Application of chemometrics methods with kinetic constraints for estimation of rate constants of second order consecutive reactions.

To determine the rate constants for the second order consecutive reactions of the form U + V -(k1)--> W -(k2)--> P, a number of chemometrics and hard modeling-based methods are described. The absorption spectroscopic data from the reaction were utilized for performing the analysis. Concentrations and extinctions of components were comparable, and all of them were absorbing species. The number of steps in the reaction was less than the number of absorbing species, which resulted in a rank-deficient response matrix. This can cause difficulties for some of the methods described in the literature. The standard MATLAB functions were used for determining the solutions of the differential equations as well as for finding the optimal rate constants to describe the kinetic profiles. The available knowledge about the system determines the approaches described in this paper. The knowledge includes the spectra of reactants and products, the initial concentrations, and the exact kinetics. Some of this information is sometimes not available or is hard to estimate. Multiple linear regression for fitting the kinetic parameters to the obtained concentration profiles, rank augmentation using multiple batch runs, a mixed spectral approach which treats the reaction using a pseudo species concept, and principal components regression are the four groups of methods discussed in this study. In one of the simulated datasets the spectra are quite different, and in the other one the spectra of one reactant and of the product share a high degree of overlap. Instrumental noise, sampling error are the sources of error considered. Our aim was the investigation of the relative merits of each method.     

Portfolio optimization with linear and fixed transaction costs

We consider the problem of portfolio selection, with transaction costs and constraints on exposure to risk. Linear transaction costs, bounds on the variance of the return, and bounds on different shortfall probabilities are efficiently handled by convex optimization methods. For such problems, the globally optimal portfolio can be computed very rapidly. Portfolio optimization problems with transaction costs that include a fixed fee, or discount breakpoints, cannot be directly solved by convex optimization. We describe a relaxation method which yields an easily computable upper bound via convex optimization. We also describe a heuristic method for finding a suboptimal portfolio, which is based on solving a small number of convex optimization problems (and hence can be done efficiently). Thus, we produce a suboptimal solution, and also an upper bound on the optimal solution. Numerical experiments suggest that for practical problems the gap between the two is small, even for large problems involving hundreds of assets. The same approach can be used for related problems, such as that of tracking an index with a portfolio consisting of a small number of assets.     

Surface properties of polypropylene/organoclay nanocomposites

Influence of nanoclay amount on surface properties of the nanocomposites was investigated using Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), contact angle measurement, scanning electron microscopy (SEM) and transmission spectroscopy (TS). Polypropylene based nanocomposites containing various loads of nanoclay were prepared by melt compounding. X-ray diffraction (XRD) characterized the dispersion of nanoclay in polymer matrix. AFM and SEM studies have shown increase in surface roughness by raising the amount of nanoclay. Contact angle measurements of the resultant nanocomposites have also shown improvement in wettability related to disperse part of surface tension. POM images illustrated an increase in the number of spherulite simultaneously with a decrease in their size; this result was also supported by differential scanning calorimetry (DSC).     

New way to produce dense double-antikaonic dibaryon system, KKNN, through Λ(1405)-doorway sticking in p+p collisions

A recent successful observation of a dense and deeply bound K nuclear system, K-pp, in the p+p→K++K-pp reaction in a DISTO experiment indicates that the double-K dibaryon, K-K-pp, which was predicted to be a dense nuclear system, can also be formed in p+p collisions. We find theoretically that the K--K- repulsion plays no significant role in reducing the density and binding energy of K-K-pp and that, when two Λ(1405) resonances are produced simultaneously in a short-range p+p collision, they act as doorways to copious formation of K-K-pp, if and only if K-K-pp is a dense object, as predicted.     

Stability results of properties related to the Bishop-Phelps-Bollobás property for operators

We prove that the class of Banach spaces Y such that the pair(?_1, Y) has the Bishop-Phelps-Bollobás property for operators is stable under finite products when the norm of the product is given by an absolute norm. We also provide examples showing that the previous stability results obtained for that property are optimal.     

Preparation of Silica‐bonded Propyl‐diethylene‐triamine‐N‐sulfamic Acid as a Recyclable Catalyst for Chemoselective Synthesis of 1,1‐Diacetates

A simple and efficient procedure for the preparation of silica‐bonded propyl‐diethylene‐triamine‐N‐sulfamic acid (SPDTSA) by reaction of 3‐diethylenetriamine‐propylsilica (DTPS) and chlorosulfonic acid in chloroform is described. Silica‐bonded propyl‐diethylene‐triamine‐N‐sulfamic acid is employed as a recyclable catalyst for the synthesis of 1,1‐diacetates from aromatic aldehydes and acetic anhydride under mild and solvent‐free conditions at room temperature. Catalyst could be recycled for several times without any additional treatment.     

Developing a Nano‐Biosensor for DNA Hybridization Using a New Electroactive Label

Development of electrochemical DNA hybridization biosensors based on carbon paste electrode (CPE) and gold nanoparticle modified carbon paste electrode (NGMCPE) as transducers and ethyl green (EG) as a new electroactive label is described. Electrochemical impedance spectroscopy and cyclic voltammetry techniques were applied for the investigation and comparison of bare CPE and NGMCPE surfaces. Our voltammetric and spectroscopic studies showed gold nanoparticles are enable to facilitate electron transfer between the accumulated label on DNA probe modified electrode and electrode surface and enhance the electrical signals and lead to an improved detection limit. The immobilization of a 15‐mer single strand oligonucleotide probe on the working electrodes and hybridization event between the probe and its complementary sequence as a target were investigated by differential pulse voltammetry (DPV) responses of the EG accumulated on the electrodes. The effects of some experimental variables on the performance of the biosensors were investigated and optimum conditions were suggested. The selectivity of the biosensors was studied using some non‐complementary oligonucleotides. Finally the detection limits were calculated as 1.35×10^?10 mol/L and 5.16×10^?11 mol/L on the CPE and NEGCPE, respectively. In addition, the biosensors exhibited a good selectivity, reproducibility and stability for the determination of DNA sequences.     

CuO nanoparticles: An efficient and recyclable nanocatalyst for the rapid and green synthesis of 3,4-dihydropyrano[c]chromenes

Copper oxide nanoparticles showed excellent catalytic activity through three-component condensation reaction of aldehydes, malononitrile, and 4-hydroxycoumarin for the synthesis of 3,4-dihyropyrano[c]chromenes in water medium in excellent yields and very short reaction times.     

Conversion of carbon dioxide to valuable petrochemicals:An approach to clean development mechanism

The increase of atmospheric carbon dioxide and the global warming due to its greenhouse effect resulted in worldwide concerns. On the other hand, carbon dioxide might be considered as a valuable and renewable carbon source. One approach to reduce carbon dioxide emissions could be its capture and recycle via transformation into chemicals using the technologies in C1 chemistry. Despite its great interest, there are difficulties in CO2 separation on the one hand, and thermodynamic stability of carbon dioxide molecule rendering its chemical activity low on the other hand. Carbon dioxide has been already used in petrochemical industries for production of limited chemicals such as urea. The utilization of carbon dioxide does not necessarily involve development of new processes, and in certain processes such as methanol synthesis and methane steam reforming, addition of CO2 into the feed results in its utilization and increases carbon efficiency. In other cases, modifications in catalyst and/or processes, or even new catalysts and processes, are necessary. In either case, catalysis plays a crucial role in carbon dioxide conversion and effective catalysts are required for commercial realization of the related processes. Technologies for CO2 utilization are emerging after many years of research and development efforts.     

Aluminium Nitrate Nonahydrate (Al(NO3)3⋅9 H2O): An Efficient Oxidant Catalyst for the One‐Pot Synthesis of Biginelli Compounds from Benzyl Alcohols

A clean and efficient tandem oxidative cyclocondensation process is reported for the synthesis of 3,4‐dihydropyrimidin‐2(1H)‐one or ‐thione derivatives from primary aryl alcohols, β‐keto esters, and urea or thiourea in the presence of Al(NO₃)₃?9 H₂O as oxidant catalyst (Scheme, Table 5).