含多个(R)-1,1''''-联萘手性高分子合成与结构表征

单体（R）．3，3＇-二碘-2，2＇-二正丁氧基-1，1＇-联萘（（R）-M-1），（R）-6，6＇-二溴-2，2＇-二正丁氧基-1，1’-联萘（（R）-M-2）分别与1，4-二乙烯基-2，3-二丁氧基萘（M-3），在钯催化下，通过Heck交叉耦合反应合成手性高分子P-1与P-2．单体和高分子进行了^1H—NMR、^13C-NMR、FT-IR、旋光度、GPC、UV、热分析、荧光光谱和CD等测试分析．高分子侧链上引入丁氧基后使得手性高分子溶解性增强并具有良好的成膜性，手性高分子P-1和P-2都能发射较强的蓝绿色荧光，荧光量子效率分别为0．42和0．48．     

DNA荧光探针—荧光素-中性红体系的研究

基于DNA对荧光素(FL)-中性红(NR)分子间荧光能量转移的抑制作用，以荧光素-中性红为荧光探针，考察该探针与DNA的结合反应，建立了准确测定DNA的新方法，在pH＝6.5条件下，hsDNA、ctDNA和smDNA的浓度与荧光素-中性红体系的荧光比值变化量Δ(Fd／Fa)成线性关系，响应线性范围分别为0．25-6．25μg／mL、0．10-5．00μg／mL、0．10-4．00μg／mL，0.025μg/mL和0．023μg／mL；分析测定了DNA合成样品，回收率91．3％-101．4％，相对标准偏差小于4．2％．     

2’-芳基-3-（1，4，5，6-四氢-6-哒嗪酮-3-羰基）氨基硫脲及其环化产物的合成

以α-酮戊二酸为起始原料，合成了1，4，5，6-四氢．6-哒嗪酮-3-甲酰肼(2)，然后将2与异硫氰酸芳基酯反应得到相应的芳基氨基硫脲衍生物3a～3f．用硫酸、醋酸汞或氢氧化钠分别将芳基氨基硫脲环化得到一系列新的1，3，4-噻二唑、1，3，4-噁二唑和1，2，4-三唑的衍生物．化合物的结构经元素分析，IR，^1HNMR和MS谱得以证实．     

SDE-GC-ECD分析水体中有机氯农药

运用单滴溶剂萃取-气相色谱-微池电子捕获检测器(SDE—GC—μECD)联用技术对水体中有机氯农药进行了分析，优化了影响单滴溶剂萃取的多种因素。该方法除了对P，P′-DDD的线性范围在0．4～4ng／mL之间外，其余的七种目标物(α-666，β-666，γ-666，δ-666，P，P′-DDE，0，P′-DDT，P，P′-DDT)线性范围均在0．04～4．0ng／mL之间，相关系数为0．9976～0．9999，回收率范围为83．3％～96．1％，相对标准偏差为2．1％～7．8％。与传统的液液萃取相比，单滴溶剂萃取不仅准确度、精密度相当，而且还具有省时、省溶剂的优点。     

2,6-二甲基-3-苯基-4a-对甲苯基-7-苯甲酰基-4a,5,6,12-四氢-1H,7H-1,3-噁嗪并[3,2-d][1,5]-苯并二氮杂-1-酮的合成及晶体结构

通过2-甲基-4-对甲苯基-1-苯甲酰基-2，3-二氢-1H－1，5-苯并二氮杂与由不对称1-苯基-2-偶氮-1，3-丁二酮热解产生的a-羰基烯酮的[2＋4]环加成反应制备了标题化合物（C34H30N2O3，Mr=514．62），用X射线衍射测定了其单晶结构。晶体属单斜晶系，空间群为P21／n，a=11．560（1），b=19．058（3），c=13．207（2）A，β=106.82（1）°，V=2785.2（7）A3，Z=4，Dc=1．230g．cm-3，MoKa（λ=0.71073A），μ=0．064mm-1，F（000）=1088，2278个可观测衍子射点，R=0．046，Rw=0．049。分子骨架为由苯环、具有类扭船式构象的七元二氮杂环和略微扭曲的唑酮环构成的三环体系。     

爪形大分子柠檬酸-1,3-丁二醇-硬酯酸十六醇的合成、表征与降滤性质研究

以1，3-丁二醇、柠檬酸为原料，设计、合成了以1，3-丁二醇为核心的柠檬酸-1，3．丁二醇-柠檬酸（cBc）爪状物小分子；再用酯化反应依次与带有功能化集团的硬酯酸、十六醇接枝合成了多元酯类爪形大分子柠檬酸-1，3-丁二醇-柠檬酸-硬酯酸-十六醇（CBC-SH）．采用核磁共振、红外光谱对合成的两种化合物进行了结构表征，表明合成的CBC和CBC-SH与所设计的分子结构相吻合．元素分析确定了CBC和CBC-SH的化学组成依次为C16H22O14和C98H184O15．合成的CBC-SH溶于非极性的有机溶剂，不溶于水．将CBC-SH按600μg／g的加剂量添加到不同的轻柴油中，柴油的冷滤点可降低6℃．     

法呢基苯乙酮及其黄烷酮化合物的全合成

以2，4，6-三羟基苯乙酮和法呢基溴为原料，经一步反应以52．0％和6．5％的收率同时得到3-法呢基-2，4，6-三羟基苯乙酮（1）和4-法呢氧基-2，6-二羟基苯乙酮（2）；然后以化合物1和3，4-二羟基苯甲醛为原料，经羟基保护、缩合、环化和去保护基共6步反应，以19．8％的总收率全合成了（±）-6-法呢基-3'，4'，5，7-四羟基黄烷酮（3）．化合物1、2和3均是从澳大利亚植物Borroniaramosa中分离得到的新天然产物，此次为首次合成．     

萃取-紫外分光光度法测定微晶蜡中3, 4-苯并芘含量

要采用萃取-紫外吸收光谱法，测定微晶微量3，4-苯并芘的含量．选择二甲亚砜作为萃取溶剂，绘制工作曲线．结果表明，3，4-苯并芘含量在50-3000ng／g的范围内，成良好的线性关系，相关系数为0．9995．检出限为16ng／g．方法重复性好，相对标准偏差为6．2％，回收率在97．0％-99．4％之间．     

高效液相色谱/串联质谱法测定奶粉中的硝基呋喃代谢物

用高效液相色谱／串联质谱（LC—MS／MS）法同时测定奶粉中呋喃唑酮、呋喃它酮、呋喃西林和呋喃妥因的代谢物。盐酸水解奶粉中蛋白结合的代谢物，同时加入2-硝基苯甲醛（2-NBA），37℃过夜衍生化。加入硫酸锌，调pH值至7．0后，再加入亚铁氰化钾去除蛋白。后用乙酸乙酯提取，正己烷净化，分析物采用电喷雾电离正离子（ESI＋）、多反应监测（MRM）模式检测，内标法定量。在添加浓度0．5—2μg/kg范围内，内标法回收率为89．5％～110．3％；相对标准偏差（RSD）小于11，3％。5-马啉代甲基-3-氨基-2-恶唑酮（5-methylmorpholino-3-amino-2-oxazolidinone，AMOZ）、3-氨基-2-恶唑酮（3-amino-2-oxazolidinone，AOZ）方法检出限为0．05μg／kg，氨基脲（semicarbazide，SEM）、1-氨基-乙内酰胺（1-amino—hydantoin，AHD）为0．1μg/kg。     

无溶剂、无催化剂条件下5-[(3-吲哚基)-芳甲基]-2,2-二甲基-l,3-二氧六环-4,6-二酮的合成

在无溶剂和催化剂条件下，由芳香醛、吲哚、丙二酸亚异丙酯的三组分缩合反 应，制备了5．[(3-吲哚基)-芳甲基]-2，2-二甲基-1，3-二氧六环-4，6-二酮，产 率为70％～85％，产物结构经～1H NMR，IR确证．     

异环二取代二茂铁衍生物的合成

从芳基二茂铁的汞化产物中首次分离出四种异环二取代产物 1-氯汞基-1'-芳基二茂铁。1-氯汞基-1'-芳基二茂铁与碘作用得到四种相应的碘代产物。氯汞基二茂铁及1-氯汞基-1'-芳基二茂铁经[ClRh(CO)~2]~2 催化偶联反应制得联二茂铁和三种1'、1''-二芳基联二茂铁。以上化合物的组成与结构经元素分析、IR 和^1H NMR确证, 其中10种为新化合物。     

含能笼型碳硼烷衍生物的合成及其热性能

以DMSO或DMF为溶剂,1-溴甲基碳硼烷(1)分别与亚硝酸钠和叠氮钠发生亲核取代反应,合成了两种新型的含能笼型碳硼烷——1-硝基甲基碳硼烷(2)和1-叠氮基甲基碳硼烷(3),其结构经1H NMR和FT-IR表征。用DSC分析了1~3的热性能,结果表明:1和2分别在162.2℃和168.7℃分解,分解热分别为130.4 J.g-1和245.6 J.g-1。     

Fermented Oyster Extract Attenuated Dexamethasone-Induced Muscle Atrophy by Decreasing Oxidative Stress

It is well known that oxidative stress induces muscle atrophy, which decreases with the activation of Nrf2/HO-1. Fermented oyster extracts (FO), rich in γ-aminobutyric acid (GABA) and lactate, have shown antioxidative effects. We evaluated whether FO decreased oxidative stress by upregulating Nrf2/HO-1 and whether it decreased NF-κB, leading to decreased IL-6 and TNF-α. Decreased oxidative stress led to the downregulation of Cbl-b ubiquitin ligase, which increased IGF-1 and decreased FoxO3, atrogin1, and Murf1, and eventually decreased muscle atrophy in dexamethasone (Dexa)-induced muscle atrophy animal model. For four weeks, mice were orally administered with FO, GABA, lactate, or GABA+Lactate, and then Dexa was subcutaneously injected for ten days. During Dexa injection period, FO, GABA, lactate, or GABA+Lactate were also administered, and grip strength test and muscle harvesting were performed on the day of the last Dexa injection. We compared the attenuation effect of FO with GABA, lactate, and GABA+lactate treatment. Nrf2 and HO-1 expressions were increased by Dexa but decreased by FO; SOD activity and glutathione levels were decreased by Dexa but increased by FO; NADPH oxidase activity was increased by Dexa but decreased by FO; NF-κB, IL-6, and TNF-α activities were increased by Dexa were decreased by FO; Cbl-b expression was increased by Dexa but restored by FO; IGF-1 expression was decreased by Dexa but increased by FO; FoxO3, Atrogin-1, and MuRF1 expressions were increased by Dexa but decreased by FO. The gastrocnemius thickness and weight were decreased by Dexa but increased by FO. The cross-sectional area of muscle fiber and grip strength were decreased by Dexa but increased by FO. In conclusion, FO decreased Dexa-induced oxidative stress through the upregulation of Nrf2/HO-1. Decreased oxidative stress led to decreased Cbl-b, FoxO3, atrogin1, and MuRF1, which attenuated muscle atrophy.     

气相色谱-质谱法测定水中有机含磷农药前处理方法比较

用气相色谱-质谱法测定了水中6种有机含磷农药残留量,并比较了全自动固相萃取(方法1#)和全自动液-液萃取(方法2#)两种样品前处理方法。结果表明:从准确度方面,方法1#优于方法2#,所测得的方法1#的回收率在73.5%～92.0%之间,而方法2#的回收率在63.7%～89.7%之间;但方法2#耗时较方法1#少。     

苯并咪唑萘酰亚胺类化合物的合成与结构确证

本文合成并分离提纯了1位和4位单取代的苯并咪唑萘酰亚胺(NBI)类化合物1~4,对化合物1的紫外-可见光谱、红外光谱、质谱、核磁共振谱(包括1H NMR、13C NMR、DEPT、1H-13C HSQC、1H-13C HMBC、1H-1HCOSY多种NMR技术)进行了详细解析,对其所有的1H和13C NMR信号进行了归属,并使用了GIAO和CSGT两种方法量化计算核磁位移,通过多种波谱学技术确证了化合物的结构。     

Experimental and theoretical studies of fused-ring persistent [1,2,4]thiadiazinyl radicals

Five persistent radicals 1a-1e were generated by the oxidation of 4H-[1,2,4]thiadiazines 2a-2e and studied with ESR and UV-vis spectroscopy. Three of the radicals, 1a, 1d, and 1e, were generated in high yields (>90%) using either SO(2)Cl(2)/amine in toluene or AgO/K(2)CO(3) in a toluene/MeCN mixture. Halogenated radicals 1d and 1e were sufficiently stable for chromatographic isolation and vacuum sublimation. The solution stability of the fluorinated 1d was measured at t(1/2) approximately 4 months in the absence of oxygen, and 1e at t(1/2) approximately 40 min in the presence of air. The crystal and molecular structures of 1d were determined by X-ray crystallography showing columns of parallel almost evenly spaced planar heterocycles connected by infinite ...N...S... chains. Cyclic voltammetry of 1d and 1e shows reversible reduction waves at about 0 V and irreversible oxidations at about 1.2 V. Spectral and electrochemical properties of 1 were well reproduced by DFT methods.     

1—苯乙酰基—4—芳酰基氨基硫脲的合成及其在碱催化下的环化反应

1-酰基-4-芳基氨基硫脲类化合物在碱性条件下环化为具有广泛生物活性的3-取代基-4-芳基-1,2,4-三唑啉-5-硫酮的反应报道甚多,但1,4-位都含羰基的酰氨基硫脲在碱性条件下环化反应迄今报道较少。我们曾研究了1-[5-(α-萘)-2H-四唑-2-乙酰基]-4-芳酰基氨基硫脲和1-(α-萘乙酰基)-4-芳酰基氨基硫脲在碱催化下环化为3-取代基-4-芳酰基-1,2,4-三唑啉-5-硫酮的反应,它们在低浓度下均有一定的生物活性。本文研究了1-苯乙酰基-4-芳酰基氨基硫脲1_(a～m)在1mol/L K_2CO_3溶液催化下的环化反应,得到环化产物3-苄基-4-芳酰基-1,2,     

(Z)-1-[2-(三苯基锡基)乙烯基]-1-茚满醇及其酯和卤代物的合成与表征

在氮气保护下,1-乙炔茚满醇与三苯基氢化锡进行游离基加成反应,获得加成物(Z)-1-[2-(三苯基锡基)乙烯基]-1-茚满醇(1);将加成物(1)与苯酐反应,得到新型邻苯二甲酸单酯有机锡衍生物(2);衍生物(2)分别与二丁基氧化锡和三苯基氧化锡进行脱水反应,分别获得两个新型邻苯二甲酸酯的有机锡衍生物(3)和(4).将加成物(1)与卤素反应后,与锡原子直接相连的苯基被取代,得到一卤代和二卤代物(5～10).通过元素分析、¹HNMR和IR等手段对化合物1～10进行了结构表征,确定了该类邻苯二甲酸单酯和邻苯二甲酸酯的有机锡衍生物的结构.并测定了加成物(1)和一溴代物(6)的晶体结构,在加成物(1)中,由于分子内存在较弱的O→Sn[0.2778(8)nm]配位作用,锡原子呈扭曲三角双锥构型.在一溴代物(6)分子中,存在分子内O→Sn[0.2364(2)nm]配位键,锡原子呈扭曲的三角双锥构型.该系列化合物分子内的O→Sn配位能力和Lewis酸性强弱的顺序为:二卤化物>一卤化物>加成物;氯代物>溴代物>碘代物>加成物.     

Olefin polymerization by (cyclopentadienyl)(ketimide)titanium(IV) complexes of the type, Cp′TiCl2(N=CBu2)-methylaluminoxane (MAO) catalyst systems

Effects of substituents on cyclopentadienyl group for homopolymerization of ethylene, 1-hexene, and for ethylene/1-hexene copolymerization using a series of nonbridged (cyclopentadienyl)(ketimide)titanium complexes of the type, Cp′TiCl₂(N=C^tBu₂) [Cp′ = Cp (1), ^tBuC₅H₄ (2), C₅Me₅ (Cp^*, 3), and indenyl (4)] have been explored in the presence of methylaluminoxane (MAO) cocatalyst. Complexes 1–3 showed the similar catalytic activities for ethylene polymerization although the activity by 4 was somewhat low, whereas the activity for 1-hexene polymerization increased in the order 1 > 4 2 > 3. These complexes showed significant activities for ethylene/1-hexene copolymerization affording high molecular weight poly(ethylene-co-1-hexene)s with unimodal molecular weight distributions, and the activity increased in the order: 4 > 1 2, 3. The r_Er_H values in the polymerization by 1–3 at 40 °C were 0.35–0.52 which clearly indicate that the 1-hexene incorporation in the copolymerization did not proceed in a random manner. The r_E values by 1–3 were 6.0–6.4 and the values were independent upon the cyclopentadienyl fragment employed; the r_E values by 4 at 40 °C were 10.2–10.9 which were close to those by ansa-metallocene complex catalysts. These values were influenced by the polymerization temperature, and the 1-hexene incorporation by 1–4 became inefficient at higher temperature, although the observed activities especially by 1, 4 were highly remarkable.