4-溴代苯酐的合成新方法

将4-硝基邻苯二甲酰亚甲胺（4-NPI）用铁粉还原为4-氨基邻苯二甲酰亚甲胺 ，再在氢氧化钠水溶液中水解成4-氨基邻苯二甲酸钠。4-氨基邻苯二甲酸钠在氢溴 酸中经Sandmeyer反应合成4-溴代苯酐。产品纯度高，是合成4-溴代苯酐的一个比较 理想的方法。     

基于脂肪酸的漂浮液滴固化分散液液微萃取-高效液相色谱法联用测定酒类样品中的4-乙基苯酚和4-乙基愈创木酚

建立了基于脂肪酸的漂浮液滴固化分散液液微萃取（FA-DLLME-SFO）方法,与高效液相色谱联用检测了酒类样品中的4-乙基苯酚和4-乙基愈创木酚。该方法萃取时间仅需4 min,仅需脂肪酸、氨水和硫酸3种对环境友好的试剂。对影响方法萃取效率的因素（包括样品的体积、萃取剂的种类和用量、氨水和硫酸的体积以及盐的加入量）进行了详细的考察。在最佳萃取条件下（10 mL样品,100 μL辛酸萃取剂,110 μL 25%～28%（质量分数）的氨水,0.8 mL 98%（质量分数）的浓硫酸,3.0 g NaCl）,4-乙基苯酚和4-乙基愈创木酚在0.02～1.0 mg/L范围内呈良好的线性关系,相关系数分别为0.9997和0.9999,相对标准偏差（n=3）分别为6.2%和3.5%,检出限分别为6.33和5.81 μg/L,富集倍数分别为79和86。在啤酒和白葡萄酒样品中,加标回收率为81.4%～108.7%,相对标准偏差（n=3）小于8.9%。该方法简单、对环境友好,可用于酒类样品中4-乙基苯酚和4-乙基愈创木酚的检测。     

N-二异丙基磷酰化氨基酸-N-4-氨基吡啶衍生物的合成及对河豚毒素(TTX)解毒生物活性的研究

通过母体化合物4-氨基吡啶(4-AP)与N-二异丙基磷酰化氨基酸(DiPP-AA)在Ph3P和C2Cl6体系下的缩合反应,将具有生物活性的氨基吡啶环引入到磷酸化氨基酸结构中,设计、合成了5个N-二异丙基磷酰化氨基酸-N-4-氨基吡啶衍生物A1～A5.所有目标化合物均经IR,1H NMR,13C NMR,31P NMR,MS的表征.初步生物活性测试结果表明:目标化合物对河豚毒素(TTX)中毒的小鼠均有一定的解毒作用,并不同程度地延长了生存时间,而且毒性比母体化合物降低了.     

Poly(4-vinylpyridinium tribromide) as metal-free, green and recoverable oxidizing polymer for the chemoselective oxidation of sulfides into sulfoxides

Poly(4-vinylpyridinium tribromide) was prepared from poly(4-vinylpyridin) and used for the selective oxidation of a variety of sulfides to the corresponding sulfoxides.The oxidation reaction was carried out heterogeneously in acetone/water,as green solvent, at room temperature.     

185 nm UV降解水中4-CP、4-NP和Rh B的研究

本文以对氯苯酚(4-CP)、对硝基苯酚(4-NP)和罗丹明B(Rh B)为模型有机物(以4-CP和4-NP为小分子模型有机物,以Rh B为大分子模型有机物),分别研究了185 nm UV对水中这3种模型有机物的降解规律、性能和效果.研究结果表明,185 nm UV直接对水中4-CP、4-NP和Rh B有很好的降解效果.研究内容包括:185 nm UV降解模型有机物的浓度、TOC(Total organic carbon)浓度、185 nm UV降解模型有机物过程中溶液pH及电导率变化、以及降解模型有机物过程中产生的无机离子等几个方面.     

一种新的绝缘膜——聚对苯二甲酸对氧代苯甲酸乙二酯

聚对苯二甲酸乙二酯（匹T）膜已广泛用于绝缘和包装行业，其耐热温度不超过12O℃，熔点较高（260“C），结晶速率较快，难以拉制成电机槽绝缘和相绝缘所需厚度大于020mm的柔软薄膜．在PET的分子链中引人4，4’一氧代二次苯基能降低共聚酯的熔点［’j，但对共聚酯的热稳定性和结晶速率有无影响未曾提及．我们以4，4’一二苯醚二甲酸（OBBA）为改性组分，合成了一系列聚对苯二甲酸对氧代苯甲酸乙二酯（PETO）并制成薄膜，该膜不仅比PET膜的熔点低，结晶速率慢，而且热稳定性也有所提高，有可能制得0．2mm厚的薄膜．1实验部分1．l原料对…     

Recognition of lipopolysaccharide pattern by TLR4 complexes

Lipopolysaccharide (LPS) is a major component of the outer membrane of Gram-negative bacteria. Minute amounts of LPS released from infecting pathogens can initiate potent innate immune responses that prime the immune system against further infection. However, when the LPS response is not properly controlled it can lead to fatal septic shock syndrome. The common structural pattern of LPS in diverse bacterial species is recognized by a cascade of LPS receptors and accessory proteins, LPS binding protein (LBP), CD14 and the Toll-like receptor4 (TLR4)–MD-2 complex. The structures of these proteins account for how our immune system differentiates LPS molecules from structurally similar host molecules. They also provide insights useful for discovery of anti-sepsis drugs. In this review, we summarize these structures and describe the structural basis of LPS recognition by LPS receptors and accessory proteins.     

Beiträge zur Chemie des Phosphors. 235. Zur Darstellung größerer Mengen von Diphosphan(4) im Laboratorium

Contributions to the Chemistry of Phosphorus. 235. On the Preparation of Larger Amounts of Diphosphane(4) in the Laboratory The preparation of several hundred grammes of diphosphane(4) by hydrolysis of calcium phosphide in a semicontinuous process as well as the handling of larger amounts of this compound are reported. In comparison with earlier results [12], the yield has been raised by 37 percent with simultaneous increase of the accessible total amount. The white solid which is formed in the preparation and purification of diphosphane(4) is not, as was believed in earlier work [25, 8], triphosphane(5) or another, novel phosphorus hydride but is rather a clathrate compound of diphosphane(4) or the phosphanes P_nH_n+2 (n = 2–4) and water, respectively.     

4-甲基咪唑磁性表面分子印迹聚合物的制备及其应用

以4-甲基咪唑(4-MI)为模板分子,甲基丙烯酸(MAA)为功能单体,利用Fe₃O₄磁性纳米微球制备了具有特异性识别能力的磁性表面分子印迹聚合物(MIP),并用红外光谱(FT-IR)、X-射线衍射(XRD)、透射电子显微镜(TEM)和振动样品磁强计(VSM)对聚合物进行了表征,结果显示磁性载体表面包覆了分子印迹聚合物薄层。用紫外分光光度法对4-MI与MAA的相互作用进行了分析,结果表明主客体主要存在形式为1个4-MI被1个MAA所包围。通过紫外分光光度法对磁性印迹聚合物的吸附性能进行了研究,静态吸附平衡实验和Scatchard分析结果表明Fe₃O₄@(4-MI-MIP)中存在两类不同的结合位点,最大吸附量分别为40.31 mg/g和23.07 mg/g,平衡解离常数分别为64.85 mg/L和30.41 mg/L。动力学研究表明准二级动力学方程能较好地拟合动力学实验结果,该过程符合准二级动力学模型。该磁性印迹聚合物应用于环境水样中4-MI的吸附,取得了较满意的结果。     

偏磷酸钾制备方法研究

偏磷酸钾是一种较理想的无氯磷钾复合肥。目前,制备偏磷酸钾的工艺主要有两种：①以磷酸和氯化钾为原料制备;②以元素磷和氯化钾为原料制备。此两种方法反应温度都较高,设备需要用特殊材质制造,副产物均有氯化氢气体,严重腐蚀设备,污染环境。为了克服这些不足,我们探索出了制备偏磷酸钾的新方法一磷酸二氢铵和氯化钾热复分解升华法。     

On synthesis, structure, and thermal stability of mercury and lead sulfates and oxide sulfates

Reactions between HgO, PbO, or PbO₂ and 2.5–95 wt.% H₂SO₄ are studied at temperatures up to the boiling point of the acid. Depending on the oxide reactant, the H₂SO₄ concentration, and synthesis temperature, HgSO₄, Hg₃O₂(SO₄), PbSO₄ and Pb₂O(SO₄) are obtained as identified reaction products. The thermal stability of HgSO₄, Hg₃O₂(SO₄), PbSO₄, Pb₂O(SO₄), and PbO₂ is examined and the results supplement and modify earlier findings. The redetermined crystal structure of Hg₃O₂(SO₄) on the basis of powder neutron diffraction data shows that its space group (P3₁) is of lower symmetry than earlier reported (P3₁2₁).     

Spectrophotometry Determination of Arsenic(III) and Antimony(III) by Means of Isonicotinoylhydrazones of 4-Dimethylaminobezaldehyde (4-Dbih) and 2-Hydroxynaphthaldehyde (2-Hnih)

Abstract

4-DBIH and 2-HNIH react with As(III) and Sb(III) respectively, in CH₃COOH medium to form colored complexes stable in presence of EDTA. As(III) and Sb(III) do not react with 2-HNIH and 4-DBIH respectively, and the Sb(III)-2-HNIH complex is extractable into isoamyl alcohol. These behaviours were used for the spectrophotometry determination of As (III) and Sb(III) in presence of several cations.     

高性能聚芳醚酮的合成与性能(Ⅰ)——对苯二酚、联苯二酚、4,4′,-二氟二苯酮三元共聚体系

聚醚醚酮(PEEK)具有突出的耐高温水解和耐辐照性能以及良好的断裂韧性,现已在核能、宇航等高技术领域得到应用。研制新型聚芳醚酮是目前十分活跃的课题。本文采用亲核取代路线,以对苯二酚、联苯二酚、4,4′-二氟二苯酮为单体合成了一系列含亚联苯结构的新型聚芳醚酮,并对基基本性能进行了测定。     

以Fe2O3为原料制备LiFePO4/C复合材料及其性能研究

以Fe2O3为铁源原料, 利用热还原法成功地制备了LiFePO4/C复合材料. 用XRD以及SEM对材料的晶体结构以及表面形貌进行了表征. 通过循环伏安和充放电测试研究了材料的电化学性能. 研究结果表明， 于700 ℃下制备的LiFePO4/C复合材料在0.1C的倍率下可以得到放电容量144.8 mA·h/g, 在循环160次后, 容量仍保持在141.4 mA·h/g. 这种以廉价的Fe2O3代替目前常用的二价铁盐原料方法, 具有减少LiFePO4合成成本的优点.     

Synthesis,Structure, Bonding,and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] and [{Cp*M(CO)2}2B2H2M(CO)4], M=Mo,W

The reaction of [(Cp*Mo)₂(μ‐Cl)₂B₂H₆] ( 1 ) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)₂}₂{μ‐η²:η²‐B₂H₄}] ( 2 ). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged C_s structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum–alkyne complex [{CpMo(CO)₂}₂C₂H₂]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)₄] fragment, [{Cp*Mo(CO)₂}₂ B₂H₂W(CO)₄] ( 3 ) was isolated upon treatment with [W(CO)₅⋅thf]. Compound 3 shows the intriguing presence of [B₂H₂] with a short B−B length of 1.624(4) Å. We isolated the tungsten analogues of 3 , [{Cp*W(CO)₂}₂B₂H₂W(CO)₄] ( 4 ) and [{Cp*W(CO)₂}₂B₂H₂Mo(CO)₄] ( 5 ), which provided direct proof of the existence of the tungsten analogue of 2 .     

Selective Separation of Gold on Amberlite xad-4 Impregnated with Dmabr

DMABR (5-(4-Dimethylaminobenzylidene)-rhodanine) is proved to be a very selective reagent for gold as it impregnated on XAD-4. Gold is selectively adsorbed on resin through the formation of Au(I)-DMABR. Distribution coefficients at different pH were determined. The selectivity and interference were studied. Less than 0.1 ppb of Au could be adsorbed on resin. It can be directly determined by NAA or cluted down with cyanide solution and determined by AAS.     

Studies on New Steroidal Saponins from Allii macrostemonis Bulbus and Their Antitumor Activities Design and Synthesis of Novel Bispecific Molecules for InducingBRD4 Protein Degradation

Proteolysis targeting chimeras(PROTACs) are bispecific molecules containing a target protein binder and a ubiquitin ligase binder connected by a linker. Recently, some heterobifunctional small molecule bromodomain-containing protein 4(BRD4) degraders based on the concept of PROTACs were designed to induce the degradation of BRD4 protein. Herein, we synthesized a new class of PROTAC BRD4 degraders. One of the most promising compound 22f exhibited robust potency of BRD4 inhibition with IC₅₀ value of (9.4±0.6) nmol/L. Furthermore, compound 22f potently inhibited cell proliferation in BRD4-sensitive cell lines RS4;11 with IC₅₀ value of (27.6±1.6) nmol/L and capable of inducing degradation of BRD4 protein at 0.5―1.0 μmol/L in the RS4;11 cells. These data establish that compound 22f is a potent and efficacious BRD4 degrader.     

固相萃取-超高效液相色谱-高分辨质谱法快速测定食用油中4种酚类环境雌激素残留

建立了固相萃取-超高效液相色谱-高分辨质谱(SPE-UPLC-HRMS)快速测定食用油中4种痕量酚类环境雌激素(双酚S(BPS)、双酚F(BPF)、双酚A(BPA)和4-壬基酚(4-NP))的分析方法。食用油样品经乙腈涡旋提取和SLC玻璃固相萃取小柱净化后,以0.05%(v/v)三乙醇胺和甲醇溶液为流动相进行梯度洗脱,采用Waters ACQUITY UPLC HSS T3色谱柱(100 mm×2.1 mm,1.8μm)进行分离,在电喷雾离子源负离子模式(ESI-)和选择性离子监测(SIM)模式下进行检测,内标法定量。4种目标物在各自的范围内有良好的线性关系,相关系数(r)0.999。方法的检出限(LOD,S/N=3)和定量限(LOD,S/N=10)分别为0.03~0.11μg/kg和0.10~0.36μg/kg。在1.0、10.0和80.0μg/kg 3个加标水平下,4种目标物的加标回收率为86.3%~96.1%,相对标准偏差(RSD)为2.2%~8.8%(n=6)。基质效应实验表明方法在低、中、高3个浓度水平下均无明显的基质干扰。该法简便、快速,能用于食用油中双酚S、双酚F、双酚A和4-壬基酚残留的快速检测。     

分散液-液微萃取与气相色谱-质谱联用分析环境水样中痕量的2,4-二硝基甲苯和磷酸三(2-氯乙基)酯

建立了分散液-液微萃取与气相色谱-质谱联用同时测定环境水样中痕量2,4-二硝基甲苯和磷酸三(2-氯乙基)酯的新方法。对影响萃取效率的因素进行了详细的考察和优化,确定采用的最佳萃取条件为: 将0.8 mL乙醇和60 μL氯仿的混合溶液快速注入5.0 mL的样品溶液中,振动混匀120 s后,离心分离,吸取沉积在试管底部的氯仿相直接进样分析。该方法对磷酸三(2-氯乙基)酯和2,4-二硝基甲苯的检出限(信噪比为3)分别为0.01和0.04 μg/L,富集倍数分别为96.6和127.5;两种物质的线性范围达3到4个数量级;日内和日间测定的相对标准偏差(RSDs, n=6)分别为8.6%～11.5%和8.9%～12.0%。将该方法用于环境水样中2,4-二硝基甲苯和磷酸三(2-氯乙基)酯的分析,其加标回收率为102.1%～110.9%。方法具有操作简单、方便快速、灵敏度高、无交叉污染和环境友好等优点。     

定点突变提高IL-4免疫毒素对淋巴瘤的选择性和杀伤活性

采用软件分析选择与IL-4分子结合与活性相关的重要位点13T,121R,通过定点突变得到IL-4突变基因cpIL4(13D121E),将其与绿脓杆菌外毒素突变基因PE38KDEL融合,成功地构建了编码免疫毒素cpIL4(13D121E)-PE38KDEL的融合基因.该基因在原核表达系统中得到了高效表达,表达量占细胞全蛋白的30%以上.表达产物经亲和色谱和阴离子交换色谱纯化后,进行细胞毒性实验,证明其对表达型IL-4受体的淋巴瘤细胞Daudi具有良好的细胞毒作用,活性是同类型IL-4免疫毒素的2倍,而对表达型IL-4受体的内皮细胞活性较低.