Cationic photopolymerization of cis‐2,3‐tetramethylene‐1,4,6‐trioxaspiro[4,4]nonane

The spiro‐orthoester, cis‐2,3‐tetramethylene‐1,4,6‐trioxaspiro[4,4]nonane (cis‐TTN) ( I ), underwent rapid cationic photopolymerization when exposed to UV light using diphenyliodonium salts as a photoinitiator. The polymer, poly[(trans‐OCB)_x′‐(cis‐OCB)_x″‐(CHO)_y] thus formed consisted of poly(trans‐2‐oxycyclohexyl butanoate) (trans‐OCB)_x′ ( II ), poly(cis‐2‐oxycyclohexyl butanoate) (cis‐OCB)_x″ ( III ), and poly‐ (1,2‐cyclohexene oxide) (CHO)_y segments, and no expected pure poly(ether‐ester), that is, poly(2‐oxycyclohexyl butanoate), was isolated. The structure of the polymer was identified, and the mechanism of the reaction was deduced. The polymer thus formed exhibited expansion in volume during cationic photopolymerization when compared to that obtained by conventional cationic polymerization using a Lewis acid (e.g., BF₃OEt₂, CH₃OSO₂CF₃, or SnCl₄) as an initiator, which demonstrated volume shrinkage during polymerization. The volume expansion of the polymer during polymerization was due to (1) the lower content of the higher density (CHO)_y segment in the polymer chain and, more importantly, (2) the higher and optimal mole ratio of (trans‐OCB)_x′ and (cis‐OCB)_x″ segments that led the polymer in a more disordered, less dense, and higher volumetric state. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3680–3690, 2009     

Synthesis and properties of chitosan‐based thermo‐ and pH‐responsive nanoparticles and application in drug release

In this research, thermo‐ and pH‐responsive nanoparticles with an average diameter of about 50–200 nm were synthesized via the surfactant‐free emulsion polymerization. The thermal/pH dual responsive properties of these nanoparticles were designed by the addition of a pH sensitive monomer, acrylic acid (AA), to be copolymerized with N‐isopropylacrylamide (NIPAAm) in a chitosan (CS) solution. The molar ratio of CS/AA/NIPAAm in the feed was changed to investigate its effect on structure, morphology, thermal‐ and pH‐responsive properties of the nanoparticles. It was found that CS‐PAA‐PNIPAAm nanoparticles could be well dispersed in the aqueous solution and carried positive charges on the surface. The addition of thermal‐sensitive NIPAAm monomer affected the polymerization mechanism and interactions between CS and AA. The particle size of the nanoparticles was found to be varied with the composition of NIPAAm monomer in the feed. The synthesized nanoparticles exhibited stimuli‐responsive properties, and their mean diameter thus could be manipulated by changing pH value and temperature of the environment. The nanoparticles showed a continuous release of the encapsulated doxycycline hyclate up to 10 days during an in vitro release experiment. The environmentally responsive nanoparticles are expected to be used in many fields such as drug delivery system. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2798–2810, 2009     

Analysis of multiple melting behavior of spherulites comprising ring‐band shell/ringless core in polymorphic poly(butylene adipate)

In‐depth interpretation of ring‐banded spherulitic morphology, crystals, polymorphism, and complex melting behavior in poly(1,4‐butylene adipate) (PBA) were analyzed via a procedure of designing composite core‐shell spherulites, in which two lamellar patterns (ring‐band vs. ringless) were packed by subjecting to crystallization at two‐step temperature schemes with specific temperatures and times. By heating to 52 °C and holding at that temperature for 30 min annealing, the core can be stripped off by melting, and analysis specifically on the ring‐shell portion (with the ringless core stripped by controlled melting) proves that the highest melting peak (P₄ at 55–57 °C) is likely associated with melting of the ring‐band lamellae. Furthermore, the unusually complex multiple melting in PBA can be attributed to all three widely proposed mechanisms: (1) multiple types of lamellae preexisting in crystallized PBA, (2) scan/heating induced remelting/reorganization, and (3) polymorphism of dual crystal cells. In addition, this study evidently shows that the extinction rings within the ring‐banded shell, regardless of alternate edge‐on and flat‐on mechanism or alternative origins, can be of all singly α‐crystal form, either initially or upon postheating temperature‐induced transformation. Thus, the type of crystal forms (α or β) in polymorphic PBA is mainly associated with temperature of crystallization (T_c = 28 or 35 °C), and not likely with lamellar orientation (flat‐on or edge‐on). © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 892–899, 2008     

Low-lying octupole excitations in 17O

Inelastic electron scattering experiments were performed on a¹⁷O gas target in a range of momentum transfer q = 0.6?1.1fm^?1; B(E3) values for twelve odd-parity levels were obtained from the measured Coulomb form factors. The results are discussed in terms of the weak coupling model.     

On the non-linear vibrations of a circular membrane

Free axisymmetric vibrations of a stretched circular membrane are studied using a membrane theory consisting of a pair of non-linear partial differential equations coupled between the transverse and radial displacements of the membrane. A systematic perturbation method, in which the amplitude of the transverse displacement is taken as the perturbation parameter, is used to obtain periodic solutions of the non-linear equations. The initial membrane strain enters the problem as a parameter which is allowed to vary over a range of values. A case of self-resonance is encountered when the initial membrane strain approaches some critical values. This self-resonance case is also treated through an appropriate modification of the perturbation method.     

On the response of an elastic membrane to a travelling ring load

Exact solutions in closed-form are presented for the dynamic response of an infinite elastic membrane to a suddenly applied, radially expanding ring load.     

对(mèng)烷的~(13)C-NMR研究顺反异构体比及顺式构象平衡常数K(35℃)

本工作是在35℃下测定对(艹孟)烷(p-Menthane)(即对位甲基异丙基环已烷)的~(13)C-NMR谱。由取代基参数,经验加和规律计算各碳化学位移数值,归属各谱峰位置。由积分值得知顺式、反式对(艹孟)烷含量之比。并根据权分法计算顺式对(艹孟)烷中构象1与构象2分子数之比。结果表明顺式对(艹孟)烷中异丙基处于平展位置的构象2为主。     

Stability of the Solution Set of Perturbed Nonsmooth Inequality Systems and Application

Stability properties of the solution set of generalized inequality systems with locally Lipschitz functions are obtained under a regularity condition on the generalized Jacobian and the Clarke tangent cone. From these results, we derive sufficient conditions for the optimal value function in a nonsmooth optimization problem to be continuous or locally Lipschitz at a given parameter.     

稀土添加剂对镍,铜刷镀层质量的影响

通过在刷镀镀液中加入稀土添加剂，研究稀土对刷镀层质量的影响。实验结果表明，稀土起到平整、光亮、细化镀层晶粒、减少镀层应力的作用，并增强镀层结合力，提高镀层的耐磨性、耐蚀性。     

Synthesis of tetrahydro-β-carbolinediketopiperazines in [bdmim][PF6] ionic liquid accelerated by controlled microwave heating

Because of their negligible vapor pressures and large dipoles, ionic liquids are excellent media for microwave-accelerated organic reactions. Using low-power microwave irradiation in the new [bdmim][PF₆] ionic liquid with temperature controlled at 60 °C, a three-step synthesis (Pictet-Spengler, Schotten-Baumann, and intramolecular ester amidation) of tetrahydro-β-carbolinediketopiperazines starting from tryptophan methyl ester was achieved with good isolated yields (49-69%) in only 5 min.