Studies on relationship between activity and electron density on carbonyl oxygen in sex pheromone mimics of the American cockroach,part XI

From the relationship between structures of the 2-substituents of verbanyl analogs and their sex pheromone activities to the American cockroach, electron density of the carbonyl oxygen atom in the substituent, as estimated by the [¹⁷O]NMR chemical shift, was estimated to be an important factor which influenced the activity, in addition to length of the substituent and the position of the carbonyl group. (+)-Verbanyl methylcarbonate (XX), possessing the highest electron density on the carbonyl oxygen atom, showed the strongest activity among the analogs.For Part X, see Manabe et al., 1983. J. Chem. Ecol. 9:533–549.     

Investigation of the microwave dielectric properties of Ca1−xMgxLa4Ti5O17 ceramics for application in coplanar patch antenna

In this paper, the dielectric properties of Ca_1−xMg_xLa₄Ti₅O₁₇ ceramics at microwave frequency have been studied. The diffraction peaks of Ca_(1−x)Mg_xLa₄Ti₅O₁₇ ceramics nearly unchanged with x increasing from 0 to 0.03. Similar X-ray diffraction peaks of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic were observed at different sintering temperatures. A maximum density of 5.3 g/cm³ can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. A maximum dielectric constant (_r) and quality factor (Q × f) of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h are 56.3 and 12,300 GHz (at 6.4 GHz), respectively. A near-zero temperature coefficient of resonant frequency (τ_f) of −9.6 ppm/°C can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. The measurement results for the aperture-coupled coplanar patch antenna at 2.5 GHz are presented. With this technique, a 3.33% bandwidth (return loss <−10 dB) with a center frequency at approximately 2.5 GHz has been successfully achieved.     

2-苯基-4-对氯苯基-1,5-苯并硫氮杂-α-(丁二酰亚胺基)-β-内酰胺的高效液相色谱法分析

采用Hypersil-ODS2(4.6mm×250mm,5μm)色谱柱,乙腈-水(70∶30)流动相,242nm检测波长,建立了测定2-苯基-4-对氯苯基-1,5-苯并硫氮杂-α-(丁二酰亚胺基)-β-内酰胺的高效液相色谱法。该法线性范为0～0.1mg/mL,回归方程为A=1.63×108c-2.86×105,相关系数r=0.9994,相对标准偏差为0.33%(c=0.06mg/mL,n=5),检出限为0.08μg/mL。平均回收率在97.2%～102.4%之间。该法重现性好,灵敏度高,简单,快速,准确。     

Cell-Based Optimization of Covalent Reversible Ketoamide Inhibitors Bridging the Unprimed to the Primed Site of the Proteasome β5 Subunit

The ubiquitin-proteasome system (UPS) is an established therapeutic target for approved drugs to treat selected hematologic malignancies. While drug discovery targeting the UPS focuses on irreversibly binding epoxyketones and slowly-reversibly binding boronates, optimization of novel covalent-reversibly binding warheads remains largely unattended. We previously reported α-ketoamides to be a promising reversible lead motif, yet the cytotoxic activity required further optimization. This work focuses on the lead optimization of phenoxy-substituted α-ketoamides combining the structure-activity relationships from the primed and the non-primed site of the proteasome β5 subunit. Our optimization strategy is accompanied by molecular modeling, suggesting occupation of P1′ by a 3-phenoxy group to increase β5 inhibition and cytotoxic activity in leukemia cell lines. Key compounds were further profiled for time-dependent inhibition of cellular substrate conversion. Furthermore, the α-ketoamide lead structure 27 does not affect escape response behavior in Danio rerio embryos, in contrast to bortezomib, which suggests increased target specificity.     

温控相分离纳米Ir催化α，β-不饱和醛、酮选择加氢

将温控相分离Ir纳米催化剂用于α,β-不饱和醛、酮的选择性加氢反应中,系统考察了其催化加氢性能。在优化的反应条件下,Ir纳米催化剂对α,β-不饱和醛的C═O键加氢选择性大于99%,对α,β-不饱和酮的C═C键加氢选择性大于99%。 Ir纳米催化剂经简单分离可直接循环使用5次,选择性均大于99%。TEM表征结果显示反应四次后的Ir纳米催化剂的平均粒径变为(1.9 ± 0.2) nm,比新制备的Ir纳米催化剂的平均粒径（1.3 ± 0.1）nm有所增大。ICP-AES测试结果表明Ir流失低于仪器检测下限（检测下限为5 μg/L）。     

α-Fe2O3/煤矸石复合光催化剂的制备及其降解五氯酚性能的研究

以Fe（NO₃）₃、煤矸石和NaOH为原料,采用沸腾回流法制得了一系列不同质量比的α-Fe₂O₃/煤矸石复合光催化剂。采用场发射扫描电子显微镜（FESEM）、X射线衍射仪（XRD）及紫外-可见漫反射光谱（UV-Vis DRS）等多种手段对产物做了表征。以五氯酚为目标降解物,考察了模拟太阳光照下样品的光催化效果。结果表明,将球形α-Fe₂O₃负载于改性煤矸石表面可有效提高其光催化活性,且α-Fe₂O₃/煤矸石复合光催化剂的性能与α-Fe₂O₃的含量有关,当α-Fe₂O₃与煤矸石的质量比为30∶100时,样品的光催化效果最佳,180 min内即可将五氯酚降解完全。此外,α-Fe₂O₃/煤矸石复合光催化剂还具有可重复使用的特点。     

不同质量比PANI/α-MnO_2超级电容器材料的制备及表征

在酸性条件下采用液相共沉淀法合成球状和海胆状的α-MnO2,并以α-MnO2为氧化剂,H2SO4溶液为介质,引发苯胺聚合制备得到不同质量比的聚苯胺(PANI)/α-MnO2复合物。采用XRD、FTIR、SEM等法对材料的形貌和物相进行表征,同时采用循环伏安、计时电位法考察了PANI/α-MnO2复合物在1 mol/L Na2SO4水系电解液中的电化学性能。结果表明,起始原料m(苯胺)∶m(α-MnO2)=1∶3制备的PANI/α-MnO2复合物,在制备电极过程中其质量未到α-MnO2质量一半的条件下,PANI/α-MnO2复合物的比电容达到64.58 F/g,是所合成的α-MnO2比电容(43.49 F/g)的1.48倍,且经过600次循环,其比电容保持率在85%以上,而α-MnO2只有57%的比电容保持率。     

α-氯代脂肪酸水热法中性水解合成α-羟基脂肪酸

开发了一条从天然脂肪酸合成α-羟基脂肪酸(α-HFA)的高产率、低污染且低成本的合成路线,即从天然脂肪酸制备α-氯代脂肪酸(α-CFA),再以α-CFA为原料通过水热法中性水解合成α-HFA。用GC-MS和IR鉴定了产物的结构,ESI-MS表征了产物的相对分子质量(以下简称分子量),纯化后α-HFA纯度达99%(GC)以上。探讨了水热中性水解反应中原料配比、反应加水量、反应温度、反应时间等因素对该水热工艺的影响,结果表明,当n(CaCO3)∶n(α-CFA)=1.05∶1,m(H2O)∶m(α-CFA)=2∶1,C12～C18的α-氯代天然脂肪酸在155℃水热条件下反应4 h后,α-HFA同系物的产率均高达98%～99%。     

抗肿瘤坏死因子-α单链抗体在大肠杆菌中的表达及表达条件的优化

目的构建抗肿瘤坏死因子-α(Tumor necrosis factor-α,TNF-α)单链抗体(Single chain fragment variable,scFv)的原核高效表达体系,并优化表达条件。方法在引物中添加编码6×His的核苷酸片段,使目的蛋白C-末端带有6×His标签。从质粒pCANTAB 5E-scFv中PCR扩增scFv基因,连接至pBV220载体,连接产物分别转化至E.coli BL21(DE3)和DH5α中,42℃诱导表达,并对诱导时间、培养基pH值和类型进行优化,Western blot分析表达产物的反应原性。结果 PCR扩增出的scFv基因片段长度约770 bp,且序列正确;重组表达质粒pBV220-scFv经酶切鉴定证明构建正确;在E.coli BL21(DE3)中可获得表达,在E.coli DH5α中不表达;表达的重组scFv相对分子质量约为28 000,以包涵体形式存在于胞浆中,表达量约占菌体总蛋白的15%,且可与抗His-Tag抗体发生特异性反应;工程菌的最佳诱导表达条件为:以E.coli BL21(DE3)为宿主菌,在pH 7.4的LB培养基中,42℃诱导5 h。结论将scFv的表达载体更换为pBV220,可提高scFv的表达量,在优化表达条件下,scFv的表达水平进一步提高。