Synthesis and crystal structures of novel glycoluril carboxylic acids conglomerates

The two novel conglomerates were obtained by crystallization of racemic (2'S,3aS,6aR)/(2'R,3aR,6aS) (glycoluril-1-yl)-3-methylbutanoic acid and (2'R,3aR,6aR)/(2'S,3aS,6aS) (4,6-dimethylglycoluril-1-yl)pentanoic acid synthesized by highly diastereoselective condensation of 4,5-dihydroxy- imidazolidin-2-ones with racemic ureido acids. The differences in the molecular geometry of synthesized racemates were studied by X-ray diffraction that showed them to crystallize as conglomerates in non-centrosymmetric space groups Pna2₁ and P2₁2₁2₁, respectively     

TDPAC and first-principles study of electronic and structural properties of a Pd-vacancy complex in undoped germanium

Pd is one of the metals suitable for inducing low-temperature crystallization in Ge. However, it is not clear how residual Pd atoms are integrated into the Ge lattice. Therefore, time-differential γ–γ perturbed angular correlations (TDPAC) technique using the ¹⁰⁰Pd(→¹⁰⁰Rh) nuclear probe produced by recoil implantation has been applied to study the hyperfine interactions of this probe in single-crystalline undoped Ge. A Pd-vacancy complex aligned along the <111> crystallographic direction with a unique interaction frequency of 8.4(5) Mrad/s has been identified. This complex was measured to have a maximum relative fraction of about 76(4)% following annealing at 350 ^°C. Further annealing at higher temperatures reduced this fraction, possibly via dissociation of the complex. Calculations suggest dissociation energy of 1.94(5) eV for the complex. DFT calculations performed in this work are in reasonable good agreement with the experimental values for the electric-field gradient of the defect complex in Ge and Si for comparison. The calculations predict a split-vacancy configuration with the Pd on a bond-centred interstitial site having a nearest-neighbour semi-vacancy on both sides (V-Pd_BI-V) in Ge and Si.     

Study on the Relationship between Emulsion Properties and Interfacial Rheology of Sugar Beet Pectin Modified by Different Enzymes

The contribution of rheological properties and viscoelasticity of the interfacial adsorbed layer to the emulsification mechanism of enzymatic modified sugar beet pectin (SBP) was studied. The component content of each enzymatic modified pectin was lower than that of untreated SBP. Protein and ferulic acid decreased from 5.52% and 1.08% to 0.54% and 0.13%, respectively, resulting in a decrease in thermal stability, apparent viscosity, and molecular weight (Mw). The dynamic interfacial rheological properties showed that the interfacial pressure and modulus (E) decreased significantly with the decrease of functional groups (especially proteins), which also led to the bimodal distribution of particle size. These results indicated that the superior emulsification property of SBP is mainly determined by proteins, followed by ferulic acid, and the existence of other functional groups also promotes the emulsification property of SBP.     

Pulse radiolysis study of the initial steps of the polymerization of cyclohexyl acrylate and cyclohexyl methacrylate

Pulse radiolysis with kinetic spectroscopic detection was applied to study the kinetics of the first steps of radiation induced polymerization of cyclohexyl acrylate and cyclohexyl methacrylate in cyclohexane solvent. The reactions were initiated by cyclohexyl radicals produced in the radiolysis of the solvent. The transient absorption spectra of the -carboxyalkyl type radicals produced in addition reaction show maxima around 300 nm. This shifts to longer wavelength with time after the pulse. This phenomenon was explained by the oligomerization reaction. From the kinetic curves average rate coefficients of termination for the oligomer radicals (2k_t) were determined as a function of time elapsed after the electron pulse. The values obtained were compared with those calculated for other (acrylate and methacrylate type) monomers.     

烟气中Hg的氧化机理的研究

本文对Ｈｇ与Ｃｌ２在烟气中的氧化反应进行了热力平衡计算和动力学计算。平衡计算的结果表明有ＣＩ元索存在时Ｈｇ的氧化率为１００％，而在相同的条件下动力学计算纺果为Ｈｇ的氧化率在２０％～８０％之间变化，与实验结果吻合。实际的氧化反应是一种超平衡状态，不能达到理想的平衡状态。因此应采用动力学与热力平衡分析相结合的方法研究Ｈｇ在烟气中的反应机理。同时，计算结果显示Ｃｌ含量对Ｈｇ的氧化率的影响很大．     

New ligands for the Fe(III)‐mediated reverse atom transfer radical polymerization of methyl methacrylate

A series of (di)picolinic acids and their derivates are investigated as novel complexing tridentate or bidentate ligands in the iron‐mediated reverse atom transfer radical polymerization of methyl methacrylate in N,N‐dimethylformamide at 100 °C with 2,2′‐azobisisobutyrontrile as an initiator. The polymerization rates and polydispersity indices (1.32–1.8) of the resulting polymers are dependent on the structures of the ligands employed. Different iron complexes may be involved in iron‐mediated reverse atom transfer radical polymerization, depending on the type of acid used. ¹H NMR spectroscopy has been used to study the structure of the resulting polymers. Chain‐extension reactions have been performed to further confirm the living nature of this catalytic system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2912–2921, 2006     

Nanostructured thermoset epoxy resin templated by an amphiphilic poly(ethylene oxide)‐block‐poly(dimethylsiloxane) diblock copolymer

An amphiphilic poly(ethylene oxide)‐block‐poly(dimethylsiloxane) (PEO–PDMS) diblock copolymer was used to template a bisphenol A type epoxy resin (ER); nanostructured thermoset blends of ER and PEO–PDMS were prepared with 4,4′‐methylenedianiline (MDA) as the curing agent. The phase behavior, crystallization, hydrogen‐bonding interactions, and nanoscale structures were investigated with differential scanning calorimetry, Fourier transform infrared spectroscopy, transmission electron microscopy, and small‐angle X‐ray scattering. The uncured ER was miscible with the poly(ethylene oxide) block of PEO–PDMS, and the uncured blends were not macroscopically phase‐separated. Macroscopic phase separation took place in the MDA‐cured ER/PEO–PDMS blends containing 60–80 wt % PEO–PDMS diblock copolymer. However, the composition‐dependent nanostructures were formed in the cured blends with 10–50 wt % PEO–PDMS, which did not show macroscopic phase separation. The poly(dimethylsiloxane) microdomains with sizes of 10–20 nm were dispersed in a continuous ER‐rich phase; the average distance between the neighboring microdomains was in the range of 20–50 nm. The miscibility between the cured ER and the poly(ethylene oxide) block of PEO–PDMS was ascribed to the favorable hydrogen‐bonding interaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3042–3052, 2006