稀释蒸汽中Na+及积炭对甲醇制丙烯催化剂性能影响

考察了稀释蒸汽中Na⁺及积炭对甲醇制丙烯(MTP)催化剂物理化学性质和催化性能影响, 及离子交换后催化性能. 采用X射线衍射(XRD)、扫描电镜(SEM)、X射线荧光(XRF)光谱、N₂吸附-脱附、程序升温氨脱附(NH3-TPD)和热重(TG)分析等方法对失活和再生催化剂进行了表征, 并在101325 Pa、470℃ 和甲醇空速(WHSV)为1.0-3.0 h^-1的反应条件下, 采用连续流动固定床微型反应器考察其催化甲醇制丙烯性能. 结果表明: MTP反应970 h后的催化剂晶体结构和形貌没有受到明显破坏, 但稀释蒸汽中Na⁺极易扩散至催化剂表面,部分取代H质子的位置, 从而使催化剂酸性逐渐下降而中毒失活; 另外, MTP催化剂表面的积炭导致分子筛微孔堵塞是造成其失活的主要原因, 可通过烧炭再生过程消除, 而水蒸汽脱铝对催化剂性能的影响缓慢但更严重. 用再生和离子交换处理后, Na⁺中毒催化剂MTP反应性能基本完全恢复. 在470 h反应过程中, 甲醇转化率保持在99%以上, 丙烯选择性大于46%, 且随着反应时间的延长, 丙烯选择性逐渐升高、乙烯选择性逐渐下降.     

QM/MM自由能模拟3-吲哚乙酸甲基转移(IAMT):催化机理和底物特异性(英文)

3-吲哚乙酸甲基转移(IAMT)催化甲基化植物激素3-吲哚乙酸(IAA)的端位自由羧酸,被认为在叶片发育过程中起到了至关重要的作用.然而,目前对于酶催化机理的详尽过程尚未被研究。在这里本文对拟南芥的甲基转移过程(AtIAMT1)进行结合量子力学和分子力学(QM/MM)的自由能模拟,并确定了其催化机制及IAMTs的底物特异性根源.研究表明,从S腺苷L甲硫氨酸(AdoMet)到3-吲哚乙酸盐(IAA)的甲基转移自由能垒要比从AdoMet到水杨酸盐的自由能垒低很多,这与之前的实验发现以及酶的底物特异性完全一致.这表明,与水杨酸相比,IAA相对高效性的甲基化是由于一部分过渡态构型的稳定性可能通过底物结合反映在反应物里,本文研究支持了之前关于计算模拟可对SABATH系列中酶的底物特异性根源进行深入理解的设想,并且可用来帮助生成可控的并具其他底物特异性的酶的实验研究.     

具有变时滞和马尔可夫切换的随机递归神经网络的弱收敛(英文)

本文研究了具有变时滞和马尔可夫切换的随机递归神经网络的弱收敛,通过运用Lyapunov函数、随机分析技巧和推广了的Halanay不等式,得到了上述模型为弱收敛的充分性条件,并且我们揭示了对上述递归神经网络模型所确定的segment过程的转移概率的极限分布是此模型的解过程的唯一的遍历不变概率测度.此外,我们还给出了例子和数值模拟来说明我们结论的正确性.     

正项级数敛散性新的根式判别法

基于几何级数的敛散性和比较判别法,给出判断正项级数敛散性的一个新的根式判别法,并举例说明其应用.     

Commuting Toeplitz operators on the hardy space of the polydisk

In this paper, we show that two Toeplitz operators T_f and T_g on the Hardy space of the polydisk can commute if and only if the Berezin transform of the commutator [T_f, T_g] is n-harmonic.     

Amarusine A,a new dioxaspiro[4.4]nonane derivative with a butyrolactone ring from Pleioblastus amarus

Amarusine A (1), a new polyketide derivative possessing an unusual dioxaspiro[4.4]nonane derivative with a butyrolactone ring, was isolated from the leaves of Pleioblastus amarus. The structure and absolute stereochemistry of compound 1 were rigorously determined using UV, IR, HRESIMS, and 1D and 2D NMR techniques and by comparing experimental and calculated electronic circular dichroism (ECD) spectra. Amarusine A (1) exhibits a good antioxidant activity for scavenging the DPPH radical. A possible biosynthetic pathway was postulated.     

Investigating the effects of side chain length on the AIE properties of water-soluble TPE derivatives

The emissive properties of fluorophores in aggregated state are important for the development of bio-sensors or bio-imaging reagents. So three water-soluble TPE derivatives with different lengths of side chains have been synthesized and we investigated the effects of side chains on aggregation-induced emission (AIE) properties in the aggregated states. The results indicate that side chains on the fluorophores play a pivotal role in their emission in aggregated state mediated by heparin or solid state, because the coplanarity of these TPE derivatives was affected by side chains. The rates of radiative decay k_f and non-radiative decay k_nr have been obtained through the quantum yields and lifetime, and a larger k_f and smaller k_nr were present for compound TPE-C4N, suggesting that the aggregated TPE-C4N should posses the most remarkable fluorescent property.     

Highly unsaturated pyranone derivatives from the basidiomycete Junghuhnianitida

Four new highly unsaturated pyranone derivatives A–D (1–4), together with one known compound 5 (−)-nitidon were isolated from cultures of the fungus Junghuhnianitida. Planar structures of the new compounds were elucidated on the basis of extensive NMR spectroscopic and mass spectrometric analyses. Absolute configurations of the new compounds were determined on the basis of biosynthetic considerations and quantum chemistry theory. Compound 1 exhibited almost the same cytotoxic activities as cis-platin.     

Tuning Structural Topologies of Two Cadmium(II) Coordination Polymers via Isomeric Dipyridyl Ligands: Syntheses,Crystal Structures,and Luminescent Properties

Abstract. Two new coordination polymers {[Cd₂(BDC)₂(3‐bpmp)(H₂O)₂] · 2H₂O}_n ( 1 ) and [Cd₂(BDC)₂(4‐bpmp)]_n ( 2 ) [H₂BDC = 5‐hydroxy‐isophthalic acid, 3‐bpmp = 1,4‐bis(3‐pyridylmethy)piperazine, and 4‐bpmp = 1,4‐bis(4‐pyridylmethy) piperazine] were synthesized via hydrothermal synthesis, and further characterized by IR spectroscopy, elemental analysis, XRD, and X‐ray crystallography. Complex 1 shows a two‐dimensional (4,4) sql topology and complex 2 features an 8‐connected hex topology. Moreover, the luminescent properties of complexes 1 and 2 were investigated in the solid state at room temperature.