Materials engineering for optoelectronic crystals related to III–V compounds

An introductory glimpse of modern approaches to the application of productive and reasonable techniques for the defined electronic materials will be presented. The paper is divided into four parts. Each is supplemented with illustrations. The first part explains the meaning of materials engineering for electronics (MEE) and for optoelectronic crystals in particular. Its interdisciplinarity is shown and also the range of problems it can solve. Graduate courses of someMEE disciplines are also given. The second part of the paper related to the feasible solution withMEE as to the optimal realization of the application requirements. The physical modelling, databases and characterization techniques are given. The third part deals with particular materials: III–V semiconductors. A brief survey of the best methods of crystal growth is given, stressing those which imply a possibility of creating crystals defined up to the atomic range. The last part is devoted to our team's orginal crystal growth methods:CAM-S (A Crystallization Method Providing Composition Autocontrol in Situ) andCOM-S (Calculation Method of Optimal Molten-Solution Composition). The combination of these methods, further modified with vibrational and magneto-hydrodinamical stirring (VS, MHD-S), allows us to grow crystalline ingots of ternary solid solutions (TSS) possessing extreme homogeneity. Illustrations on In?Ga?Sb system are supplied. We conclude with a discussion of the impact of such methods and approaches on a device quality and to other fields.     

Effect of Different Purification Techniques on the Characteristics of Heteropolysaccharide-Protein Biopolymer from Durian (<em>Durio zibethinus</em>) Seed

Natural biopolymers from plant sources contain many impurities (e.g., fat, protein, fiber, natural pigment and endogenous enzymes), therefore, an efficient purification process is recommended to minimize these impurities and consequently improve the functional properties of the biopolymer. The main objective of the present study was to investigate the effect of different purification techniques on the yield, protein content, solubility, water- and oil-holding capacity of a heteropolysaccharide-protein biopolymer obtained from durian seed. Four different purification methods using different chemicals and solvents (i.e., A (isopropanol and ethanol), B (isopropanol and acetone), C (saturated barium hydroxide), and D (Fehling solution)] to liberate the purified biopolymer from its crude form were compared. In most cases, the purification process significantly (p < 0.05) improved the physicochemical properties of heteropolysaccharide-protein biopolymer from durian fruit seed. The present work showed that the precipitation using isopropanol and acetone (Method B) resulted in the highest purification yield among all the tested purification techniques. The precipitation using saturated barium hydroxide (Method C) led to induce the highest solubility and relatively high capacity of water absorption. The current study reveals that the precipitation using Fehling solution (Method D) most efficiently eliminates the protein fraction, thus providing more pure biopolymer suitable for biological applications.     

Novel methods for calculating the fine vibronic spectra of polyatomic molecules

Novel approximate methods for calculating the vibrational structure of the electronic spectra of polyatomic molecules—a method for the direct calculation of the overlap integrals of vibrational wave functions for the electronic states involved in a transition and a variational method for the solution of the vibrational problem for the excited states—are discussed. The methods are based on the consideration of the displacement and entanglement of normal coordinates, the quasiorthogonality of the Dushinsky transformation, and the classification of the states by total vibrational quantum numbers. Matrix perturbation theory is employed. It is shown that the accuracy of these methods compares well with the accuracy of the available “exact” techniques (the errors are ∼1 cm⁻¹ for frequency and 10% for relative intensity). At the same time, calculations by the new methods are performed more than two orders of magnitude faster than by the previously known methods. K. A. Timiryazev Agricultural Academy, Moscow. Translated fromZhurnal Strukturnoi Khimii, Vol. 36, No. 2, pp. 217–230, March–April, 1995. Translated by I. Izvekova     

The location of transition states: A comparison of Cartesian,Z-matrix,and natural internal coordinates

A comparison is made between geometry optimization in Cartesian coordinates, in Z-matrix coordinates, and in natural internal coordinates for the location of transition states. In contrast to the situation with minima, where all three coordinate systems are of comparable efficiency if a reliable estimate of the Hessian matrix is available at the starting geometry, results for 25 different transition states covering a wide range of structural types demonstrate that in practice Z-matrix coordinates are generally superior. For Cartesian coordinates, the commonly used Hessian update schemes are unable to guarantee preservation of the necessary transition state eigenvalue structure, while current algorithms for generating natural internal coordinates may have difficulty handling the distorted geometries associated with transition states. The widely used Eigenvector Following (EF) algorithm is shown to be extremely efficient for optimizing transition states. © 1996 by John Wiley & Sons, Inc.     

The optimization of an ICP injection technique and the application to the direct analysis of small-volume serum samples

The optimization and the analytical properties of an injection technique for the analysis of small-volume samples (50–200 μl) by inductively coupled plasma atomic emission spectroscopy (ICP-AES) are described. Samples are injected into a small funnel connected to a concentric glass nebulizer. A 3 kW argon/nitrogen ICP with power stabilization is used as excitation source. When operating the nebulizer at an argon pressure of 5 bar, relative detection limits for calcium, copper, iron, magnesium and zinc (0.2–50 $\text{ng}\text{ml}$) are a factor of 2 to 10 higher when compared with ICP methods using continuous nebulization. However, the full power of detection of the injection method is obtained at a 50 μl sampling volume. Matrix effects caused by sodium salt concentrations of 5 $\text{g}\text{l}$ are lower than 10%. Relative standard deviations s_r,(I_X) ranged from 0.03 to 0.07. The method was applied to the sequential determination of trace elements (copper, iron and magnesium) in human serum samples after a 1 + 4 dilution with Herrmann solution. The accuracy of the method is illustrated by the analysis results for calcium, copper, iron, magnesium and zinc in a series of test serum samples.     

Flameless atomic absorption spectrometry of antimony

Flameless atomic absorption spectrometry of antimony has been investigated with a carbon rod device. Antimony may be determined in solution at a level of 10^-10 g with a sample volume of 0.5 μl. Optimal conditions and interferences are described. Matrix effects on antimony necessitated a preliminary solvent extraction of the chloride complex from hydrochloric acid solution containing nitrite with methyl isobutyl ketone. The determination of antimony in metallurgical samples was shown to be satisfactory.     

Stoichiometry of the oxidation of arylhydrazines with ferricyanide : Quantitative measurements of absorption spectra of aryldiazenes

A novel method for generating aryldiazenes quantitatively by the oxidation of arylhydrazines with exactly two equivalents of ferricyanide has been confirmed with o-, m-, and p- tolylhydrazine and with o- and p-hydrazinobenzoic acid. The rapidity and stoichiometry of the reaction permit accurate measurements of UV and visible absorption spectra in aqueous solution. Although oxidation of acetylphenylhydrazine by ferricyanide was slower, the product was shown to be acetylphenyldiazene. Acetylphenyldiazene is partially hydrogenated during mass spectrometric analysis. The source of hydrogen was shown to be H₂O in the spectrometer. This phenomenon, previously reported only in quinones, was also observed in the mass spectrum of methyl phenyldiazenecarboxylate.     

Transiting the molecular potential energy surface along low energy pathways: The TRREAT algorithm

The Transition Rapidly exploring Random Eigenvector Assisted Tree (TRREAT) algorithm is introduced to perform searches along low curvature pathways on a potential energy surface (PES). The method combines local curvature information about the PES with an iterative Rapidly exploring Random Tree algorithm (LaValle, Computer Science Department, Iowa State University, 1998, TR98–11) that quickly searches high‐dimensional spaces for feasible pathways between local minima. Herein, the method is applied to identifying conformational changes of molecular systems using Cartesian coordinates while avoiding a priori definition of collective variables. We analyze the pathway identification problem for alanine dipeptide, cyclohexane and glycine using nonreactive and reactive forcefields. We show how TRREAT‐identified pathways can be used as valuable input guesses for double‐ended methods such as the Nudged Elastic Band when ascertaining transition state energies. This method can be utilized to improve/extend the reaction databases that lie at the core of automatic chemical reaction mechanism generator software currently developed to build kinetic models of chemical reactions. © 2013 Wiley Periodicals, Inc.     

Mild, powerful, and robust methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively

We developed two efficient practical methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively. The present mild and robust reaction was performed by two separate methods both by combining cheap and readily available amines, N-methylimidazole, and N,N,N′,N′-tetramethylethylenediamine (TMEDA). Method A uses catalytic N-methylimidazole and TMEDA with an equimolar amount of K₂CO₃, whereas Method B uses equimolar amounts of N-methylimidazole and TMEDA. The salient features are as follows. (i) With regard to reactivity, Method B was superior to Method A for esterification and thioesterification, whereas cost-effective Method A was superior to Method B for amide formation. (ii) Amide formation proceeded smoothly between acid chlorides and less nucleophilic and stereocongested amines such as 2,6-dichloroaniline. (iii) This protocol was applied to the successful synthesis of two agrochemicals, bromobutide and carpropamid.     

Deposition and extension approach to find longest common subsequence for thousands of long sequences

The problem of finding the longest common subsequence (LCS) for an arbitrary number of sequences is a very interesting and challenging problem in computer science. This problem is NP-complete, but because of its importance, many heuristic algorithms have been proposed, such as Long Run, Expansion Algorithm and THSB. However, the performance, either in result quality or in process time, of many current heuristic algorithms deteriorates fast when the number of sequences and sequence length increase. In this paper, we have proposed a post-process heuristic algorithm for the LCS problem, the Deposition and Extension Algorithm (DEA). This algorithm first generates common subsequence by “sequence deposition” based on fine tuning of search range, and then extends this common subsequence. The algorithm is proven to generate Common Subsequences (CSs) with guaranteed lengths. The experiments on different dataset showed that the results of DEA algorithm were better than those of Long Run and Expansion Algorithm, especially on many long sequences. The algorithm also had superior efficiency both in time and memory space.     

Viscosity of aqueous solutions of polysaccharides and hydrophobically modified polysaccharides: Application of Fedors equation

Amphiphilic polysaccharides have been obtained by hydrophobic modification of a neutral bacterial polysaccharide, dextran. Various amounts and types of aliphatic hydrocarbon groups have been attached to dextran.The solution behaviour of unmodified dextran samples and amphiphilic dextran derivatives is characterized by viscometric measurements. The overall viscosity behaviour of unmodified polysaccharides is described up to C × [η] = 3, using the equation of Fedors [Fedors RF. Polymer 1979;20:225] which involves only a concentration parameter. The latter is shown to depend on the hydrodynamic volume of the macromolecules in solution.The equation of Fedors is shown to conveniently estimate the viscosity behaviour of amphiphilic dextran derivatives up to C × [η] = 1. The interdependence between Fedors parameter and other viscometric characteristics (intrinsic viscosity, Huggins coefficient) is evidenced. These results are extended to the data of other authors.     

The Detection and Stability of DNA Duplexes Probed by MALDI Mass Spectrometry

Matrix‐assisted laser desorption/ionization (MALDI) with nonacidic matrices is shown to generate intact gas‐phase ions of double‐stranded DNA. Control experiments show that specific DNA duplexes are detected by this method, while nonspecific adducts form only when high monomer concentrations are present in the MALDI sample. The relative intensity of the duplex‐ion signal is found to reflect the solution‐phase stability of the double‐stranded DNA.     

Effect of ionizing radiation on the quantitative detection of Salmonella using real-time PCR

Food irradiation is an economically viable technology for inactivating foodborne pathogens, but irradiation can mask pathogens in unhygienically prepared food. The aim of this study was to investigate the effect of irradiation treatment on the detection of Salmonella using real-time PCR. Three commercially available kits were tested, of which the InstaGene Matrix procedure was most effective in preparing template DNA from Salmonella exposed to radiation in broth culture. The minimum level of detection by real-time PCR combined with InstaGene Matrix was 3 log units of Salmonella per milliliter. However, when pure cultures of Salmonella were irradiated at 3 and 5 kGy, the cycle threshold (C_T) increased 1–1.5-fold compared to irradiation at 0 and 1 kGy. This indicated that irradiation treatment may result in an underestimation of bacterial counts due to radiation-induced DNA lesions. We also compared C_T values in inoculated chicken homogenates before and after irradiation, which in this model caused a 1.3–3.3-fold underestimation of bacterial counts with respect to irradiation dose.     

Tyrosine absorption spectroscopy: Backbone protonation effects on the side chain electronic properties

The UV–vis spectrum of Tyrosine and its response to different backbone protonation states have been studied by applying the Perturbed Matrix Method (PMM) in conjunction with molecular dynamics (MD) simulations. Herein, we theoretically reproduce the UV–vis absorption spectrum of aqueous solution of Tyrosine in its zwitterionic, anionic and cationic forms, as well as of aqua‐p‐Cresol (i.e., the moiety that constitutes the side chain portion of Tyrosine). To achieve a better accuracy in the MD sampling, the Tyrosine Force Field (FF) parameters were derived de novo via quantum mechanical calculations. The UV–vis absorption spectra are computed considering the occurring electronic transitions in the vertical approximation for each of the chromophore configurations sampled by the classical MD simulations, thus including the effects of the chromophore semiclassical structural fluctuations. Finally, the explicit treatment of the perturbing effect of the embedding environment permits to fully model the inhomogeneous bandwidth of the electronic spectra. Comparison between our theoretical–computational results and experimental data shows that the used model captures the essential features of the spectroscopic process, thus allowing to perform further analysis on the strict relationship between the quantum properties of the chromophore and the different embedding environments. © 2018 Wiley Periodicals, Inc.     

Kinetic analysis of thermogravimetric data

Computer programs are given in Fortran language for three integral methods of deriving kinetic parameters from TG curves. Method 1 is a computerized variant of Doyle's curve-fitting method and performs the calculation of the exponential integralp(x) by means of author's empirical formula. Methods 2 and 3 are variants of the Coats-Redfern linearization method. Testing of the methods on both theoretical and experimental TG curves shows them to be almost equivalent as far as the results obtained are concerned, but Method 1 needs a ten-fold higher computer time.     

Determination of biphenyl in the presence of polyphenyls : Water solubility method

Prior work had shown that the principal products of the pyrolysis of p-terphenyl are biphenyl and certain higher polyphenyls. Since the three terphenyls as well as particular higher polyphenyls are being investigated as heat transfer media for atomic energy reactors, the determination of biphenyl, as a major or minor product of their pyrolysis, becomes of prime importance in order to follow the trend of reaction products.Because of the greater solubility of biphenyl in water, as compared to other polyphenyls, biphenyl is completely extracted from such mixtures by water and can be determined spectrophotometrically in aqueous solution. Effects of temperature, rates of solution, and the presence of polyphenyls were studied. The solubility of biphenyl is about 0.9 mg/100 ml of water, but the suggested working limit in 0.4 mg biphenyl/100 ml of solvent.As little as 0.1% biphenyl in p-terphenyl may be detected and as high as 20% may be determined in higher polyphenyls.     

A scheme for the analysis of monazite and monazite concentrates

A scheme using ion-exchange methods is described for the analysis of monazites and monazite concentrates. The sample is opened up with concentrated sulphuric acid, and the resultant solution is applied to a column of Zeocarb 225 resin. After phosphate has been washed out, lead, aluminium, titanium, iron, uranium, calcium and magnesium are eluted with N hydrochloric acid and determined by specific, mainly spectrophotometric, methods. Rare earth elements are eluted with 3 N hydrochloric acid. Cerium is separated from the other rare earths by solvent extraction of its nitrate with methyl iso-butyl ketone; both groups are determined gravimetrically. Thorium is eluted from the ion-exchange resin with 3.6 N sulphuric acid and determined spectrophotometrically with thorin.The sulphuric acid-insoluble minerals are brought into solution by a double fusion method, and the determinations are carried out by a combination of ion-exchange and photometric procedures. Silica, phosphorus pentoxide, tin and chromium are determined by photometric methods, using separate portions of the sample.Lanthanum, yttrium and ytterbium are determined in a 1 M perchloric acid solution of the mixed rare earth oxides (less cerium) using flame photometry. Samarium, praseodymium and neodymium are determined by spectrophotometry.     

An alternative to the “Star Path” enhancement of the ADMA linear scaling method for protein modeling

With the aim of improving the performance of macromolecular quantum chemistry conformation analysis and reaction path following methods, the Adjustable Density Matrix Assembler (ADMA) method has already been combined with some faster although less accurate density matrix extrapolation methods, such as the Löwdin‐Inverse‐Löwdin (LIL) extrapolation along a potential energy surface, and a strategically arranged back‐and‐forth switching between these methods has been proven to be advantageous. Here, an alternative approach is proposed and investigated, based on several actual test calculations, where the “inexpensive” LIL density matrix extrapolation steps are replaced by only somewhat more expensive, but still ADMA‐based calculations, where in the “rough‐search stage,” only interactions of shorter distances within the macromolecule are considered. It is shown that this approach is viable, as an alternative to the “Star Path” method including both ADMA and LIL steps. © 2017 Wiley Periodicals, Inc.