Synthesis of Esters of Dioxane Alcohols and Their Performance as Plasticizers for Polyvinyl Chloride Compounds

A procedure was developed for preparing a plasticizer for polyvinyl chloride compounds from the fraction of dioxane alcohols. The main physicochemical properties of the new plasticizer were determined. Items prepared from formulations containing the new plasticizer were fabricated and tested in laboratory.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 6, 2005, pp. 972–976.Original Russian Text Copyright © 2005 by Glazko, Gur’yanova, Levanova, Kozlova, Neiman.     

Λ-Shaped Policies to Schedule Deteriorating Jobs

We study a problem of scheduling deteriorating jobs, i.e. jobs whose processing times are an increasing function of their starting times. We consider the case of a single machine and linear job-independent deterioration. The objective is to minimize the sum of weighted completion times, with weights proportional to the basic processing times. The optimal schedule is shown to be Λ-shaped, i.e. the sequence of the basic processing times has a single local maximum. Moreover, we show that the problem is solved in O(N log N) time. In the last section we test heuristics for the case of general weights.     

Acetylcholinesterase complexed with bivalent ligands related to huperzine a: experimental evidence for species-dependent protein-ligand complementarity

Acetylcholinesterase (AChE) inhibitors improve the cognitive abilities of Alzheimer patients. (-)-Huperzine A [(-)-HupA], an alkaloid isolated from the club moss, Huperzia serrata, is one such inhibitor, but the search for more potent and selective drugs continues. Recently, alkylene-linked dimers of 5-amino-5,6,7,8-tetrahydroquinolinone (hupyridone, 1a), a fragment of HupA, were shown to serve as more potent inhibitors of AChE than (-)-HupA and monomeric 1a. We soaked two such dimers, (S,S)-(-)-bis(10)-hupyridone [(S,S)-(-)-2a] and (S,S)-(-)-bis(12)-hupyridone [(S,S)-(-)-2b] containing, respectively, 10 and 12 methylenes in the spacer, into trigonal TcAChE crystals, and solved the X-ray structures of the resulting complexes using the difference Fourier technique, both to 2.15 A resolution. The structures revealed one HupA-like 1a unit bound to the "anionic" subsite of the active-site, near the bottom of the active-site gorge, adjacent to Trp84, as seen for the TcAChE/(-)-HupA complex, and the second 1a unit near Trp279 in the "peripheral" anionic site at the top of the gorge, both bivalent molecules thus spanning the active-site gorge. The results confirm that the increased affinity of the dimeric HupA analogues for AChE is conferred by binding to the two "anionic" sites of the enzyme. Inhibition data show that (-)-2a binds to TcAChE approximately 6-7- and > 170-fold more tightly than (-)-2b and (-)-HupA, respectively. In contrast, previous data for rat AChE show that (-)-2b binds approximately 3- and approximately 2-fold more tightly than (-)-2a and (-)-HupA, respectively. Structural comparison of TcAChE with rat AChE, as represented by the closely related mouse AChE structure (1maa.pdb), reveals a narrower gorge for rat AChE, a perpendicular alignment of the Tyr337 ring to the gorge axis, and its conformational rigidity, as a result of hydrogen bonding between its hydroxyl group and that of Tyr341, relative to TcAChE Phe330. These structural differences in the active-site gorge explain the switch in inhibitory potency of (-)-2a and 2b and the larger dimer/(-)-HupA potency ratios observed for TcAChE relative to rat AChE. The results offer new insights into factors affecting protein-ligand complementarity within the gorge and should assist the further development of improved AChE inhibitors.     

Estimation of micropore size distribution in active carbons from adsorption isotherms of water vapor

A possibility of estimation of the micropore size distribution in the carbon adsorbents with the developed micro-and mesoporous structure by analysis of the adsorption isotherms of water vapors was considered. At saturation water condenses in micropores in a form of a weakly compressed liquid. However, water molecules in micropores are packed not so closely as in the liquid because of steric hindrance. Therefore, the real density of water adsorbed in the micropores is lower than that of water adsorbed on an open surface and lower than the density of the normal liquid. An analysis of the adsorption isotherms of water vapors with account for the both opposite effects on the water density gives reliable data on the micropore sizes of the carbon adsorbents. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 40–43, January, 2007.     

Stability of lyophobic sols

The coagulation of positively charged sol of hydrous ferric oxide of different average sizes for potassium sulphate has been studied in the presence of glucose and urea which stabilise the sol. The degree of stabilisation increases with the fineness of dispersed particles. It has been concluded that the adhesive tendency of the surface of dispersed particles decreases in the presence of said non-electrolytes leading to a decrease in the frequency of collisions resulting in stabilisation. The stability ratioW increases in the presence of glucose and urea for the same amount of the coagulant.

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Zusammenfassung Die Koagulation positiv geladener Sole von wäßrigem Ferrioxid verschiedener mittlerer Partikelgrößen mit Kaliumsulfat wird in Gegenwart von Glykose und Harnstoff, die beide das Sol stabilisieren, untersucht. Der Grad der Stabilisierung hängt von der Teilchengröße ab. Es wird geschlossen, daß die Adhäsionstendenz der Oberflächen der dispergierten Partikel in Gegenwart besagter Nichtelektrolyte abnimmt und so zur Abnahme der Kollisionshäufigkeit und damit zur Stabilisierung führt. Das StabilisierungsverhältnisW wächst in Anwesenheit von Glykose und Harnstoff für gleiche Beträge des Koagulators.

     

Synthesis of silver nanoparticles with polystyrylcarboxylate ligands

Silver nanoparticles stabilized by polystyrylmonocaboxylate ligands with varied chain lengths are synthesized via the low-temperature reduction of silver polystyrylmonocaboxylate with triethylamine. Silver nanoparticles have small dimensions, narrow size distributions, high stability, and ability to redisperse in nonpolar solvents. The kinetic features of the reaction are studied via high-performance liquid chromatography; UV, visible and IR spectroscopy; and transmission electron microscopy. It is shown that the reduction of silver occurs in the cores of reverse micelle species organized by diphilic macromolecules of silver polystyrylmonocarboxylates.     

Simulations of remote mutants of dihydrofolate reductase reveal the nature of a network of residues coupled to hydride transfer

Recent experimental and theoretical studies have proposed that enzymes involve networks of coupled residues throughout the protein that participate in motions accompanying chemical barrier crossing. Here, we have examined portions of a proposed network in dihydrofolate reductase (DHFR) using quantum mechanics/molecular mechanics simulations. The simulations use a hybrid quantum mechanics‐molecular mechanics approach with a recently developed semiempirical AM1‐SRP Hamiltonian that provides accurate results for this reaction. The simulations reproduce experimentally determined catalytic rates for the wild type and distant mutants of E. coli DHFR, underscoring the accuracy of the simulation protocol. Additionally, the simulations provide detailed insight into how residues remote from the active site affect the catalyzed chemistry, through changes in the thermally averaged properties along the reaction coordinate. The mutations do not greatly affect the structure of the transition state near the bond activation, but we observe differences somewhat removed from the point of C? H cleavage that affect the rate. The mutations have global effects on the thermally averaged structure that propagate throughout the enzyme and the current simulations highlight several interactions that appear to be particularly important. © 2014 Wiley Periodicals, Inc.     

The bimolecular hydrogen-deuterium exchange behavior of protonated alkyl dipeptides in the gas phase

As part of an ongoing characterization of the intrinsic chemical properties of peptides, thermal hydrogen-deuterium exchange has been studied for a series of fast-atom-bombardment-generated protonated alkyldipeptides and related model compounds in the reaction with D₂O, CH₃OD, and ND₃ in a Fourier transform ion cyclotron resonance mass spectrometer. Despite the very large basicity difference between the dipeptides and the D₂O and CH₃OD exchange reagents, efficient exchange of all active hydrogen atoms occurs. From the kinetic data it appears that exchange of the amino, amide, and hydroxyl hydrogens proceeds with different efficiencies, which implies that the proton in thermal protonated dipeptides is immobile. The selectivity of the exchange at the different basic sites is governed by the nature of both the dipeptide and the exchange reagent. The results indicate that reversible proton transfer in the reaction complexes, which effectuates the deuterium incorporation, is assisted by formation of multiple hydrogen bonds between the reagents. Exchange is considered to proceed via the intermediacy of different competing intermediate complexes, each of which specifically leads to deuterium incorporation at different basic sites. The relative stabilization of the competing intermediate complexes can be related to the relative efficiencies of deuterium incorporation at different basic sites in the dipeptide. For all protonated dipeptides studied, the exchange in the reaction with ND₃ proceeds with unit efficiency, whereas all active hydrogen atoms are exchanged equally efficiently. Evidently specific multiple hydrogen bond formations are far less important in the reversible proton transfers with the relatively basic ammonia, which allows effective randomization of all active hydrogen atoms in the reaction complexes.     

Design, synthesis, and properties of neoglycolipids based on ethylene glycoles conjugated with lactose as components of targeted delivery systems of biologically active compounds

Synthesis has been developed of a series of new aliphatic lactose derivatives as components of liposomal targeted delivery systems distinguished by the length and the number of aliphatic chains and also by the length of the spacer fragment. The structure of compounds synthesized has been established by means of 1H NMR spectroscopy.     

Bicriteria problems to minimize maximum tardiness and due date assignment cost in various scheduling environments

We study bicriteria problems of minimizing maximum tardiness and total due date assignment cost in various scheduling environments. We assume that each job can be assigned a different due date without any restriction, and that each due date assignment cost is a non-decreasing function of the quoted due date. We settle the complexity of most of the problems studied by either proving that they are NP-hard or finding a polynomial time solution for them. We also include approximation and non-approximability results for several parallel-machine problems.