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11.
A prospective study of the relation between nerve palsy and the surgical approach used for total hip arthroplasty was performed on 1,000 consecutive patients. A postoperative neuropathy was diagnosed in eight patients for an overall prevalence of 0.8%. The overall prevalence of nerve palsy with the posterior approach was 0.6% and 1.0% with the lateral transtrochanteric approach. In both primary and revision surgeries, there were no statistical differences between the two approaches. Our data suggest that it is the anatomic variations and complexity of the reconstruction that are associated with nerve injury and not the surgical approach per se. The increased prevalence of nerve palsy seen in revision surgeries (1.4%) regardless of the approach supports this position.  相似文献   
12.
A cascade dehydrogenative Morita–Baylis–Hillman reaction of the C(sp3)–H of primary alcohols with the C(sp2)–H of electron-deficient olefins for forming allylic alcohols mediated by SO2F2 was developed. This method provides a mild process for the preparation of allylic alcohol moieties without the requirement of transition metals.

A cascade dehydrogenative Morita–Baylis–Hillman reaction of the C(sp3)–H of primary alcohols with the C(sp2)–H of electron-deficient olefins for forming allylic alcohols mediated by SO2F2 was developed.

Allylic alcohols are valuable scaffolds that are used in the construction of multifunctional building blocks and complex natural products.1 The versatility of these molecules has been demonstrated in the preparation of a series of biologically active compounds.2 A representative protocol for the synthesis of allylic alcohols is the well-known Morita–Baylis–Hillman reaction, one of the most widely applied methods for C–C bond formation.3In fact, C–C bond formation is among the most significant processes in chemistry and plays a central role in the construction of new organic molecules,4 in which transition metal catalysed C–C bond formation has particularly attracted great interest in recent years.5 For instance, a reaction for the direct formation of C–C bonds using two different unfunctionalized C–H bond partners was reported (Scheme 1a).6 Despite the great advantages of these dehydrogenative reactions for the formation of C–C bonds7 there are still certain limitations, such as that precious metal catalysts are still required (metal catalysts are sometimes undesirable).8 To overcome the limitations, we developed a new protocol for the formation of allylic alcohol motifs using abundant and inexpensive reagents.Open in a separate windowScheme 1Dehydrogenative reactions for the formation of C–C bonds.Alcohols, as a class of cheap and abundant industrial chemicals, have great advantages in green chemistry and organic synthesis.9 Sulfuryl fluoride (SO2F2), is also another inexpensive (about $1 per kg) and abundant chemical, which has attracted significant attention for chemical transformation.10 As part of our continuous efforts on the use of SO2F2 in exploring new synthetic methods to access important chemicals,10cl herein, we report a one-pot process for the construction of valuable allylic alcohols through a dehydrogenative Morita–Baylis–Hillman reaction of the C(sp3)–H of primary alcohols with the C(sp2)–H of electron-deficient olefins (Scheme 1b).Initially, we examined the feasibility of this transformation using (4-nitrophenyl)methanol 1a as a model substrate to react with methyl methacrylate 2a to generate the corresponding allylic alcohol 3a. It has been widely established that tertiary amines such as trimethylamine (Me3N), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,4-diazabicyclo[2.2.2]octane (DABCO) are effective for the Baylis–Hillman reaction,11 which inspired us to carry out our preliminary experiments using these bases. The use of Me3N and DBU provided the desired product 3a in only 5% and 41% yields, respectively (
EntryBase (X eq.)2a (Y eq.)Temperature (°C)Yieldb (3a, %)
1Me3N (3.0)3.0rt5
2DBU (3.0)3.0rt41
3DABCO (3.0)3.0rt74
4 DABCO (3.0) 3.0 40 83
5DABCO (3.0)3.05077
6DABCO (1.0)3.04042
7DABCO (5.0)3.04085
8DABCO (3.0)1.04052
9DABCO (3.0)5.04084
Open in a separate windowaGeneral reaction conditions: a mixture of (4-nitrophenyl)methanol (1a, 0.2 mmol), K2CO3 (0.24 mmol, 1.2 eq.) and DMSO (1.5 mL, 0.13 M) under an atmosphere of SO2F2 (balloon) was stirred at room temperature for 12 h before base (X eq.) and methyl acrylate 2a (Y eq.) were added. The resulting mixture was stirred at the corresponding temperature for an additional 36 h.bHPLC yields using the pure methyl 2-(hydroxy(4-nitrophenyl)methyl)acrylate (3a, 0.2 mmol) as the external standard (tR = 3.021 min, λmax = 272.5 nm, MeOH/H2O = 70 : 30 (v/v)).We subsequently investigated the substrate scope of benzyl alcohols 1 under the optimized conditions, and the results are summarized in Open in a separate windowaGeneral reaction conditions: benzyl alcohols (1, 1.0 mmol), K2CO3 (1.2 mmol, 1.2 eq.), DMSO (7.5 mL, 0.13 M), SO2F2 balloon, rt, 12 h. Then DABCO (3.0 mmol, 3.0 eq.) and methyl acrylate 2a (3.0 mmol, 3.0 eq.), 40 °C, 36 h. Isolated yield.bHPLC yield.c40 °C, 72 h.d40 °C, 5 days.e40 °C, 6 h.To further demonstrate the generality and substrate scopes of the process, we also examined some long-chain aliphatic alcohols under the standard conditions for the coupling with methyl acrylate 2a ( Open in a separate windowaGeneral reaction conditions: long-chain aliphatic alcohols (1, 1.0 mmol), K2CO3 (1.2 mmol, 1.2 eq.), DMSO (7.5 mL, 0.13 M), SO2F2 balloon, rt, 12 h. Then DABCO (3.0 mmol, 3.0 eq.) and methyl acrylate 2a (3.0 mmol, 3.0 eq.), 40 °C, 36 h. Isolated yield.In order to demonstrate the practicality of the process, a couple of gram-scale reactions were performed under the standard conditions (Scheme 2). Despite a slight decline in the yield, 1i was successfully converted to its corresponding allylic alcohol 3i in 70% yield. Pyridine-containing benzylic alcohol 1s was also smoothly transformed into the corresponding allylic alcohol 3s in 75% yield without any deterioration in efficiency.Open in a separate windowScheme 2Gram-scale reactions.In conclusion, we have developed a cascade dehydrogenative Morita–Baylis–Hillman reaction of the C(sp3)–H of primary alcohols with the C(sp2)–H of electron-deficient olefins to form allylic alcohols mediated by SO2F2. This new protocol has the features of a wide scope and great functional group compatibility. Using this method, inexpensive, easily accessible, and abundant alcohols can be directly transformed to highly valuable allylic alcohols under mild conditions without the use of precious transition metals.  相似文献   
13.
无公害辛夷栽培技术探讨     
胡娅婷  胡心怡  朱星语  孟祥霄  王瑀  刘霞 《世界科学技术-中医药现代化》2019,21(4):784-791
辛夷是中国传统药材,来源于木兰科望春花Magnolia biondii Pamp.、玉兰Magnolia denudata Desr.或武当玉兰Magnolia sprengeri Pamp.的干燥花蕾。辛夷主要具有发散风寒、宣通鼻窍之效,其野生资源少,野生资源少,市场的需求量随着人们生活水平的提高越来越大,种植出优质无公害辛夷栽培品已成为重要研发目标。因此,无公害辛夷的栽培将是未来辛夷产业发展的主流。本文从辛夷产地生态适宜性栽培用地的区划出发,根据栽培环境要求、科学种植技术、施肥规范、病虫害防治、采收加工及质量标准等内容制定了辛夷无公害农田栽培技术体系,为辛夷的栽培生产提供科学性的指导。  相似文献   
14.
高温促进黄花蒿中青蒿素生物合成的机制研究     
鹿江南  张栋  丁丹丹  高翰  韩宗贤  刘霞  向丽 《中国中药杂志》2018,(20):4169-4176
黄花蒿Artemisia annua又名青蒿,是中国传统中药,其有效成分青蒿素是一种含过氧桥基团结构的倍半萜内酯类化合物,是一种能有效抗疟的药物。很多理化因子例如盐分、水分、光照、植物激素等均能诱导黄花蒿中次生代谢产物青蒿素的合成,温度作为一种重要的生长因素对青蒿素的合成也有极大地影响。该文旨在研究高温诱导对黄花蒿中青蒿素生物合成的影响。将黄花蒿幼苗放置在25,40℃条件下,分别在0,3,12,36 h后取样,利用液相色谱-质谱联用法测定各个样品中的青蒿素含量;提取样品的总RNA,进行转录组测序并且利用实时荧光定量PCR技术定量分析青蒿素合成途径及竞争途经关键酶基因的表达。结果显示40℃处理3,12,36 h后,青蒿素质量分数分别提高20%,42%,68%;FDS,ALDH1,CYP71AV1和ADS的表达量分别上调4. 3,3. 3,2. 5,1. 9倍,SQS和BPS的表达量下调了37%和90%。综上,高温可以通过促进青蒿素合成途径合成酶基因表达量,并且抑制青蒿素竞争途径合成酶基因的表达量从而促进青蒿素的生物合成。  相似文献   
15.
经典名方羌活胜湿汤指纹图谱建立及功效物质预测分析          下载免费PDF全文
姚子豪  熊富良  刘霞  张雪琼  汪沁柔  颜莉娟  杨元喜  陶正恒  李心愿 《中国现代中药》2024,26(5):815-822
目的 基于网络药理学方法和指纹图谱,分析预测经典名方羌活胜湿汤(QSD)的质量标志物(Q-marker)。方法 采用高效液相色谱法建立QSD指纹图谱,对共有峰进行归属和指认,并基于可测性和可溯源性筛选活性成分;运用网络药理学筛选靶点和通路,构建QSD的成分-靶点-通路相互作用网络,预测QSD的Q-marker。结果 共标定了20个共有峰,通过对照品指认出升麻素苷、洋川芎内酯Ⅰ、蛇床子素、紫花前胡苷、甘草酸铵、藁本内酯、阿魏酸、异欧前胡素、5-O-甲基维斯阿米醇苷、二氢欧山芹醇当归酸酯10个色谱峰,相似度均大于0.862;采用网络药理学方法对6个活性成分进行成分-靶点-通路网络构建与分析,富集的通路包括癌症中的蛋白聚糖、癌症的途径、化学致癌作用-受体激活、内分泌抵抗等。根据成分、靶点及通路之间的连接度初步预测二氢欧山芹醇当归酸酯、升麻素苷、甘草酸铵、异欧前胡素、蛇床子素、5-O-甲基维斯阿米醇苷6个活性成分可能通过调节这些信号通路达到祛风、胜湿和止痛的作用。结论 通过建立QSD指纹图谱,基于网络药理学方法分析预测QSD中的Q-marker,进一步明确QSD质量控制标准,有利于提高其质量控制水平,也为后期深入研究QSD的作用机制提供参考。  相似文献   
16.
探索psbA-trnH序列对竹茹、天竺黄及其近缘物种的鉴定   总被引:1,自引:0,他引:1  
樊佳佳  张婉冰  向丽  张雅琴  刘霞 《世界科学技术-中医药现代化》2014,16(11):2349-2354
目的:采用psbA-trnH序列对竹茹、天竺黄及其近缘物种进行DNA条形码鉴定研究,保障临床用药准确、安全。方法:收集竹茹、天竺黄及其近缘物种共71份材料,提取基因组DNA、PCR扩增并双向测序,经CodonCode Aligner V 4.2拼接获得序列,应用MEGA5.0比对分析,计算种内及种间Kimura-2-Parameter(K2P)遗传距离并构建系统发育树。结果:竹茹、天竺黄各基原及其近缘物种基于psbA-trnH序列的种内最大K2P遗传距离均小于其与近缘物种的种间最小K2P遗传距离;NJ树图结合MEGA比对结果显示,基原植物青杆竹与青皮竹之间无法区分,而竹茹、天竺黄及其他基原物种之间均可较好地区分并呈现明显的单系性。结论:基于psbA-trnH序列可以准确地鉴定多基原药材竹茹、天竺黄及其近缘物种。  相似文献   
17.
羧甲基壳聚糖-聚乙二醇作为胰岛素载体的研究          下载免费PDF全文
吴珊珊  熊富良  宋豪源  李良红  张雪琼 《中国医院药学杂志》2017,37(10):906-910,915
目的:制备胰岛素-羧甲基壳聚糖-聚乙二醇纳米粒。方法:利用红外光谱(FTIR)和核磁共振氢谱(1H-NMR)对羧甲基壳聚糖-聚乙二醇的结构进行表征,用粒度分析仪测定纳米粒的粒径分布及电位,采用动态透析法考察纳米粒的释药性能,用CCK-8试剂盒检测纳米粒细胞毒性,以糖尿病小鼠为模型,研究纳米粒的降血糖作用。结果:聚乙二醇成功接枝到羧甲基壳聚糖上,包埋胰岛素的纳米粒的平均粒径为(257.5±12.1)nm,Zeta电位为(-15.2±0.3)mV,负载胰岛素的羧甲基壳聚糖-聚乙二醇纳米粒在中性释放介质中,5 h内胰岛素的释放速度较快,之后8 h趋于平稳,胰岛素的累计释放量可达到80%,CCK-8试剂盒显示纳米粒对L929细胞基本无细胞毒性,50 U·kg-1的纳米粒溶液经灌胃给药后,血糖浓度明显降低。结论:胰岛素-羧甲基壳聚糖-聚乙二醇纳米粒基本无毒性,具有良好的生物相容性,对糖尿病小鼠有效发挥降血糖作用。  相似文献   
18.
NOTCH1对T-ALL抑癌基因ID4的负调控作用     
刘娟  燕莞瑶  楼一层 《肿瘤防治研究》2016,43(2):123-128
目的 研究DNA结合抑制因子4(inhibitor of DNA binding 4, ID4)在急性T淋巴细胞白血病(T-cell acute lymphoblastic leukemia, T-ALL)中的表达水平,探讨NOTCH1与ID4的相关性及其调控机制。方法 通过Oncomine和Pieters R数据库分析T-ALL患者与正常捐献者中ID4的表达差异及T-ALL患者中NOTCH1与ID4的相关性,用qRT-PCR和Western blot检测阻断NOTCH1或激活NOTCH1后ID4的表达变化进行验证。用生物信息学的方法特异预测出microRNA-342(miR-342)靶向ID4,通过双荧光素酶报告体系进行验证。过表达或沉默miR-342后,qRT-PCR和Western blot检测ID4的表达变化。阻断NOTCH1或激活NOTCH1,qRT-PCR检测miR-342的表达变化。结果 ID4在T-ALL患者中的表达较正常组显著下调(P<0.01);ID4受NOTCH1负调控(P<0.05);双荧光素酶报告系统验证预测结果正确;过表达miR-342后,ID4的表达受到显著抑制(P<0.05),沉默miR-342后,ID4的表达明显上调(P<0.05);NOTCH1信号的阻断能够抑制miR-342的表达,NOTCH1信号的激活能够上调miR-342的表达。结论 NOTCH1通过激活miR-342对ID4的负调控作用从而下调抑癌基因ID4的表达,促进T-ALL的发生。  相似文献   
19.
20 years ago: The British Homoeopathic Journal,January 1974     
《The British homoeopathic journal》1994,83(1):51
  相似文献   
20.
Chinese herbal medicine resources:Where we stand     
Ran-ran Gao  Ya-ting Hu  Yang Dan  Li-jun Hao  Xia Liu  Jing-yuan Song  ? 《中草药(英文版)》2020,12(1):3-13
In recent years, the development of Chinese herbal medicine (CHM) has been challenged by shortages of CHM resources and drug safety concerns related to end products. There have been significant efforts by Chinese scholars to tackle these challenges, which are revealed by analyzing the research trend of CHM resources via surveying Chinese Traditional and Herbal Drugs (Zhong Cao Yao), a representative journal in CHM. Our study focused on 781 articles in CHM resources from 2013 to 2018 and included four subject areas: germplasm resources, quality analysis and evaluation, cultivation, and bioengineering of CHM. Discussion and prospective for future investigations were also presented, including: construct the core germplasm of medicinal plants and expand germplasms; combine molecular research with field experiments and promote the deeper study of cultivation of CHM plants; improve the quality evaluation method of CHM and strengthen the identification of Chinese patented medicines; promote the sustainable development of CHM resources by utilizing bioengineering and synthetic biology. This study helps international scholars understand the status quo of CHM research and provides theoretical support for the healthy, modern, and international development of CHM, and it will facilitate the sustainable development of the traditional Chinese medicine industry.  相似文献   
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