Calorimetric Behaviour of Anhydrous β-Cyclodextrin at Very Low Temperature

Heat capacities of anhydrous -cyclodextrin were measured between 10 K to 300 K using an adiabatic low-temperature calorimeter. Two distinct types of thermal behaviour were observed in the temperature range 50–130 K, depending on the way the sample was cooled. In the absence of hydration water molecules, we assumed that the two types of thermal behaviour could be attributed to freezing in more or less ordered states of the hydroxyl groups engaged in the intramolecular interglucose flip-flop-type interactions.     

Study of Very Low Temperature Crystallization Process in Ethylene/α-Olefin Copolymers

Summary: The crystallization behavior of Ziegler-Natta (ZN) and single site (SS) based ethylene/1-butene and ethylene/1-hexene copolymers and SS copolymer fractionated by composition and molar mass (MM) has been studied by differential scanning calorimetry. It was observed that in addition to the high temperature crystallization peak (HTCP), and for ZN copolymers in addition also to low temperature crystallization peak (LTCP), a very-low temperature crystallization peak (VLTCP) is present at temperatures in between 60–75 °C. Peak temperature of VLTCP, T_VLTCP, decreases with increasing comonomer content (C_comon) at fixed MM. If C_comon is kept approximately constant, T_VLTCP increases with increasing MM. It turns out that T_VLTCP does not depend on the type of catalyst used. The degree of crystallinity calculated from the VLTCP is independent of the chemical nature of the comonomers present, but slightly changes with C_comon. It also steeply increases with MM and levels off at MM around 50 kg/mol. It was found that the crystallinity as related to the area of the VLTCP is catalyst type dependent, and is higher for the SS catalyst used compared to the ZN catalyst.     

Very empirical treatment of solvation and entropy: a force field derived from Log Po/w

A non-covalent interaction force field model derived from the partition coefficient of 1-octanol/water solubility is described. This model, HINT for Hydropathic INTeractions, is shown to include, in very empirical and approximate terms, all components of biomolecular associations, including hydrogen bonding, Coulombic interactions, hydrophobic interactions, entropy and solvation/desolvation. Particular emphasis is placed on: (1) demonstrating the relationship between the total empirical HINT score and free energy of association, G _interaction; (2) showing that the HINT hydrophobic-polar interaction sub-score represents the energy cost of desolvation upon binding for interacting biomolecules; and (3) a new methodology for treating constrained water molecules as discrete independent small ligands. An example calculation is reported for dihydrofolate reductase (DHFR) bound with methotrexate (MTX). In that case the observed very tight binding, G _interaction–13.6 kcal mol^–1, is largely due to ten hydrogen bonds between the ligand and enzyme with estimated strength ranging between –0.4 and –2.3 kcal mol^–1. Four water molecules bridging between DHFR and MTX contribute an additional –1.7 kcal mol^–1 stability to the complex. The HINT estimate of the cost of desolvation is +13.9 kcal mol^–1.     

Very long-distance magnetic coupling in a dicopper(II) metallacyclophane with extended π-conjugated diphenylethyne bridges

Self-assembly of the rigid rodlike ligand N,N'-4,4'-diphenylethynebis(oxamate) (dpeba) and Cu(2+) ions affords a novel dinuclear copper(II) metallacyclophane (nBu(4)N)(4)[Cu(2)(dpeba)(2)]·4MeOH·2Et(2)O (1) featuring a very long intermetallic distance (r = 15.0 ?). Magnetic susceptibility measurements for 1 reveal a moderately weak but nonnegligible intramolecular antiferromagnetic coupling between the two metal centers across the double para-substituted diphenylethynediamidate bridge (J = -3.9 cm(-1); H = -JS(1)S(2), where S(1) = S(2) = S(Cu) = (1)/(2)). Density functional electronic structure calculations on 1 support the occurrence of a spin polarization mechanism.     

Very short OH?hydrogen bond in l-histidinium difluoride

The crystal structure of C₆H₁₁N₃O₂²⁺·2F²⁻ is reported. The structure contains a fluoride ion strongly H-bonded to a carboxylic O atom, a rare, very strong, hydrogen bond. The donor-acceptor distance is 2.3818(10) Å, the shortest value reported to date, considerably less than the sum of the van der Waals radii of the atoms implicated, as expected from a very strong hydrogen bond. The di-cation has an open conformation. There is an extensive H-bonding network between anions and cations assembling rings on the ac plane and chains in several directions. Two extra intermolecular interactions of the type CH?π are found, exhausting the aromatic π electron system ability to act as a proton acceptor.     

Influence of the Water Content on the Thermal Behaviour of β-Cyclodextrin at Low and Very Low Temperature

Heat capacities of -CD·9.7H₂O weremeasured by adiabatic calorimetry in the temperature range10–300 K. Differential scanning calorimetry wasused to follow the evolution of the thermalbehaviour versus hydration ratio between 170 and300 K. At least three different behaviours wereobserved, according to the number, n, of watermolecules: 0 < n < 7, 7 < n < 10, and n > 10.These macroscopic results are discussed in terms oforganization differences between the most or theleast hydrated -CD. The structuring effectof the hydration water molecules is emphasised. Theexistence of two energetically distinct -CDhydrates (n < 10 and n > 10) seems to be confirmed. Thishypothesis is discussed in comparison with previousspectroscopic and structural studies.     

A Paramagnetic Diniobium Complex with a Very Short Nb-Nb Distance: Evidence for a Pseudo Nb-Nb Triple Bond?

In spite of the short Nb-Nb distance (2.268 ?) and the presumable existence of an Nb identical withNb bond, the paddle-wheel-shaped diniobium(II) complex 1 is paramagnetic. Theoretical calculations indicate that the presence of LiCl moieties on the intermetallic axis lowers the Nb-Nb bond order and is responsible for the observed paramagnetism.     

Degradation of the Side Chain of (−)‐Sclareol: A Very Short Synthesis of nor‐Ambreinolide and Ambrox

Abstract

The synthesis of nor‐Ambreinolide (8) from (‐)‐sclareol (1) was carried out by treatment with KMnO₄‐Ac₂O and further alkaline hydrolysis. 8 was directly transformed into (‐)‐ambrox (11) by reduction with metal borohydride in the presence of Lewis acids.     

Very sensitive differential pulse adsorptive stripping voltammetric determination of 4-nitrophenol at poly (diphenylamine)/multi-walled carbon nanotube-β-cyclodextrin-modified glassy carbon electrode

In this work, a glassy carbon electrode (GCE) modified with poly (diphenylamine)/multi-walled carbon nanotubes-β-cyclodextrin (PDPA/MWCNT-β-CD) film was constructed and used for the determination of 4-nitrophenol (4-NP). Diphenylamine was successfully electropolymerised onto MWCNT-β-CD-modified GCE by cyclic voltammetry in monomer solution and 5 mol L^?1 H₂SO₄. The surface morphology of PDPA/MWCNT-β-CD film was characterised using scanning electron microscopy and electrochemical impedance spectroscopy. After adsorption of 4-NP on PDPA/MWCNT-β-CD at 0.2 V for 150 s, it showed a well-defined reduction peak in phosphate buffer solution at pH = 7. The PDPA/MWCNT-β-CD film enhanced the reduction peak current due to the complex formation between β-CD and 4-NP, presence of conductive polymer film as electron transfer mediator and also ability of MWCNTs for strong adsorptive and catalytic effect. Peak current increased linearly with 4-NP concentration in the range of 0.1 to 13.9 µg L^?1. The detection limit was obtained as 0.02 µg L^?1, which is better than other reported detection limits for the determination of 4-NP. The results showed that modified electrode has good sensitivity and selectivity. This sensor was used for the determination of 4-NP in water samples.     

Very fast and efficient synthesis of some novel substituted 2-arylbenzimidazoles in water using ZrOCl2·nH2O on montmorillonite K10 as catalyst

Abstract  A simple and eco-friendly protocol for the synthesis of some novel substituted 2-arylbenzimidazoles was developed. In this process, these compounds were prepared in water as the solvent using ZrOCl₂·nH₂O supported on montmorillonite K10 as an efficient water tolerating Lewis acid. The reaction was performed under mild conditions with good to excellent yields and remarkable chemoselectivity in the absence of any byproduct. Graphical Abstract        

Silicon Oxide Coatings with Very High Rates (>10?nm/s) by Hexamethyldisiloxane-Oxygen Fed Atmospheric-Pressure VHF Plasma: Film-Forming Behavior Using Cylindrical Rotary Electrode

Silicon oxide films are deposited in atmospheric-pressure (AP) He/O₂/HMDSO plasma excited by a 150?MHz VHF power using a cylindrical rotary electrode. The atomic bonding configurations and deposition rate are studied by controlling the O₂ concentration (O₂/HMDSO source ratio) and VHF power density, the other parameters being maintained constant. Under the addition of 0.03?% O₂ to the process gas mixture (O₂/HMDSO????0.09), AP-VHF plasma greatly enhances the fragmentation and oxidation of HMDSO, so that an almost inorganic film is obtained at a very high deposition rate of 33?nm?s^?1. A silicon oxide coating on a polycarbonate pane is demonstrated with no significant thermal deformation of the pane, showing that AP-VHF plasma would be an efficient coating tool for polymer substrates.     

Theoretical Description of Excess Molar Functions in the Case of Very Small Excess Values. Investigation of Excess Molar Volumes of Propan-2-ol + Alkanol Mixtures

The densities of propan-2-ol + pentan-1-ol, + hexan-1-ol, + heptan-1-ol, + octan-1-ol + nonan-1-ol and speeds of sound in propan-2-ol + pentan-1-ol, + heptan-1-ol, + nonan-1-ol have been measured over the whole composition range at 298.15 K. Excess molar functions determined from the experimental data have been plotted as functions of composition. The excess molar volumes have been interpreted on the basis of the Symmetrical Extended Real Associated Solution Model (S-ERAS).