苯丙乳液制备及其电纺微纳米纤维结构的研究

通过乳液聚合的方法制备了水相苯丙乳液(PSBA)，并将其应用于静电纺丝制备出微纳米纤维结构。采用红外光谱、差示扫描量热仪（DSC）和动态光散射仪分析并表征了聚合物的化学组成、热稳定性，并得到了均一稳定的苯丙乳液。通过扫描电镜（SEM）研究了纺丝电压及纺丝液中苯丙乳液与聚乙烯醇（PVA）质量比对苯丙乳液电纺微纳米纤维结构的影响，结果表明，改变纺丝液PSBA、PVA质量比能够得到可控性的纤维结构；纺丝电压对纤维中串珠状结构形成有一定影响，且电压越高，纤维直径越小。     

Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

The insertion reaction mechanism of CBr2 with CH3CH2O has been studied by using the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) at single point. The geometries of reactions,transition state and products were completely optimized. All the transition state is verified by the vibrational analysis and the internal re-action coordinate (IRC) calculations. The results show that reaction (1) is the dominant reaction path,which proceeds via two steps: i) two reactants form an intermediate (IM1),which is an exothermal re-action of 8.62 kJ·mol?1 without energy barrier; ii) P1 is obtained via the TS1 and the H-shift,in which the energy barrier is 44.53 kJ·mol?1. The statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters of this reaction in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature ranges from 200 to 1900 K at 1.0 atm,in which the reaction has a bigger spontaneity capability,equi-librium constant (K) and higher rate constant (k).     

不可逆加成-断裂链转移剂正丁基-2-苯基烯丙基硫在苯乙烯乳液聚合中的研究

基于不可逆加成断裂链转移机理,研究了正丁基-2-苯基烯丙基硫（BPAS）作为分子量调节剂对苯乙烯乳液聚合速率、乳胶粒子大小和聚合物数均分子量的影响。结果表明，BPAS存在下的苯乙烯乳液聚合速率有所下降，乳胶粒子粒径减小，这是由于乳胶粒子中自由基的解吸附；平均一个乳胶粒子中的自由基个数依赖于BPAS浓度；BPAS在苯乙烯乳液聚合整个过程中能有效调节聚合物分子量，其调节效率与温度无关，同时能与经典的数均分子量数学模型相匹配。     

A multiphoton ionization study of acetone using time-of-flight mass spectrometry

The 3p Rydberg states of acetone and photodissociation of the acetone cation were studied using time-of-flight (TOF) mass spectrometry. The 3p Rydberg state spectroscopy of acetone was investigated with linearly polarized two-photon resonance enhanced multiphoton ionization (REMPI) from 320 to 337 nm. Several new transition bands were observed in the spectra. In addition to the CH₃COCH₃ ⁺ ion, CH₃CO⁺ and CH₃ ⁺ fragments were observed. The laser power dependences suggest that the CH₃COCH₃ ⁺, CH₃CO⁺ and CH₃ ⁺ ions are produced in three-, four-, and four-photon processes, respectively. Production of CH₃CO⁺ and CH₃ ⁺involves excitation of the ground state acetone cation by an additional photon and subsequent decomposition of the excited acetone ion. The average translational energies of CH₃CO⁺ and CH₃ ⁺ from dissociation in CH₃COCH₃ ⁺(X) + hv → CH₃CO⁺ + CH₃ and CH₃COCH₃ ⁺(X) + hv → CH₃ ⁺ + CH₃CO, respectively, were derived from the ion TOF peak profiles.     

Lithium bond structures of HnY （n=2, 3; Y=O,S, N）…LiNH2 and the abnormal blue shift of N-Li bond

The optimized geometries of the complexes between HnY （n=2, 3; Y=O, S, N） and LiNH2 have been calculated at the B3LYP/6-311＋＋G^＊＊ and MP2/6-311＋＋G^＊＊ levels. Three stable complexes were obtained. Frequency analysis showed that the enlarged 2N-4Li presents the abnormal blue shift in three complexes. The calculated binding energy with basis set super-position error （BSSE） and zero-point vibrational energy （ZPE） corrections of complex Ⅰ-Ⅲ is -58.65, -31.66 and -69.59 kJ·mol^-1 （MP2）, respectively. Natural bond orbital theory （NBO） analysis has been performed, and the results revealed that the H2O…LiNH2 （complex I） and H3N…LiNH2 （complex Ⅲ） are formed with coexisting σ-s and n-s type lithium bond interactions, complex Ⅱ is formed with ττ-s type lithium bond interaction between HnY （n=2,3; Y=O, N） and LiNH2, and H2S…LiNH2 （complex Ⅱ） is formed with n-s type lithium bond interaction between H2S and LiNH2. Natural resonance theory （NRT） and atom in molecule （AIM） theory have also been studied to investigate the bond order and topological properties of the lithium bond structures.     

Oscillating chemiluminescence in rhodamine B-induced Belousov-Zhabotinsky reaction catalyzed by Ce(Ⅳ)

It was found that rhodamine B could induce oscillating chemiluminescence (OCL) from the Ce4+-cata-lyzed Belousov-Zhabotinsky reaction. This new OCL system, i.e., rhodamine B-malonic acid-bromate-Ce(Ⅳ)-sulfuric acid, exhibited two clearly distinguished emission peaks in each oscillation period. The initial concentrations of the reactants strongly influenced the oscillation pattern. For the study of the CL mechanism, a platform for a versatile and simultaneous potential and CL measurement was estab-lished to ...     

强场原子分子物理实验研究中的符合测量技术及其应用

飞秒激光具有超短的脉冲宽度和超强的峰值功率，已经成为测量和操控原子分子超快动力学行为的重要工具．但是强激光场下，原子分子行为非常复杂，多个反应通道纠缠在一起．全微分符合测量技术能够提供特定反应通道精确的动力学数据，推动了强场原子分子物理研究的快速发展．本文结合北京大学新建的冷靶反冲离子动量谱仪，介绍全微分符合测量技术在强场原子分子物理实验研究中的重要应用以及在强场原子分子物理实验研究方面取得的一些重要进展．     

Comparison of changes of typical river segment ecosystem service value in LRGR

Land use changes of river segment ecosystems from the Lancang River and Yuanjiang River were studied from 1985 to 2000 in order to compare their changes of service values and analyze the driving mechanisms based on eco-economic and GIS methods. Results showed that forest areas in both the river segment ecosystems were reduced. The reduced forest in the Lancang River (LR) segment ecosystem was mostly transformed into glebe with the conversion rate of 56.0%, while the reduced forest in the Yuanjiang River (YR) segment ecosystem was mostly transformed into residence land with the conversion rate of 42.5%. Both change amount and change rate of areas of each land use type in the LR segment ecosystem were much larger than those in the YR segment ecosystem. The total service value of the LR segment ecosystem was decreased with the change rate of 15.3%, while that of YR segment ecosystem was increased with the change rate of 0.6%. Manwan Hydropower development was the major anthropogenic driving factor which led to the change of service value of the LR segment ecosystem with the contribution rate of 93%. Agricultural activities were the most important driving factors in the YR segment ecosystem with the contribution rate of 59%. The loss of value of Sediment transportation service resulting from Manwan Hydropower Project construction should take responsibility for the significant decrease of service value of waters, even for the whole LR segment ecosystem. The ecosystem service coefficients of forest and grassland in the study area were much higher than the average level in China, so were the ratios of indirect value to direct value of both the river segment ecosystems. Under the impacts of human activities, the capacity of river ecosystem for providing products was enhanced, while it was weakened to maintain natural ecosystem health.

     

Theoretical characterization of single-electron iodine-bond weak interactions in CH3…I-Y（Y=BH2,H,CH3,C2H3,C2H,CN,NC）systems

Iodine-involved single-electron halogen bonds (SEXBs) weak interactions in the systems of CH3···I-Y(Y = BH2, H, CH3, CH==CH2, C≡CH, CN, NC) were investigated for the first time using B3LYP/6-311++G(d,p) and MP2/aug-cc-pVTZ computational levels (the relativistic effective core potential basis set of Lanl2dz was used on iodine atom). The interaction energies between two moieties with basis set super-position error corrections for the seven complexes are -0.57, -1.36, -3.80, -2.17, -4.49,-6.33 and -8.64 kJ mol-1 (MP2/aug-cc-pVTZ ), respectively, which shows that SEXBs interactions are all weak. Natural bond orbital theory analysis revealed that charges flow from CH3 to the I-Y moiety. The total amount of natural bond orbital charge transfer (ΔNC) from the CH3 radical to I-Y increases in the order CH3…IBH2 < CH3…IH ≈ CH3…ICH3 ≈ CH3···IC2H3 < CH3…ICCH< CH3…ICN< CH3…INC. Atoms-in-molecules theory was used to investigate the topological properties of the bond critical points in the seven SEXB structures.     

含结合水的钯二亚胺催化剂催化1-辛烯水相均聚及共聚合研究

以含结合水的钯二亚胺 [(ArN=C(An)—C(An)=NAr)Pd(CH₂)₃C(O)OMe] (BAr’₄)·H₂O为催化剂,以水为分散介质,进行了1-辛烯均聚合及1-辛烯与丙烯酸甲酯（MA）的共聚合反应,通过GPC、DSC、¹H-NMR、光散射测定了聚合物的分子量、熔点、分子结构以及聚合物粒子的粒径。结果表明:该催化剂在水相聚合体系中可以催化1-辛烯的均聚合及1-辛烯与MA的共聚合反应;得到的聚合物重均分子量均可达3.3×10⁴以上,且分子量分布较窄(Mw/Mn在1.4~2.1之间);共聚物为半结晶性聚合物,Tg为-34.8℃,Tm为32.3℃,聚合所得均聚物和共聚物的支化度均较高;共聚合可得到较为稳定的乳液体系,光散射测得乳胶粒子的粒径约为266nm。