concept via the use of a resin (XAD L-323) to bind the product (and residual substrate) of the conversion rather than the cofactors or enzymes, thus allowing a new method of recycle, potentially overcoming existing problems.     

“On-water” catalyst-free,one-pot synthesis of quaternary centered and spiro-tetrahydrothiophene-barbiturate hybrids

A green and efficient method have been developed for the synthesis of quaternary centered and spiro-barbiturate-tetrahydrothiophene hybrids via Knoevenagel condensation,1,4-thia-Michael and intramolecular Aldol reactions using “on water” concept under catalyst-free conditions. Systematic studies were carried out to find the role of the water and total reaction concentration (0.086 M) to promote the reaction in two steps (one-pot). The use of water as a reaction medium, catalyst-free conditions, broad substrate scope, one-pot approach for the creation of quaternary centered and spiro molecules are the advantages of this method.     

Efficient Amide Bond Formation through a Rapid and Strong Activation of Carboxylic Acids in a Microflow Reactor

The development of highly efficient amide bond forming methods which are devoid of side reactions, including epimerization, is important, and such a method is described herein and is based on the concept of rapid and strong activation of carboxylic acids. Various carboxylic acids are rapidly (0.5 s) converted into highly active species, derived from the inexpensive and less‐toxic solid triphosgene, and then rapidly (4.3 s) reacted with various amines to afford the desired peptides in high yields (74 %–quant.) without significant epimerization (≤3 %). Our process can be carried out at ambient temperature, and only CO₂ and HCl salts of diisopropylethyl amine are generated. In the long history of peptide synthesis, a significant number of active coupling reagents have been abandoned because the highly active electrophilic species generated are usually susceptible to side reactions such as epimerization. The concept presented herein should renew interest in the use of these reagents.     

成果导向教育在物理化学教学中的应用

In this paper, we take the instruction of additional pressure and vapor pressure under the curved surface as an example and use the advanced concept of outcome-oriented education as a guide. We analyzed the current situation of traditional classroom teaching, and classified the teaching objectives by using the Bloom classification method, finally reformed the teaching practice process.     

Measurement uncertainty – a reliable concept in food analysis and for the use of recovery data?

 Steps which are taken to implement the concept of measurement uncertainty in analytical chemical laboratories should take full account of existing internationally agreed protocols for analytical quality assurance and reflect the needs of particular analytical sectors. For the food sector this may mean that for official purposes the use of the term measurement uncertainty is replaced by the term measurement reliability and that a quantitative estimation of this is made based on existing collaborative trial data. In many analytical sectors, the differing strategies currently followed for the determination and use of recovery information are an important cause of the non-comparability of analytical results. Guidelines which are being prepared for the estimation and use of recovery information in analytical measurement may provide a more unified approach which includes measurement uncertainty as a key concept in the use of recovery data. Received: 4 November 1997 · Accepted: 3 February 1998     

Investigation of polyelectrolyte adsorption by means of a novel concept based upon the use of model surfaces and model polyelectrolytes

A concept to study the influence of molecular parameters in the adsorption of polyelectrolytes is presented. Characteristic for this approach is the use of model surfaces and model polyelectrolytes. The properties of both the surfaces and polyelectrolytes can be varied in a well defined way and over a broad range. First experiments show that the method is able to give structural information about the adsorbed polyelectrolytes. The method is very sensitive, adsorption experiments with polyelectrolyte concentrations in the region of micromoles per litre are possible.     

Evaluation of canonical and microcanonical nonadiabatic reaction rate constants by using the Zhu-Nakamura formulas

We consider a problem of calculating both thermal and microcanonical rate constants for nonadiabatic chemical reactions. Instead of using the conventional transition state theory, we use a generalized seam surface and introduce a concept of a coordinate dependent effective nonadiabatic transition probability based on the Zhu-Nakamura theory which can treat the nonadiabatic tunneling properly. The present approach can be combined with Monte Carlo method so as to be applicable to chemical reactions in complicated systems. The method is demonstrated to work well in wide energy and temperature range. Numerical tests also show that it is very essential for accurate evaluation of the thermal rate constant to use the generalized seam surface and take into account the nonadiabatic tunneling effect.     

Application of a special in-house validation procedure for environmental–analytical schemes including a comparison of functions for modelling the repeatability standard deviation

For some years, a special in-house validation concept according to the Commission Decision 2002/657/EC of the European Union is employed. The validation concept is based on a variance component model, which allows to consider matrix- and operation-induced deviations and to calculate critical concentrations for given α-errors. The approach relies on a comprehensive mathematical model to asses simultaneously the in-house reproducibility and its components. One important component, the repeatability standard deviation, is estimated by means of a power function of the Horwitz-type. In this study, several performance characteristics were compared based on the use of four recommended estimations for the standard deviation depending on the concentration level of the analyte. A special factorial design for calibration, considering three factors influencing the variance of the measurement values, was applied for the determination of arsenic in surface water samples collected at several abandoned mining sites in Germany. The advantageous applicability of the validation method presented for analytical procedures referring to environmental tasks was demonstrated.     

A new theory of determination of vibrational raman intensities in crystal lattices

Quantum-chemical methods have been used for the calculation of the intensities of Raman-active internal and external modes in crystalline oxamide. In a first step the frequencies and eigenvectors of the modes in oxamide are calculated by use of the concept of a flexible vibrating molecule within the intermolecular atom-atom forces. The quantum-mechanical aspects are considered and finally, a semiempirical method is extended to cover the relative Raman intensities of the external and internal modes.     

电解醇制氢

发展了利用甲醇直接电解制氢这种经济的制氢方法, 实验结果表明电解甲醇制氢能够极大地降低电能消耗. 此方法的新颖之处在于方法简单和成本低. 将直接甲醇燃料电池膜电极作为电解装置, 可以达到任何规模的要求. 如果将这种电解装置与太阳能电池联用, 可非常经济地制氢及氢气储存, 或直接向燃料电池或其它化学工程装置供氢.     

钢铁中稀土合金化的内耗研究及其理论

扼要地回顾了稀土钢及其合金化研究的发展历程；阐明合金化、合金化耗及用内耗研究合金化的基本思想和铁内耗谱及其机制等理论理论基础；介绍了用内耗方法研究钢中稀土合金化取得的进展；最后，从钢中稀土的作用结构材料的发展，展望了用稀土处理钢的前景。     

Far-Infrared Fourier Spectroscopy as a Method for Structure Determination in Chemistry

Couched in the often confusing term “Fourier Spectroscopy” is the combined exploitation of a fundamental physical concept, a simple mathematical principle, and use of modern data technology. Introduction of this relatively young method into instrument technology has given great impetus to nuclear magnetic resonance and infrared spectroscopy. The infrared spectroscopic investigation of low frequency molecular vibrations has especially profited; in this connection one speaks of far infrared (FIR) Fourier Spectroscopy, which has opened up numerous interesting applications in organic, inorganic, and physical chemistry.     

Multiresidue analysis of beta-agonists in bovine and porcine urine,feed and hair using liquid chromatography electrospray ionisation tandem mass spectrometry

The use of β-agonists as growth promoters in cattle breeding is forbidden in many countries for reasons of fair trade and consumer protection. In recent years the use of liquid chromatography (LC) tandem mass spectrometry (MS/MS) has been shown to be the method of choice for the control of β-agonists. In this study an LC-MS/MS multiresidue analysis method is presented for trace analysis of 22 β-agonists. A truly generic concept has been designed based on mixed-mode solid-phase extraction and positive electrospray ionisation LC-MS/MS operated in the multiple reaction monitoring mode. This method allows application to a wide variety of sample matrices such as urine, feed and hair, following minor modifications to the analysis procedure only. The method features fit-for-purpose sensitivity in urine as shown by CCα and CCβ values of less than 0.2 and less than 0.5 μg/l respectively, for all β-agonists studied (terbutaline and reproterol, less than 0.3 and less than 1.0 respectively). Similar but semiquantitative application to feed and hair showed CCβ values of less than 10.0 and less than 5.0 μg/kg, respectively. A further simplification and improvement is demonstrated using Ultra Performance LC (UPLC™) and fast-switching MS/MS. The successful validation of this method following the latest EU requirements and its application to real samples demonstrate that a new versatile tool has been achieved for veterinary control of β-agonists.     

Two new criteria for the service life prediction of plastics pipes

In this contribution, two new criteria and related methodologies for the prediction of the long-term (creep rupture) behavior of single layer and multilayer plastics pipes under hydrostatic pressure are presented. One of these is the ultimate strain extrapolation method (USEM) and the other is called the distortion energy extrapolation method (DEEM). The strain concept is based on the use of the failure strain criteria instead of the normally employed stress concept. A related long-term extrapolation methodology is presented that employs the ultimate strain instead of the rupture stress. The strain energy concept is based on the use of the distortion energy corresponding to the failure stress. For both of these two criteria, related extrapolation methodologies are introduced. An example is presented that compares the classical standard extrapolation method (SEM) with the ultimate strain and the energy methods. For correlation of various models, an example of a PVC-U pipe under internal hydrostatic pressure at T=20 °C was studied. The three models employed were the stress-based, the strain-based, and the energy-based regression analyses. Direct regression analysis was performed for all three failure criteria. However, for comparison, the modified version of the SEM was also used. In all cases, a complete match between the independent model and the modified SEM analysis was obtained. A backward calculation of failure stress from the long-term failure distortion energy gave a 50-year failure stress equal to 18.59 MPa. This value was lower than the stress-based extrapolation (25.37 MPa) and higher than the strain-based extrapolation. The proposed USEM is suitable for materials which fail due to the ultimate strain state and not necessarily due to the maximum stresses. Thus, the proposed strain extrapolation criteria may prove to be especially suitable for brittle and fiber reinforced materials. The strain-based extrapolation can be used in connection with rupture data in internal hydrostatic tests or creep rupture of pipe samples under other loading conditions. The DEEM, on the other hand, is believed to be applicable to a broad range of material types. The proposed methodologies can be used as a new guideline for prediction of the service life of single layer brittle thermoplastics pipes, glass fiber reinforced laminate pipes, and multilayer plastics pipes with fiber reinforced layers.     

Quantification of the Interaction of SmI2 with Substrates and Ligands

The method developed and introduced here enables for the first time (to the authors’ knowledge), a quantitative assessment of the interaction of SmI₂ with substrates prior to the electron transfer stage. As a proof of concept, equilibrium constants for some model substrates including carbonyl compounds and aromatic nuclei are reported here. In addition, the first equilibrium constants with some common ligands were also determined. The equilibrium constants range from approximately 0.07 m ⁻¹ for diisopropyl ketone to 2500 m ⁻¹ for hexamethylphosphoramide (HMPA). It is shown that the data acquired by this method, which is based on the concept of shift reagents, can shed light on the most intimate details of the reaction mechanism, and this method is a useful tool for planning a synthetic process.     

Getting the Most out of Solar Irradiation: Efficient Use of Polychromatic Light for Water Splitting

To increase the fraction of utilizable polychromatic light, a new reactor concept was developed and manufactured by using rapid prototyping technologies. Investigation of the prototypes revealed enhancements of the photocurrent by up to one order of magnitude, when TiO₂ was used as the photoanode in combination with commercially available photovoltaic cells. The reported concept is scalable and an easy transfer to technical scale is expected from a technological as well as an economical perspective. Experimental results underline the conclusion that to achieve efficient overall use of solar irradiation both the material as well as the reactor/process must be considered. Combining these complementary approaches allows largest possible optimization potential. With respect to ongoing research, the concept also breaks ground for the development of catalysts.