Facile Preparation of Organometallic Nanorods from Various Ethynyl-Substituted Molecules

A facile method to prepare one-dimensional (1D) organometallic nanomaterials from various ethynyl-substituted molecules is reported. The reactions of 3-chloro-1-ethynylbenzene, p-tBu-phenylacetylene and 4-ethynylbiphenyl with Cu⁺ ions in acetonitrile yield nanorod-shaped copper acetylides (Cu−C≡C−R) crystals. In the case of linear alkynes, namely, propyne, 1-pentyne and 1-hexyne, it was found that using an aqueous ammonia/ethanol mixed solvent instead of acetonitrile is a better approach to obtain 1D nanostructures. This procedure also enables us to prepare functional 1D nanomaterials. We demonstrate the preparation of a paramagnetic nanorod from the organic radical p-ethynylphenyl nitronyl nitroxide, and fluorescent nanorods from 9-ethynylphenanthrene and 2-ethynyl-9,9′-spirobifluorene.     

The virtual origin of riblets in an open channel flow

In this paper, a method using the mean velocity profiles for the buffer layer was developed for the estimation of the virtual origin over a riblets surface in an open channel flow. First, the standardized profiles of the mixing length were estimated from the velocity measurement in the inner layer, and the location of the edge of the viscous layer was obtained. Then, the virtual origins were estimated by the best match between the measured velocity profile and the equations of the velocity profile derived from the mixing length profiles. It was made clear that the virtual origin and the thickness of the viscous layer are the function of the roughness Reynolds number. The drag variation coincided well with other results.Nomenclature f _r skin friction coefficient - f _ro skin friction coefficient in smooth channel at the same flow quantity and the same energy slope - g gravity acceleration - H water depth from virtual origin to water surface - H ⁺ u*H/ - H false water depth from top of riblets to water surface - H ⁺ u*H/ - I _e streamwise energy slope - I _b bed slope - k riblet height - k ⁺ u*k/ - l mixing length - l _s standardized mixing length - Q flow quantity - Re Reynolds number volume flow/unit width/v - s riblet spacing - u mean velocity - u* friction velocity = - u* false friction velocity = - y distance from virtual origin - y distance from top of riblet - y ₀ distance from top of riblet to virtual origin - y _v distance from top of riblet to edge of viscous layer - y ⁺ u*y/ - y ⁺ u*y/ - y ₀ ⁺ u*y ₀/ - u ⁺ u*y/ - shifting coefficient for standardization - thickness of viscous layer=y ₀+y - ⁺ u*/ - ⁺ u*/ - eddy viscosity - ridge angle - v kinematic viscosity - density - shear stress     

Novel functional polymers: Poly(dimethyl siloxane)–polyamide multiblock copolymers. XI. The effects of sequence regularity on the thermal and mechanical properties

Poly(aramid silicone) (PAS) multiblock copolymers were synthesized by the low‐temperature solution polycondensation of isophthaloyl dichloride (IPC) and two diamines, diamino poly(dimethyl siloxane) (PDMS; number‐average molecular weight = 1680) and 3,4′‐diaminodiphenylether (3,4′‐DAPE), in tetrahydrofuran/dimethylacetamide (2/1 v/v). Two synthetic methods for the control of the PAS sequence were used: a one‐step synthesis that presumably gave PAS with a random sequence and the polymerization of 3,4′‐DAPE with a presynthesized dimer, IPC–PDMS–IPC (two‐step synthesis), that presumably gave PAS with an alternating sequence of 3,4′‐DAPE and PDMS segments. In a ¹H NMR study of the amide protons of the 3,4′‐DAPE component in PAS, the relative length of the 3,4′‐DAPE segment of randomly sequenced PAS to that of ideally sequenced PAS could be estimated. The glass‐transition temperatures of the 3,4′‐DAPE and PDMS segments of random PAS were 152–234 and ?104 to ?117 °C, respectively, whereas the alternating PAS sequences showed no glass transition for the 3,4′‐DAPE segments. A tensile test indicated that randomly sequenced PAS behaved like a rubber‐toughened material at lower PDMS contents and like a thermoplastic elastomer at higher PDMS contents, whereas the alternately sequenced PAS behaved like a very soft rubber, showing a high value of elongation at the breaking point. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 841–852, 2003     

Denaturation of alpha-lactalbumin and ubiquitin studied by electrospray and laser spray

Electrospray and laser spray mass spectra of human alpha-lactalbumin and bovine ubiquitin were studied, with an emphasis on the denaturation induced by laser spray. There were no remarkable differences in the electrospray and laser spray mass spectra for acidic and basic aqueous solutions of alpha-lactalbumin in positive and negative modes of operations. This originates from the fact that this protein is tightly folded with four disulfide bonds. For ubiquitin, however, denaturation was induced by laser spray for the positive mode of operation and the [M+nH](n+) with a maximum of n = 13 was observed, i.e., all the acidic amino acid residues are fully neutralized (protonated). In contrast, the laser-induced denaturation was not observed for the negative mode of operation, i.e., denaturation of ubiquitin is largely suppressed in the negatively charged liquid droplets. The marked difference observed in the positive and negative modes of operations for ubiquitin is ascribed to the difference in the susceptibility of side-chain/main-chain interactions in the positive-ion excess and in the negative-ion excess liquid droplets. That is, the interactions between the basic residues and main-chain amide carbonyl groups (-NH(3) (+)***O=C< or -NH(2)***O=C<) which play an important role in stabilizing the protein structures are not so affected in the negative mode of operation but are weakened in the positive mode of operation.     

Impact of limited oxidation on protein ion mobility and structure of importance to footprinting by radical probe mass spectrometry

The effect of hydroxyl radical induced oxidation on the collision cross-sections of hen egg lysozyme and bovine ubiquitin was investigated by travelling wave ion mobility mass spectrometry for the first time. The oxidized ions of lysozyme and ubiquitin share common collision cross-sections with their unoxidized counterparts suggesting that they share common structures that were unaffected by limited oxidation. In the case of bovine ubiquitin, two distinct conformers were detected for the protein in its unoxidized and oxidized states though no change in the levels of each was observed upon oxidation. This supports the validity of Radical Probe Mass Spectrometry (RP-MS) using an electrical discharge source for protein footprinting experiments. Travelling wave ion mobility mass spectrometry has been used for the first time to confirm that limited oxidation does not have an impact on the global structure of proteins.     

Effects of a vanadate-support on the reactivity of theBis(Methallyl)Rhodium Complex [{(η3-C4H7)2Rh}2(V4O12)]2−. A comparison with the acetylacetonato complex

The methallyl moieties of [{(³-C₄H₇)₂Rh}₂(V₄O₁₂)]^2– couple to yield 2,5-dimethyl-1,5-hexadiene in a selective manner by the action of P(OEt),₃, while the reaction of [( ³-C₄H₇)₂ Rh(acac)] with P(OEt)₃ produces a mixture of organic compounds. The result shows that the vanadate support has a significant influence on the reactivity of organometallic complexes.     

Synthesis and Characterization of Samarium （Ⅲ） Containing Poly-（N-vinylacetamide） Complex

Poly (N-vinylacetamide) (PNVA) was synthesized by the free radical polymerization and its samarium (Ⅲ) binary complex was prepared and characterized by means of IR, UV-vis, X-ray photoelectron spectroscopy (XPS) and fluorescence spectra. The fluorescent intensity of samarium (Ⅲ) characteristic emission was increased significantly due to efficient energy transfer from polymeric ligand to Sm (Ⅲ) ion in the complex.     

Cationic polymerization with p-substituted benzyl p-hydroxyphenyl methyl sulfonium salts: Effect of substituents and mechanistic aspects of initiation reaction

Various p-substituted benzyl p-hydroxyphenyl methyl sulfonium salts ( 2 ) were synthesized and their initiator activities were evaluated in bulk polymerization of glycidyl phenyl ether (PGE). The order of the activity was found to be 2b (X = CH₃) > 2a (X = H) ≈ 2c (X = Cl) > 2d (X = NO₂), indicating that the introduction of an electron-donating group enhanced the activity. In Hammett's plots, the logarithm of the ratio of the polymerization rates (log k_x/k_H) was correlated with σ⁺_ρ better than with σ_p and a negative ρ⁺ value (-1.18) was obtained. Reaction of 2a with benzyl mercaptan mainly gave dibenzyl sulfide and p-hydroxyphenyl methyl sulfide. The obtained results seemed to demonstrate that the OH group of the aryl group yielded no proton as initiator for the polymerization, whereas the benzyl group caused the polymerization, which was initiated by the corresponding benzyl cation formed by C? S bond cleavage. © 1993 John Wiley & Sons, Inc.     

特殊形态接枝高分子颗粒的合成

表面接枝高分子微球具有分子结构的可设计性 ,分散稳定性好 ,被用于高效催化剂的载体、药物释放控制和疾病治疗等生物医学领域 ,因而引起了许多高分子材料和生物医学工作者的极大兴趣[1～ 3] .我们用链转移自由基聚合法合成了一端为苯乙烯基封端的聚乙二醇 ( PEG)和聚 ( N -异丙基丙烯酰胺 )等亲水性大分子单体 .在与疏水性单体如苯乙烯等的二元分散共聚反应中 ,利用接枝共聚物在溶液中的自组装 ,制备了粒径分布均一 ,颗粒表面形态光滑 ,同时表面具有功能性高分子链的微球 [4～ 8] .传统的合成高分子微球的研究主要是以苯乙烯或甲基丙烯酸…