结晶聚合物中间层理论与实验佐证

概述了Ｆｌｏｒｙ和Ｙｏｏｎ由晶格模型出发，从理论上证明了结晶聚合物中间层的存在以及近年来许多学者采用多种实验技术确认中间层存在的事实。     

Evolution of TiO2 coating layers on lamellar sericite in the presence of La and the pigmentary properties

TiO₂-coated sericite powders were prepared by the chemical deposition method starting from lamellar sericite and TiCl₄ in the presence or absence of La³⁺ cations. After calcination at 900 °C for 1 h, the resultant TiO₂ nanoparticles on the sericite surfaces existed in anatase phase. The light scattering indexes of the TiO₂-coated lamellar sericite powders were dozens of times higher than that of the naked lamellar sericite powders. The presence of La³⁺ in the deposition solution was beneficial to the formation of the small-sized anatase TiO₂ nanoparticles, resulting in the formation of the dense and uniform island-like TiO₂ coating layers in a large range of the weight ratios of TiO₂ to sericite from 5% to 20%. The TiO₂-coated lamellar sericite powders prepared in the presence of La³⁺ had higher light scattering index than that prepared in the absence of La³⁺. XPS analysis shows that when La³⁺ cations were absent in the reaction solution, TiO₂ coating layers anchored at the sericite surface via the Ti-O-Si and Ti-O-Al bonds. The presence of La³⁺ cations caused the formation of Si-O-La and Al-O-La bonds at the sericite surface and Ti-O-La bond at the surface of TiO₂ coating layers. After coating TiO₂ on the sericite surface, the yellowness of the TiO₂-coated sericite powders obviously increased and the brightness slightly decreased.     

聚（β－羟基丁酸酯）／聚双酚A羟基醚共混体系相容性及结构的研究

ＤＳＣ和ＦＴＩＲ测试表明，结晶／非晶共混体系聚（β－羟基丁酸酯）（ＰＨＢ）／聚双酚Ａ羟基醚（ＰＢＨＥ）是部分相容的．熔融结晶退火可以大大提高共混物的结晶度，增加其相容性，７５／２５组分ＰＨＢ相结晶度最大，５０／５０组分（０２０）、（１３０）晶面微晶尺寸最大．ＳＡＸＳ研究表明，纯ＰＨＢ的中间层约为１．５ｎｍ，片层厚约４．０ｎｍ；共混物的中间层在２．０ｎｍ左右，片层厚在５．０—７．２ｎｍ之间，５０／５０组分片层最厚．７５／２５组分晶相和非晶相的密度差最大．     

淤泥质河口港池回淤计算

本文根据淤泥质河口泥沙运动的特点，提出以悬沙落淤及浮泥层回填相结合的港池疏浚回淤的估算方法，经验证表明与实测值基本相符.     

环六肽Thermoactinoamide A的固相合成及其抗菌活性

采用固相-液相两步法合成一种天然抗菌环肽Thermoactinoamide A。在9-芴甲氧羰基(Fmoc)固相合成的基础上,通过优化N,N-二异丙基乙胺(DIPEA)的添加量,得到直链肽,收率为84%,在此基础上,采用液相环合的方法对直链肽进行环合,通过优化环合体系中混合液的配比、初始pH等条件,得到Thermoactinomide A,收率为51%,总收率43%。抑菌实验结果表明,Thermoactinoamide A对金黄色葡萄球菌的最小抑菌浓度为32μg/m L。固相合成与液相环合两步法合成步骤少、过程简单、产率较高,为进一步研究该天然产物的生物活性及构效关系奠定了基础。     

二芳氧基稀土氯化物(ArO)2YCl(THF)2·MePh的合成、表征及晶体结构(ArO=2,6-二叔丁基-4-甲基酚基)

无水YCl3 与二倍量的ArONa(ArO =2 ,6 二叔丁基 4 甲基酚基 )在四氢呋喃 (THF)中反应 ,经甲苯溶液重结晶 ,高产率地合成了二芳氧基稀土氯化物 (ArO) 2 YCl(THF) 2 ·MePh。产物经元素分析和核磁共振表征 ,并测定了其晶体结构。配合物属正方晶系 ,I4( 1) /acd空间群 ,晶胞参数为a =1.8913( 1)nm ,b =1.8913( 1)nm ,c =5 .2 2 39( 1)nm ,V =18.6 86 ( 1)nm3 ,Z =16 ,Dc=1.137mg·m- 3 ,μ =1.342mm- 1 (MoKα) ,F( 0 0 0 ) =6 848,R =0 .0 46 9,Rw=0 .112 2。中心金属钇原子与二个芳氧基中的氧原子、一个氯原子和两个THF分子中的氧原子配位 ,形成一个五配位的扭曲的三角双锥几何构型。Y O(Ar)和Y Cl的键长分别为 0 .2 10 1( 3)和 0 .2 5 17( 6 )nm。     

Modulating the pH Activity Profiles of Phenylalanine Ammonia Lyase from <Emphasis Type="Italic">Anabaena variabilis</Emphasis> by Modification of Center-Near Surface Residues

Phenylalanine ammonia lyase from Anabaena variabilis (Av-PAL) is a candidate for the treatment of phenylketonuria (PKU). However, Av-PAL shows its optimal pH at 8.5 and maintains only 70% of its highest activity when pH decreases to 7.3–7.4 (the condition of human plasma). The objective of the study was to shift its optimal pH by mutating surface amino acid residues which interact with the general base Tyr78. Based on the crystal structure and the online program GETAREA, we selected five sites: Asn69, Glu72, Glu75, Asn89, and Val90. Removing negative charges or introducing positive charges near the general base Tyr78 by mutation, the pH optima were successfully shifted to more acidic range. Especially, the pH optima of E75A, E75L, and E75Q were shifted to 7.5 with 35, 30, and 24% higher specific activities than that of the wild, respectively. Half-lives of E75L and E75Q at 70 °C prolonged to 190 and 180 min from 130 min of the wild, respectively. In addition, the higher resistance to a low pH of 3.5 and protease made E75L a candidate for oral medicine of PKU. This work would improve the therapeutic prospect of Av-PAL and provide guidance in modulating optimal pH of enzymes.     

Schiff碱改性法制备SBA-15型介孔分子筛负载的纳米氧化镍

基于Schiff碱功能单体的改性作用,采用共缩聚方法,制备了SBA-15型介孔分子筛负载的氧化镍纳米粒子。 采用小角X射线散射（small angle XRD）、广角X射线衍射（wide angle XRD）、紫外-可见光谱（UV-Vis）、高分辨透射电子显微镜（HRTEM）和N2吸附-脱附测定对制得的样品进行了表征。 结果表明,制得的样品具有SBA-15型介孔分子筛典型的二维六方有序结构,NiO纳米粒子主要分布于SBA-15型介孔分子筛的孔道内。 当功能单体的含量不超过10%时,SBA-15型介孔分子筛的孔径在6~8 nm范围内;而当功能单体的含量达到15%时,SBA-15型介孔分子筛的孔道被严重堵塞,孔径降为3.8 nm。 NiO纳米粒子的尺寸随着功能单体含量的增加而增大。     

Hemostasis mechanism and applications of N‐alkylated chitosan sponge

Chitosan (CHI) is a versatile biological material that is well known for its hemostatic properties. This preliminary study evaluated several self‐assembling hydrophobically modified chitosan (HM–CHI) sponges to determine their efficacy on hemostasis . Fourier transform infrared (FT‐IR) spectroscopy was used to determine the successful graft of dodecyl groups onto the nitrogen atoms of CHI molecules. A platelet aggregation assay revealed that HM–CHI accelerated the platelet aggregation rate. Fluorescence spectroscopy showed that the HM–CHI changed the structure of fibrinogen in blood. Activated partial thromboplastin time, prothrombin time, fibrinogen time, and thromboelastographic assays were used to explore the effect of HM–CHI on the autologous blood coagulation pathway. Finally, a hemostatic sponge was made with HM–CHI and freeze‐dried zeolite composite film and was applied to the rat femoral artery hemostasis model. A hemostasis time of 86 ± 5 sec was achieved, which was significantly better than the one composed with pure CHI. The experimental results of the HM–CHI hemostatic materials are inspiring and will encourage the research and development of such materials. HM–CHI may be a strong candidate as a safe and effective hemostatic material. Copyright © 2017 John Wiley & Sons, Ltd.