Elastic properties of single amylose chains in water: a quantum mechanical and AFM study

Recent single-molecule atomic force microscopy (AFM) experiments have revealed that some polysaccharides display large deviations from force-extension relationships of other polymers which typically behave as simple entropic springs. However, the mechanism of these deviations has not been fully elucidated. Here we report the use of novel quantum mechanical methodologies, the divide-and-conquer linear scaling approach and the self-consistent charge density functional-based tight binding (SCC-DFTB) method, to unravel the mechanism of the extensibility of the polysaccharide amylose, which in water displays particularly large deviations from the simple entropic elasticity. We studied the deformations of maltose, a building block of amylose, both in a vacuum and in solution. To simulate the deformations in solution, the TIP3P molecular mechanical model is used to model the solvent water, and the SCC-DFTB method is used to model the solute. The interactions between the solute and water are treated by the combined quantum mechanical and molecular mechanical approach. We find that water significantly affects the mechanical properties of maltose. Furthermore, we performed two nanosecond-scale steered molecular dynamics simulations for single amylose chains composed of 10 glucopyranose rings in solution. Our SCC-DFTB/MM simulations reproduce the experimentally measured force-extension curve, and we find that the force-induced chair-to-boat transitions of glucopyranose rings are responsible for the characteristic plateau in the force-extension curve of amylose. In addition, we performed single-molecule AFM measurements on carboxymethyl amylose, and we found that, in contrast to the results of an earlier work by others, these side groups do not significantly affect amylose elasticity. By combining our experimental and modeling results, we conclude that the nonentropic elastic behavior of amylose is governed by the mechanics of pyranose rings themselves and their force-induced conformational transitions.     

Initial Value Problems of the Sine-Gordon Equation and Geometric Solutions

Recent results using inverse scattering techniques interpret every solution φ(x, y) of the sine-Gordon equation as a nonlinear superposition of solutions along the axes x=0 and y=0. This has a well-known geometric interpretation, namely that every weakly regular surface of Gauss curvature K=−1, in arc length asymptotic line parametrization, is uniquely determined by the values φ(x, 0) and φ(0, y) of its coordinate angle along the axes. We introduce a generalized Weierstrass representation of pseudospherical surfaces that depends only on these values, and we explicitely construct the associated family of pseudospherical immersions corresponding to it.Mathematics Subject Classifications (2000): 53A10, 58E20.     

Open charm and beauty at ultrarelativistic heavy ion colliders

Important goals of BNL RHIC and CERN LHC experiments with ion beams include the creation and study of new forms of matter, such as the quark gluon plasma. Heavy quark production and attenuation provide unique tomographic probes of that matter. We predict the suppression pattern of open charm and beauty in Au+Au collisions at RHIC and LHC energies based on the DGLV formalism of radiative energy loss. A cancellation between effects due to the sqrt[s] energy dependence of the high p(T) slope and heavy quark energy loss is predicted to lead to surprising similarity of heavy quark suppression at RHIC and LHC.     

A deprotonated intermediate in the amide methanolysis reaction of an N4O-ligated mononuclear zinc complex

Treatment of [(ppbpa)Zn](ClO4)2 (1(ClO4)2, ppbpa = N-((6-(pivaloylamido)-2-pyridyl)methyl)-N,N-bis((2-pyridyl)methyl)amine) with 1 equiv of Me(4)NOH.5H(2)O in methanol-acetonitrile solution results within minutes in the stoichiometric formation of a complex having a deprotonated amide, [(ppbpa-)Zn]ClO4 (3). Complex 3 has been characterized by 1H and 13C NMR, FTIR, and elemental analysis. Notably, upfield shifts of specific 1H NMR resonances of the amide-appended pyridyl moiety in 3, versus those found for 1(ClO4)2, indicate delocalization of the anionic charge within the amide-appended pyridyl donor of this complex. Heating of analytically pure 3 in methanol-acetonitrile results in amide alcoholysis. Overall, this alcoholysis reaction is second-order, with a first-order dependence on both 3 and methanol. Analysis of the rate of decay of 3 as a function of temperature yielded activation parameters consistent with an intramolecular amide cleavage process (DeltaH++ = 15.0(3) kcal/mol, DeltaS++ = -33(1) eu). A possible reaction mechanism for amide alcoholysis is presented which involves reaction of the deprotonated amide intermediate 3 with methanol to produce a Lewis activated-type structure from which amide cleavage may be initiated. Additional support for this mechanistic pathway has been obtained through examination of the analogous ethanolysis reaction and via evaluation of the effect of varying steric hindrance near the amide carbonyl unit.     

Unusual binding ability of vancomycin towards Cu2+ ions

Vancomycin, a "last chance" antibiotic, is a glycopeptide consisting of an oligopeptide unit being potentially the effective binder of Cu2+ ions. The potentiometric and spectroscopic studies (UV-Vis, CD, EPR, NMR) have shown that, indeed, the peptide unit binds cupric ions very effectively forming almost instantly the 3N complex involving the N-terminal nitrogen donors in the metal ion coordination. The comparison of the binding ability of vancomycin with other peptide chelators clearly shows the efficiency of this antibiotic in metal ion coordination. It is very likely that Cu2+ ions may play a crucial role in the pharmacology of vancomycin, particularly when administered in high doses.     

Effects of inclusion of cetirizine hydrochloride in β-cyclodextrin

Following the preparation of inclusion complex of cetirizine (CTZ) and β-cyclodextrin (β-CD), the compound was investigated to assess the possibility of modifying the physicochemical properties (solubility, release, stability, permeability) of CTZ after complexation that are vital for subsequent formulation studies involving the said complex. Changes in FT-IR/Raman spectra, DSC thermograms and XRD diffractograms confirmed the formation of a CTZ–β-CD system. Hydrophilic interaction chromatography with a DAD detector was employed to determine alterations of the CTZ concentration during studies following complexation. An analysis of a phase-solubility diagram of c_CTZ?=?fc_β-CD indicated a linear rise in the solubility of CTZ as the concentration of β-CD increased. The inclusion of CTZ in a system with β-CD significantly reduced the instability of CTZ in the presence of oxidizing factors. It was also found that regardless of the pH of the acceptor fluids used in the release studies an increase was observed in the concentration of CTZ in CD system compared to its free form. The ability to permeate artificial biological membranes manifested by CTZ after complexation was enhanced as well. In summary, CD has significant potential to mask the bitter taste of CTZ and to counter the instability induced by oxidizing factors.     

Physicochemical properties of ceramic tape involving Ca<Subscript>0.05</Subscript> Ba<Subscript>0.95</Subscript> Ce<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3</Subscript> as an electrolyte designed for electrolyte-supported solid oxide fuel cells (IT-SOFCs)

Energetic materials such as a mixture of guanidine nitrate (GN)/basic copper nitrate (BCN) are used as gas generators in automotive airbag systems. However, at the time of the airbag inflation, the gas generators release toxic combustion gases such as CO, NH₃, and NO_x. In this study, we investigated the combustion and thermal decomposition behaviors of GN/BCN mixture, focusing primarily on their exhaust gas composition. As a result, when the exhaust gas of the combustion under constant pressure in an inert gas stream was analyzed using a detection tube, the amount of NO_x (mainly NO) yielded greater decrease with increasing atmospheric pressure as compared to the amounts of CO and NH₃. Thus, provided GN/BCN is ignited in a closed container, a large amount of NO_x is presumed to have been released during the initial stage of combustion, which yielded comparatively low pressure. Results of the thermogravimetry–differential scanning calorimetry–Fourier transform infrared spectroscopy (TG/DSC/FTIR) indicated that the GN/BCN mixture caused endothermic decomposition at 170 °C and exothermic decomposition at 208 °C, which was accompanied by 66% mass loss. The decomposition gases, CO₂, N₂O, and H₂O, were detected via FTIR spectrum. Because N₂O was not detected in the combustion gas, it was suggested that the detected N₂O was generated at a low temperature and decomposed in high-temperature combustion.     

New thermal study of polymerization and degradation kinetics of methylene diphenyl diisocyanate

Journal of Thermal Analysis and Calorimetry - This work investigates the thermal polymerization process of a methylene diphenyl diisocyanate (MDI) monomer as well as its thermal degradation...     

Dual‐Input Regulation and Positional Control in Hybrid Oligonucleotide/Discotic Supramolecular Wires

The combination of oligonucleotides and synthetic supramolecular systems allows for novel and long‐needed modes of regulation of the self‐assembly of both molecular elements. Discotic molecules were conjugated with short oligonucleotides and their assembly into responsive supramolecular wires studied. The self‐assembly of the discotic molecules provides additional stability for DNA‐duplex formation owing to a cooperative effect. The appended oligonucleotides allow for positional control of the discotic elements within the supramolecular wire. The programmed assembly of these hybrid architectures can be modulated through the DNA, for example, by changing the number of base pairs or salt concentration, and through the discotic platform by the addition of discotic elements without oligonucleotide handles. These hybrid supramolecular‐DNA structures allow for advanced levels of control over 1D dynamic platforms with responsive regulatory elements at the interface with biological systems.