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511.
Gaudreault R Whitehead MA van de Ven TG 《The journal of physical chemistry. A》2006,110(10):3692-3702
Describing interactions among large molecules theoretically is a challenging task. As an example, we investigated gas-phase interactions between a linear nonionic oligomer and various model compounds (cofactors), which have been reported to associate experimentally, using PM3 semiempirical molecular orbital theory. As oligomer, we studied the hexamer of poly(ethylene oxide) (PEO), and as cofactors, we studied corilagin and related compounds containing phenolic groups (R-OH). These systems are of interest because they are models for PEO/cofactor flocculation systems, used in industrial applications. The PM3 delocalized molecular orbitals (DLMO) describe the bonding between (PEO)6 and cofactors, and some of them cover the complete complex. The DLMOs which cover the traditionally considered hydrogen bonds R-OH...O or R-CH...O show a distinct "pinch", a decrease of the electron density, between the H...O atoms. Calculations of Gibbs free energy, entropy, and enthalpy show that the PEO/cofactor complexes do not form at room temperature, because the loss of entropy exceeds the increase in enthalpy. The change in enthalpy is linearly related to the change in entropy for the different complexes. Even though bond lengths, bond angles, DLMOs, and electron densities for the PEO/cofactor complexes are consistent with the definition of hydrogen bonds, the number of intermolecular R-OH...O and R-CH...O bonds does not correlate with the enthalpy of association, indicating that the bonding mechanism for these systems is the sum of many small contributions of many delocalized orbitals. 相似文献
512.
Xiao S Tang J Beetz T Guo X Tremblay N Siegrist T Zhu Y Steigerwald M Nuckolls C 《Journal of the American Chemical Society》2006,128(33):10700-10701
This study details a new derivative of the contorted HBCs that self-organizes into one-dimensional, single-crystalline fibers. X-ray diffraction, transmission electron microscopy, and electron diffraction studies show that they have an orthorhombic unit cell with dimensions of 5.8 nm x 4.5 nm x 0.45 nm. Each fiber is composed of a few thousands columns. A method is put forth that utilizes elastomer stamps to manipulate and position isolated fibers in organic field effect transistors. 相似文献
513.
Middle Infrared Spectroscopy (Mid-IR) and Infrared Emission Spectroscopy (IES) were employed to characterise Cu-exchanged montmorillonites, which were derived from two different types of montmorillonite clays, Ca-exchanged montmorillonite (Cheto clay) and Na-exchanged montmorillonite (Miles clay). Copper was exchanged under both acidic and basic conditions at different Cu/clay ratios. All Cu-exchanged montmorillonites experienced a shift in most of non-lattice bands, with hydroxyl bands playing a major role in the characterisation of the clays. Furthermore, a relationship between the ratio of bands at 3630 and 3500 cm(-1) and the Cu concentration of the starting solutions was indicated and used to compare the degree of cation exchange between two preparation methods. Two dehydration stages were observed in the IES experiments. Additional bands were observed in all Cu-exchanged montmorillonites prepared with the 'basic conditions method,' and these bands were assigned to ammonia molecules trapped within the clay structure or absorbed on the surface of the clay. 相似文献
514.
Christian S. Schacht Sara Bahramali Daniel Wilms Holger Frey Joachim Gross Theo W. de Loos 《Fluid Phase Equilibria》2010
Phase equilibrium data have been measured for the ternary system hyperbranched polyglycerol + methanol + carbon dioxide at temperatures of 313–450 K and pressures up to 13.5 MPa. Phase changes were determined according to a synthetic method using the Cailletet setup. At elevated temperatures the system shows a liquid–liquid–vapor region with lower solution temperatures. Besides the vapor–liquid and liquid–liquid equilibria, the vapor–liquid to vapor–liquid–liquid and vapor–liquid–liquid to liquid–liquid phase boundaries are reported at different polymer molar masses and can serve as test sets for thermodynamic models. A distinct influence of the polymer molar mass on the vapor–liquid equilibrium can be noticed and indicates the existence of structural effects due to the polymer branching. Modeling the systems with the PCP-SAFT equation of state confirms these findings. 相似文献
515.
Theo Fromme Lucie K. Tintrop Dr. Sven Reichenberger Prof. Dr. Torsten C. Schmidt Prof. Dr. Stephan Barcikowski 《Chemphyschem》2023,24(11):e202300089
Laser ablation in liquids has been established as a scalable preparation method of nanoparticles for various applications. Particularly for materials prone to oxidation, it is established to suppress oxidation by using organic solvents as a liquid medium. While this often functionalizes the nanoparticles with a carbon shell, the related chemical processes that result from laser-induced decomposition reactions of the organic solvents remain uncertain. Using a systematic series of C6 solvents complemented by n-pentane and n-heptane during the nanosecond laser ablation of gold, the present study focuses on the solvent-dependent influence on gas formation rates, nanoparticle productivity, and gas composition. Both the permanent gas and hydrogen formation was found to be linearly correlated with ablation rate, ΔHvap, and pyrolysis activation energy. Based on this, a decomposition pathway linked to pyrolysis is proposed allowing the deduction of first selection rules for solvents that influence the formation of carbon or permanent gases. 相似文献
516.
Ralph J.S. van Mechelen Jarno E.J. Wolters Sebastian Fredrich Christian J.F. Bertens Marion J.J. Gijbels Albert P.H.J. Schenning Leonard Pinchuk Theo G.M.F. Gorgels Henny J.M. Beckers 《Macromolecular bioscience》2023,23(10):2300075
Fibrosis of the filtering bleb is one of the main causes of failure after bleb-forming glaucoma surgery. Intraoperative application of mitomycin C (MMC) is the current gold standard to reduce the fibrotic response. However, MMC is cytotoxic and one-time application is often insufficient. A sustained-release drug delivery system (DDS), loaded with MMC, may be less cytotoxic and equally or more effective. Two degradable (polycaprolactone (PCL) and polylactic-co-glycolic acid (PLGA)) MMC-loaded DDSs are developed. Release kinetics are first assessed in vitro followed by rabbit implants in conjunction with the PRESERFLO MicroShunt. As a control, the MicroShunt is implanted with adjunctive use of a MMC solution. Rabbits are euthanized at postoperative day (POD) 28 and 90. The PLGA and PCL DDSs release (on average) 99% and 75% of MMC, respectively. All groups show functioning blebs until POD 90. Rabbits implanted with a DDS show more inflammation with avascular thin-walled blebs when compared to the control. However, collagen is more loosely arranged. The PLGA DDS shows less inflammation, less foreign body response (FBR), and more complete degradation at POD 90 when compared to the PCL DDS. Further optimization with regard to dosage is required to reduce side effects to the conjunctiva. 相似文献
517.
518.