荧光粉Ba5-3x/2B4O11∶xEu3+的制备及发光性能

采用高温固相烧结法成功制备了Ba_5-3x/2B₄O₁₁∶xEu³⁺(x=0.02~0.22)荧光粉,利用XRD和SEM等对荧光粉进行了结构和形貌表征。 在激发波长为393 nm的条件下,发射峰(596、621、657和706 nm)与Eu³⁺的⁵D₀-⁷F_J(J=1,2,3,4)电子跃迁相对应,其中621 nm最强发射峰由Eu³⁺离子⁵D₀→⁷F₂电偶极跃迁造成。 文章还研究了Eu³⁺掺杂浓度对Ba_5-3x/2B₄O₁₁∶xEu³⁺发光性能的影响,结果表明,荧光粉的发光强度随着Eu³⁺掺杂量的增加呈现先增大后减小的趋势,Eu³⁺最佳掺杂量为0.16。     

高性能甲苯烷基化合成二甲苯催化剂研究

通过对比不同孔结构分子筛的甲苯甲醇烷基化催化性能,发现分子筛孔道尺寸与目标芳烃分子动力学尺寸的有效匹配以及孔道空间限制效应对反应路径的约束管理,对实现高性能烷基化至关重要。并结合XRD、BET、NH₃-TPD和SEM表征分析,通过先后负载La₂O₃和P₂O₅对硅铝比为60的ZSM-5进行复合改性修饰,提升其骨架水热稳定性的同时,选择性地消除内外表面大部分强酸中心,保留弱+中强酸作为烷基化催化活性位,所得MAT-HZSM-5催化该反应表现出很高的甲醇烷基化效率和良好的反应稳定性,在氮气反应气氛下,连续运行500 h无明显失活迹象,甲苯转化率维持在35%-38%,二甲苯选择性60%-77%,甲醇烷基化效率大于90%。     

4-甲基-1，2，3-噻二唑-5-甲酸构筑的锌配合物的合成、晶体结构及与DNA作用

由4-甲基-1,2,3-噻二唑-5-甲酸（HMTC,C₄H₄N₂O₂S）分别和1,3-双（4-吡啶基）-丙烷（bpp）、菲咯啉（phen）合成了2个锌配合物[Zn（MTC）₂（bpp）]_n（1）和[Zn（MTC）（phen）（H₂O）₂]（MTC）（2）。用元素分析、红外光谱、粉末X射线衍射、热重分析对配合物进行了表征,并通过单晶X射线衍射测定了配合物的晶体结构。结果表明：配合物1是二维网状结构,属于单斜晶系,P2₁/c空间群,中心金属锌（Ⅱ）离子的配位构型是扭曲的四面体结构。配合物2是二维层状结构,属于三斜晶系,P1空间群,中心金属锌（Ⅱ）离子的配位构型是变形的三角双锥结构。用溴化乙锭荧光探针法测定了配体和配合物对EB-DNA复合体系相互作用,实验结果显示无论配体还是配合物均能使EB-DNA复合体系发生不同程度的荧光猝灭,且配合物的作用强度远大于配体。     

Synthesis of New Azocompounds and Fused Pyrazolo[5,1‐c][1,2,4]triazines Using Heterocyclic Components

Diazotization of 3‐methyl‐4‐phenyl‐1H‐pyrazol‐5‐amine 1 in hydrochloric acid has been reported to afford the corresponding diazonium salt 2 . The latter underwent azocoupling with a variety of active methylene compounds (barbituric 3a and thiobarbituric 3b acid, 2‐hetarylpyrimidine‐4,6‐dione 6a , 6b , 4‐hydroxy‐6‐methylpyridin‐2(1H)‐one 10a , 4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one 10b , 4‐hydroxy‐1‐p‐tolyl‐1H‐pyrazole‐3‐carboxylic acid ethyl ester 14 , 1,3‐thiazolidine‐2,4‐dione 16a , 2‐thioxo‐1,3‐thiazolidin‐4‐one 16b ) to yield new pyrazolylazo derivatives. Fused pyrazolo[5,1‐c][1,2,4]triazines 5 , 9a , 9b , 12 , 13 were obtained by heterocyclization reactions. Copyright © 2013 HeteroCorporation     

Viscoelastic properties of poly(ε‐caprolactone) – hydroxyapatite micro‐ and nano‐composites

Various composites have been proposed in the literature for the fabrication of bioscaffolds for bone tissue engineering. These materials include poly(ε‐caprolactone) (PCL) with hydroxyapatite (HA). Since the biomaterial acts as the medium that transfers mechanical signals from the body to the cells, the fundamental properties of the biomaterials should be characterized. Furthermore, in order to control the processing of these materials into scaffolds, the characterization of the fundamental properties is also necessary. In this study, the physical, thermal, mechanical, and viscoelastic properties of the PCL‐HA micro‐ and nano‐composites were characterized. Although the addition of filler particles increased the compressive modulus by up to 450%, the thermal and viscoelastic properties were unaffected. Furthermore, although the presence of water plasticized the polymer, the viscoelastic behavior was only minimally affected. Testing the composites under various conditions showed that the addition of HA can strengthen PCL without changing its viscoelastic response. The results found in this study can be used to further understand and approximate the time‐dependent behavior of scaffolds for bone tissue engineering. Copyright © 2012 John Wiley & Sons, Ltd.     

Spectrophotometric study of the complexation of iodine with 1,7-diaza-15-crown-5 in chloroform solution

The complex formation reaction between iodine and 1,7-diaza-15-crown-5 (DA15C5) has been studied spectrophotometrically in chloroform at 25°C. The resulting 1:2 (DA15C5:I₂) molecular complex was formulated as (DA15C5...;I⁺)I ₃ ^– . The spectrophotometric results, as well as the conductivity measurements, revealed that the gradual release of triiodide ion from its contact ion paired form in the molecular complex into the solution is the rate determining step of the reaction. The rate constant was calculated ask=(8.8±0.2)×10^–3 min^–1. The formation constant of the molecular complex was evaluated from the computer fitting of the absorbance-mole ratio data as logK _f=6.89±0.09.     

ZSM-5分子筛酸位分布及其甲醇制烯烃催化性能的定向管理与调控

ZSM-5分子筛在甲醇制烯烃(MTO)过程中的催化性能和反应机理与其孔道中酸位点分布位置紧密相关. 本文证明在水热合成过程中加入适量的钠离子(Na⁺)可以增加ZSM-5分子筛交叉腔酸位点比例; 从而促进高级甲基苯的生成并加速芳烃循环, 有利于乙烯生成. 相反, 在合成过程中不添加钠离子, 所制备的ZSM-5分子筛直孔道和正弦孔道酸位点比例明显提高, 有利于促进烯烃循环并提高丙烯和C₃₊烯烃选择性.     

Cryptotympana pustulata Extract and Its Main Active Component,Oleic Acid,Inhibit Ovalbumin-Induced Allergic Airway Inflammation through Inhibition of Th2/GATA-3 and Interleukin-17/RORγt Signaling Pathways in Asthmatic Mice

Cicadae Periostracum (CP), derived from the slough of Cryptotympana pustulata, has been used as traditional medicine in Korea and China because of its diaphoretic, antipyretic, anti-inflammatory, antioxidant, and antianaphylactic activities. The major bioactive compounds include oleic acid (OA), palmitic acid, and linoleic acid. However, the precise therapeutic mechanisms underlying its action in asthma remain unclear. The objective of this study was to determine the antiasthmatic effects of CP in an ovalbumin (OVA)-induced asthmatic mouse model. CP and OA inhibited the inflammatory cell infiltration, airway hyperresponsiveness (AHR), and production of interleukin (IL)7 and Th2 cytokines (IL-5) in the bronchoalveolar lavage fluid and OVA-specific imunoglobin E (IgE) in the serum. The gene expression of IL-5, IL-13, CCR3, MUC5AC, and COX-2 was attenuated in lung tissues. CP and OA might inhibit the nuclear translocation of GATA-binding protein 3 (GATA-3) and retinoic acid receptor-related orphan receptor γt (RORγt) via the upregulation of forkhead box p3 (Foxp3), thereby preventing the activation of GATA-3 and RORγt. In the in vitro experiment, a similar result was observed for Th2 and GATA-3. These results suggest that CP has the potential for the treatment of asthma via the inhibition of the GATA-3/Th2 and IL-17/RORγt signaling pathways.     

混合熔盐法低温合成Sm2Ti2S2O5及其光催化分解水产氢

以TiO2、TiS2及Sm2O3为前驱体,分别加入LiCl-KCl与LiCl-CsCl的最低共熔混合物作为熔盐,在较低温度下成功合成了Sm2Ti2S2O5(STSO)颗粒。通过对比不同温度下所制备产物的X射线衍射图,首次表明STSO的热力学结晶温度在520℃左右,远低于之前报道的650℃的最低合成温度。扫描电子显微镜照片显示,采用2种混合熔盐制备的STSO都呈片状形貌;同一合成温度下,采用LiCl-CsCl熔盐制备的STSO的厚度小于LiCl-KCl所得产物。采用出射光波长大于420 nm的氙灯作为光源,在含有Na2S-Na2SO3空穴牺牲剂的溶液中,所制备的STSO颗粒表现出最高35μmol·h-1的光催化分解水产氢活性以及20 h以上的产氢稳定性。     

[2+2]-Photocycloaddition von Cyclohexen an 2-Acetyl-5,5-dimethyl-1,3-cyclohexandion und 3-Acetyl-1,5,5-trimethyl-2,4-pyrrolidindion

Summary Irradiation of solutions of excess cyclohexene and 2-acetyl-5,5-dimethyl-1,3-cyclohexanedione (1), and 3-acetyl-1,5,5-trimethyl-2,4-pyrrolidinedione (4) results mainly in the formation of 1,5-diones2 and5. These originate from intermediate cycloadducts of cyclohexene and theexo-enols of the cyclic 1,3-diketones. The yields decrease with increasing polarity of the solvent. In solution2 and5 are in equilibrium with the cyclic hemiacetales3 and6.