Formation of Polymer Nanolayers with Special Properties at Polymer Surfaces

A principal possibility of the utilization of polymer peroxides for the modification of polymer surfaces that provides an immobilization of the tailored quantity of peroxide groups at them has been established. The processes of polymer surface activation with following “grafting from” or “grafting to” utilizing immobilized peroxide groups has been studied using a FTIR-ATR spectroscopy, ellipsometry and measurements of contact angles. The proposed technique of polymer surface activation is based on the universal ability of carbon chain polymer to participate the free radical reactions.     

A family of 2D and 3D coordination polymers involving a trigonal tritopic linker

Five new coordination polymers, namely, [Zn(2)(H(2)O)(2)(BBC)](NO(3))(DEF)(6) (DUT-40), [Zn(3)(H(2)O)(3)(BBC)(2)] (DUT-41), [(C(2)H(5))(2)NH(2)][Zn(2)(BBC)(TDC)](DEF)(6)(H(2)O)(7) (DUT-42), [Zn(10)(BBC)(5)(BPDC)(2)(H(2)O)(10)](NO(3))(DEF)(28)(H(2)O)(8) (DUT-43), and [Co(2)(BBC)(NO(3))(DEF)(2)(H(2)O)](DEF)(6)(H(2)O) (DUT-44), where BBC--4,4',4'-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))tribenzoate, TDC--2,5-thiophenedicarboxylate, BPDC--4,4'-biphenyldicarboxylate, DEF--,N-diethylformamide, were obtained under solvothermal conditions and structurally characterized. It has been shown that compounds DUT-40, DUT-41 and DUT-44 exhibit 2D layered structures with large hexagonal channels. Utilization of additional angular dicarboxylic TDC linker led to the formation of the DUT-42 compound with the structure consisting of three interpenetrated 3D networks. Using the linear co-linker dicarboxylic BPDC, DUT-43 was obtained which forms a complicated 3D architecture arising from the polycatenation of triple-layered 2D building units and 2D single layer units. The pore accessibility of the synthesized compounds in the liquid phase was proved by the adsorption of dye molecules.     

The water hexamer: cage, prism, or both. Full dimensional quantum simulations say both

State-of-the-art quantum simulations on a full-dimensional ab initio potential energy surface are used to characterize the properties of the water hexamer. The relative populations of the different isomers are determined over a wide range of temperatures. While the prism isomer is identified as the global minimum-energy structure, the quantum simulations, which explicitly include zero-point energy and quantum thermal motion, predict that both the cage and prism isomers are present at low temperature down to almost 0 K. This is largely consistent with the available experimental data and, in particular, with very recent measurements of broadband rotational spectra of the water hexamer recorded in supersonic expansions.     

TEM studies of structure in OFHC copper processed by equal channel angular rolling

In this study, UFG (ultrafine-grained) structure formed through ECAR (equal-channel angular rolling) process has been studied by methods of electron microscopy. The microstructure, mechanical properties and microhardness were investigated in OFHC (oxygen free high conductivity) copper after 1st–13th passes. The interpretation of microstructure changes was performed using a model which describes mechanism of UFG structures formation. It was found that ECAR is a tool used for the purpose of achieving significant structural refinement resulting in a final grain size d ～ 400 nm. Moreover, this method provides such specific structural changes which have highly advantageous influence on mechanical properties (yield stress, ultimate tensile strength, reduction of area) as well as microhardness.     

Lanthanum tetrazinc,LaZn4

The structure of lanthanum tetrazinc, LaZn₄, has been determined from single‐crystal X‐ray diffraction data for the first time, approximately 70 years after its discovery. The compound exhibits a new structure type in the space group Cmcm, with one La atom and two Zn atoms occupying sites with m2m symmetry, and one Zn atom occupying a site with 2.. symmetry. The structure is closely related to the BaAl₄, La₃Al₁₁, BaNi₂Si₂ and CaCu₅ structure types, which can be presented as close‐packed arrangements of 18‐vertex clusters, in this case LaZn₁₈. The kindred structure types contain related 18‐vertex clusters around atoms of the rare earth or alkaline earth metal.     

Quantification of local hydration at the surface of biomolecules using dual-fluorescence labels

By using four labels of the 3-hydroxyflavone family displaying selective sensitivity to hydrogen bond (HB) donors and poor response to other polar molecules, we developed an approach for measuring local water concentration [H(2)O](L) (or partial volume of water: W(A) = [H(2)O](L)/55.6) in the label surrounding both in solvent mixtures and in biomolecules by the intensity ratio of two emissive forms of the label, N*/T*. Using a series of binary water/solvent mixtures with limited preferential solvation effects, a linear dependence of log(N*/T*) on the local concentration of HB donor was obtained and then used as a calibration curve for estimating the W(A) values in the surroundings of the probes conjugated to biomolecules. By this approach, we estimated the hydration of the labels in different peptides and their complexes with DNAs. We found that W(A) values for the label at the peptide N-terminus are lower (0.63-0.91) than for free labels and depend strongly on the nature of the N-terminal amino acid. When complexed with different DNAs, the estimated hydration of the labels conjugated to the labeled peptides was much lower (W(A) = 0-0.47) and depended on the DNA nature and linker-label structure. Thus, the elaborated method allows a site-specific evaluation of hydration at the surface of a biomolecule through the determination of the partial volume of water. We believe the developed procedure can be successfully applied for monitoring hydration at the surface of any biomolecule or nanostructure.     

Highly π electron-rich macro-aromatics: bis(p-aminophenyl)-carbo-benzenes and their DBA acyclic references

A series of stable quadrupolar bis(p-aminophenyl)-carbo-benzenes, featuring both donor-donor-donor π-frustration and central macro-aromaticity, is described and compared to the acyclic dibutatrienylacetylene (DBA) reference series.     

Contracting with asymmetric demand information in supply chains

We solve a buyback contract design problem for a supplier who is working with a retailer who possesses private information about the demand distribution. We model the retailer’s private information as a space of either discrete or continuous demand states so that only the retailer knows its demand state and the demand for the product is stochastically increasing in the state. We focus on contracts that are viable in practice, where the buyback price being strictly less than the wholesale price, which is itself strictly less than the retail price. We derive the optimal (for the supplier) buyback contract that allows for arbitrary allocation of profits to the retailer (subject to the retailer’s reservation profit requirements) and show that in the limit this contract leads to the first-best solution with the supplier keeping the entire channel’s profit (after the retailer’s reservation profit).     

Highly magnetizable superparamagnetic colloidal aggregates with narrowed size distribution from ferrofluid emulsion

An empirical model for the concentrations of monomeric and micellized surfactants in solution is presented as a consistent approach for the quantitative analysis of data obtained with different experimental techniques from surfactant solutions. The concentration model provides an objective definition of the critical micelle concentration (cmc) and yields precise and well defined values of derived physical parameters. The use of a general concentration model eliminates subjective graphical procedures, reduces methodological differences, and thus allows one to compare directly the results of different techniques or to perform global fits. The application and validity of the model are demonstrated with electrical conductivity, surface tension, NMR chemical shift, and self-diffusion coefficient data for the surfactants SDS, CTAB, DTAB, and LAS. In all cases, the derived models yield excellent fits of the data. It is also shown that there is no need to assume the existence of different premicellar species in order to explain the chemical shifts and self-diffusion coefficients of SDS as claimed recently by some authors.