Synthesis and characterization of modular polyphosphonate homopolymers and copolymers

Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]_n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt₂)₂ and a diol (HOR′OH = 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, tetraethylene glycol, or 1,12-dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt₂)₂ and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O]_{(x + 2)} –[P(Ph)(X)OR′O]_{(x + 3)}– (X = S or Se) have been synthesized by the polycondensations of Et₂N[P(Ph)(X)OR′O]_{(x + 2)}P(Ph)NEt₂ oligomers with HOR′O[P(Ph)(X)OR′O]_{(x + 3)}H oligomers followed by reaction with a chalcogen. The Et₂N[P(Ph)(X)OR′O]_{(x + 2)}P(Ph)NEt₂ oligomers are prepared by the reaction of an excess of P(Ph)(NEt₂)₂ with a diol while the HOR′O[P(Ph)(X)OR′O]_{(x + 3)}H oligomers are prepared by the reaction of P(Ph)(NEt₂)₂ with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using ¹H, ¹³C{¹H}, and ³¹P{¹H} NMR spectroscopy, TGA, DSC, and SEC. ³¹P{¹H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and T_g profiles. The polymers have weight average MWs of up to 3.8 × 10⁴ Da.     

Quantitative 31P‐NMR spectroscopy for the determination of fosfomycin and impurity A in pharmaceutical products of fosfomycin sodium or calcium

A quantitative ³¹P‐NMR method for the determination of fosfomycin and impurity A in pharmaceutical products of fosfomycin sodium or calcium has been developed. In this method, coaxial inserts containing trimethyl phosphate are used as external standard. The method is convenient and robust, and gives both high accuracy and precision. It is shown that an accurate determination is possible using different probes and coaxial inserts. Copyright © 2015 John Wiley & Sons, Ltd.     

Elucidating structure and dynamics of crystalline α-zirconium phosphates intercalated with water and methanol by multinuclear solid-state MAS NMR: A comprehensive NMR approach

Solid-state NMR experiments on ²H, ³¹P, ¹³C, and ¹H nuclei, including ³¹P T₁, ¹H T₁, and ¹H T_1ρ measurements, as well as on the kinetics of proton-phosphorus cross-polarization have been performed to characterize the crystalline and amorphous α-zirconium phosphates, which were intercalated with D₂O and/or CD₃OD. The ¹³C{¹H} CP MAS NMR experiment performed for compound 1-CD ₃ OD (Zr (HPO₄)₂ ^. 0.2CD₃OD) with carbon cross-polarization via protons of phosphate groups has provided a prove that the methanol was intercalated into the interlayer spaces of this compound. The variable-temperature ²H solid-echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD₃ rotations around the C₃-axis. It has been demonstrated that the intercalated species, D₂O and CD₃OD, do not affect the high-frequency motions of the phosphate groups. By utilizing local structural models that satisfy the constraints of the experimental data, it has been suggested that the immobile methanol molecules are located in the cavity between two neighboring layers of the zirconium phosphates. Thus, the present work illustrates the reliable criteria in a comprehensive NMR approach to structural and dynamic studies of such systems.     

Packing,covering and tiling in two-dimensional spaces

Packing, covering and tiling is a fascinating subject in pure mathematics. It mainly deals with arrangement patterns and efficiencies of geometric objects. This subject has a long and rich history, even back to Kepler, Newton, Lagrange and Gauss. Inspired by its applications and with the help of computing methods, in recent years it has become a very active research area in mathematics once again. Most of the fundamental problems in this subject can be characterized as simple sounding but challenging. This subject has important applications in many other areas such as Number Theory, Logic, Complex Analysis, Optimization, Coding Theory, Crystallography, Material Science, Industry, and even Biology. In spite of the long history, many of its key problems are still open, even in the plane. The purpose of this paper is to present a comprehensive review for packing, covering and tiling in the two-dimensional spaces. We will focus on the key problems, the fundamental results, the creative ideas, some important applications, and some significant connections with other areas.     

Quasiregular maps on Carnot groups

In this paper we initiate the study of quasiregular maps in a sub-Riemannian geometry of general Carnot groups. We suggest an analytic definition for quasiregularity and then show that nonconstant quasiregular maps are open and discrete maps on Carnot groups which are two-step nilpotent and of Heisenberg type; we further establish, under the same assumption, that the branch set of a nonconstant quasiregular map has Haar measure zero and, consequently, that quasiregular maps are almost everywhere differentiable in the sense of Pansu. Our method is that of nonlinear potential theory. We have aimed at an exposition accessible to readers of varied background. Dedicated to Seppo Rickman on his sixtieth birthday J.H. was partially supported by NSF, the Academy of Finland, and the A. P. Sloan Foundation. I.H. was partially supported by the EU HCM contract no. CHRX-CT92-0071.     

A Characterization of Monotone and Regular Divergences

In this paper we characterize the local structure of monotone and regular divergences, which include f-divergences as a particular case, by giving their Taylor expansion up to fourth order. We extend a previous result obtained by 31u2w0563655/xxlarge268.gif" alt="Ccaron" align="BASELINE" BORDER="0">encov, using the invariant properties of Amari's 31u2w0563655/xxlarge945.gif" alt="agr" align="BASELINE" BORDER="0">-connections.     

Conformations of 2-C:1-N-carbonyl-2-deoxy-d-glycopyranosylamines

Geometry and molecular conformation of theN-toluenesulfonyl1 andN-acetyl-2 derivatives of peracetylated 2-C:1-N-carbonyl-2-deoxy-31p50746/xxlarge945.gif" alt="agr" align="BASELINE" BORDER="0">-d-glucopyranosylamine were investigated with the use of X-ray diffraction methods. Compound1 (C₂₀H₂₃NSO₁₀) crystallizes in the monoclinic P2₁ space group, withZ=2 anda=8.238(1),b=7.988(1),c=16.928(2)Å, 31p50746/xxlarge946.gif" alt="beta" align="MIDDLE" BORDER="0">=99.12(1)°. Compound2 (C₁₅H₁₉NO₉) crystallizes in orthorhombic P2₁2₁2₁ space group withZ=4 anda=8.385(1),b=8.550(1),c=24.000(2) Å. Analysis of differences in bond lengths and angles between compounds1 and2 and other compounds of this class showed that the electronwithdawing effect by the residue located at the nitrogen atom can be manifested by lengthening of the 31p50746/xxlarge946.gif" alt="beta" align="MIDDLE" BORDER="0">-lactam C-N bonds, with simultaneous shortening of the distance between two carbon atoms at the ring fusion. Semi-empirical calculations suggested that the title compounds displayed two positively charged centers, susceptible for attack of nucleophiles, one at the carbonyl group of 31p50746/xxlarge946.gif" alt="beta" align="MIDDLE" BORDER="0">-lactam and the second at the anomeric carbon atom. Atomic charges, however, calculated for compounds1 and2 did not explain their different reaction directions during alcoholysis.Part 3. For part 1 and 2, see Refs. 5 and 6.     

AZ31B镁合金I型材室温弯曲成型研究

由于镁合金AZ31B材料在拉伸与压缩时的力学性能差异,使AZ31B型材在室温下成型规律很难掌握.文章以AZ31B镁合金I型材为研究对象,通过对I型材弯曲过程的数值分析,研究了I型材成型过程与加强筋的高度与厚度的关系,同时对成型过程中的受力、回弹现象及翘曲做了深入的分析,得出了对工程有实用性的结论,可以指导工程实际.