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51.
52.
目的探讨风湿性关节炎中环瓜氨酸肽抗体(CCP)与抗角蛋白抗体(AKA)诊断价值。方法本次共选择类风湿性关节炎(RA)患者100例,均为我院2012年1月—2014年1月收治,就CCP、AKA检测资料与同期收治的非RA30例硬皮病、系统性红斑狼疮患者进行对比。结果 RA组经检测示,AKA阳性率、CCP阳性率、RF阳性率均显著高于非RA组,差异均有统计学意义(P〈0.05)。AKA、CCP联合RF,有高达97%的灵敏度。结论综合分析显示,CCP、AKA、RF联合检测,有较高灵敏度,在早期确诊和初步筛查RA作用重大,可降低误诊、漏诊率,有助于实现早宣教、早诊治,对骨质破坏程度进行预测,进而保障患者生存质量。  相似文献   
53.
Globally, abortion has emerged as a critical determinant of maternal morbidity and mortality. The Ghana government amended the country's abortion law in 1985 to promote safe abortion. This article discusses the findings of a qualitative study that explored the decision-making experiences of 28 female abortion seekers aged between 15 and 30 years in Ghana. Key findings from the study are that individuals claimed autonomy in their abortion decisions; underlying the abortion decisions were pragmatic concerns such as economic difficulties, child spacing, and fear of parental reaction. In conclusion, we examine the health implications of Ghanaian women's abortion decisions.  相似文献   
54.
Innexins in invertebrates are considered to play roles similar to those of connexins and pannexins in vertebrates. However, it remains poorly understood how innexins function in biological phenomena including their function in the nervous systems. Here, we identified inx‐4, a member of the innexin family in C. elegans, by a forward screening of thermotaxis‐defective mutants. The inx‐4 mutants exhibited abnormal migration to a temperature slightly higher than the cultivation temperature, called mild thermophilic behavior. Rescue experiments revealed that INX‐4 acts in the major thermosensory neuron AFD to regulate thermotaxis behavior. INX‐4::GFP fusion protein localized exclusively along axons in AFD neurons. In addition, over‐expression of INX‐4 in AFD neurons induced a cryophilic behavior, which is opposite to inx-4 mutants. Our findings suggest that INX‐4/Innexin in AFD may fine‐tune the execution of thermotaxis behavior when moving to desired temperatures.  相似文献   
55.
目的梳理胰腺癌诊断筛查方式的历史沿革,探究在中国人口基数大、经济处于发展中的背景下,如何实现胰腺癌的"早诊早治"。方法采用系统回顾的方法进行分析。计算机检索CNKI、VIP、WanFang Data、Web of Science、PubMed和EMbase数据库,同时由两名研究员独立检索百度搜索引擎,检索时限均从建库至2018年2月28日,搜集胰腺癌筛查方法及效果评价的相关报道,进行定性描述。结果共117篇文献纳入研究。国内对胰腺癌筛查方式的探索经历了萌芽、启蒙和成长三个阶段。现有筛查方式有临床表现、影像学方法、血清肿瘤标记物和分子生物学基因诊断四种,各有利弊。单一手段无法实现较高特异性和灵敏度,联合检测成为必然趋势。考虑到应用过程中的效益问题,在高危人群中进行筛查可以有效缩小人群范围,实现精准筛查。结论我国针对胰腺癌筛查方面的研究较国外有较大差距。筛查方法呈现多样性,联合检测是必然趋势。在高危人群中进行胰腺癌筛查将成为技术瓶颈下的突破口。  相似文献   
56.
Optimization of the ionomer materials in catalyst layers (CLs) which sometimes is overlooked has been equally crucial as selection of the membranes in membrane electrode assembly (MEA) for achieving a superior performance in proton exchange membrane fuel cells (PEMFCs). Four combinations of the MEAs composed of short-side-chain (SSC) and long-side-chain (LSC) perfluorosulfonic acid (PFSA) polymers as membrane and ionomer materials have been prepared and tested under various temperatures and humidity conditions, aiming to investigate the effects of different side chain polymer in membranes and CLs on fuel cell performance. It is discovered that SSC PFSA polymer used as membrane and ionomer in CL yields better fuel cell performance than LSC PFSA polymer, especially at high temperature and low RH conditions. The MEA with the SSC PFSA employed both as a membrane and as an ionomer in cathode CL demonstrates the best cell performance amongst the investigated MEAs. Furthermore, various electrochemical diagnoses have been applied to fundamentally understand the contributions of the different resistances to the overall cell performance. It is illustrated that the charge transfer resistance (Rct) made the greatest contribution to the overall cell resistance and then membrane resistance (Rm), implying that the use of the advanced ionomer in CL could lead to more noticeable improvement in cell performance than only the substitution as the membrane.  相似文献   
57.
目的观察针刀干预对颈椎病兔软骨终板整合素β1-FAK力学信号通路相关因子整合素β1、磷酸化黏着斑激酶(p-FAK)mRNA和蛋白表达的影响,探讨针刀在延缓椎间盘退变恢复颈椎力学平衡过程中的可能作用机制。方法将40只新西兰雄性兔随机分为空白组、模型组、电针组及针刀组,每组10只,空白组不做干预处理,其余建立颈椎病动物模型,持续12周。造模成功后电针组于兔颈肌两侧"天柱""颈百劳""大杼"穴处行毫针干预,隔天治疗1次,每周3次,共3周;针刀组于兔颈肌硬结、条索以及棘突等处行针刀干预,每周1次,共3次。干预结束后1周,采用实时荧光定量PCR法检测椎间盘软骨终板整合素β1、p-FAK的mRNA表达水平,采用Western Blot技术检测椎间盘软骨终板整合素β1、p-FAK的蛋白含量。结果与空白组相比,模型组软骨终板整合素β1 mRNA和蛋白表达水平均明显降低(P<0.01),软骨终板p-FAK蛋白表达水平升高(P<0.05)。与模型组相比,电针组软骨终板整合素β1、p-FAK蛋白表达水平均升高(P<0.05)。针刀组软骨终板整合素β1、p-FAK mRNA和蛋白表达水平均明显升高(P<0.01)。与电针组相比,针刀组软骨终板p-FAK mRNA和蛋白表达水平升高(P<0.05)。结论针刀干预可调节软骨终板整合素β1、p-FAK mRNA和蛋白表达,这可能是针刀减缓椎间盘退变,重建颈椎力学平衡,治疗颈椎病的作用机制之一。  相似文献   
58.
An addition of H-phosphonates to aryl alkynes was realized under solvent- and metal-free conditions, affording Markovnikov-selective α-vinylphosphonates in moderate to good yields. A wide range of aryl alkynes could be applied for the reaction. A tentative mechanism of addition–substitution was proposed based on in situ31P {1H} NMR studies.

Synthesis of α-vinylphosphonates from terminal alkynes and H-phosphonates as only the Markovnikov-regioisomer under metal- and solvent-free conditions.

Vinyl phosphorus compounds are of high importance because of their wide application in the fields of biological metabolism,1 functional materials,2 and as synthetic blocks of organophosphorus compounds.3 Some reviews have documented the preparations and applications of the vinyl phosphorus.4 Normally, the compounds can be acquired from alkynes, via the addition with H–P species. Aromatic ketones and aldehydes are also used as the sources of vinyl phosphorus, via multi-step conversions.1b,5 The recently developed methods to obtain vinyl phosphorus involving H–P species include decarboxylation of cinnamic acid,6 dehydrogenation of active alkene,7 and dehydration of alcohols.8The addition of H–P species to alkynes is undoubtedly the most effective and atom economical method. The addition was usually catalysed by metals.4e,9 One of the authors has reported palladium and rhodium catalysed additions of H–P species to alkynes.9ad Similar additions could be realized by catalysis with copper, nickel, molybdenum and ytterbium (Chart 1).10 The metal-catalysed procedures also include Suzuki reaction and others.11 Although much progress has been made in this area, problems associated with narrow substrate scope, the need to use expensive transition metals and a stoichiometric amount of additives, and poor regio- and stereo-control have encouraged researchers to search for new and more efficient methods.Open in a separate windowChart 1Comparison of the construction of C(sp2)–P bonds to our current work.Recently, triflic anhydride (Tf2O) has been applied for electrophilic activation of amides and P Created by potrace 1.16, written by Peter Selinger 2001-2019 O species, and the activated intermediates could be used for the substitutions with various nucleophilic reagents.7b,12 The conversions of P Created by potrace 1.16, written by Peter Selinger 2001-2019 O species to C(sp2)–P bonds are quite rare. Miura and coauthors have reported a Tf2O promoted activation of secondary phosphine oxides, which is applied for phosphination and intramolecular cyclization with alkynes.13 However, the scopes are limited with inner-alkynes. The application of H-phosphonates was not reported for the reaction (Chart 1).Herein we enclosed a novel Tf2O promoted reaction of terminal alkyne with H-phosphonates. Vinyl phosphonates were afforded under metal- and solvent-free conditions, in excellent Markovnikov-regio selectivity.Phenylacetylene (1a) was initially treated with diethyl phosphite (2a) in the presence of Tf2O in a molar ratio of 1 : 1 : 1. To our delight, diethyl 1-phenyl ethenylphosphonate (3aa), a Markovnikov addition product, was obtained in high regio-selectivity but in poor yield (10%). The reaction conditions were subsequently optimized with 1a and 2a. Considering Tf2O was moisture sensitive, all experiments were performed under nitrogen. Two equivalents 2a was used to ensure 1a was consumed as much as possible. The conversion and isolated yield were calculated based on 1a (
EntryMolar ratio of 1a/2a/CatBaseTemp.Solvent (1 mL)Conversion% (isolated yield%)b
11 : 2 : 1Rt12
21 : 2 : 140 °C46
31 : 2 : 160 °C92
41 : 2 : 165 °C98 (53)
51 : 2 : 180 °C98 (56)
61 : 2 : 0.565 °C79
71 : 2 : 0.865 °C92
81 : 2 : 1.265 °C86
91 : 2 : 165 °C0c
101 : 2 : 165 °CCH2Cl23
111 : 2 : 165 °CToluene9
121 : 2 : 165 °CTHF0
131 : 2 : 165 °CEtOAc22
141 : 2 : 1Na2CO365 °C0d
151 : 2 : 1Pyridine65 °C99 (64)d
161 : 2 : 12,6-Lutidine65 °C99 (54)d
171 : 2 : 1DBU65 °C99 (64)d
Open in a separate windowaReaction conditions: 1a (0.2 mmol), 2a (0.40 mmol) and Tf2O (0.2 mmol) stirring at different temperatures for 24 h.bThe conversions were estimated based on 1H NMR spectrum, and isolated yields were calculated based on 1a.cTfOH was used.d1.0 equiv. of base was used.When the mixture of 1a, 2a and Tf2O was stirred at room temperature, a new signal at 17.1 ppm was observed on 31P NMR spectrum. The two doublet peaks at 6.35 and 6.17 ppm on proton NMR spectrum, assigned as 3aa, was detected in 12% (entry 1 of 14 The conversion cannot be further improved at higher temperature such as 80 °C.When 0.5 equiv. Tf2O was used, the conversion of 1a was dropped to 79%. The usage of 0.8 equivalent of Tf2O led 92% conversion (entries 6 and 7). However, excessive Tf2O, such as 1.2 equivalents, resulted in the reduced conversion (86%, entry 8).Once triflic acid was used to replace Tf2O, 3aa was not detected (entry 9).To carry the reaction in some solvent such as dichloromethane, toluene, THF or ethyl acetate, gave worse result than neat condition (entries 10–13). In the presence of sodium carbonate, the reaction cannot take place (entry 14). The presence of pyridine, 2,6-lutidine or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) slightly increased the conversion (entries 15–17).Adopting the above optimized condition, the reaction of alkyne with H-phosphonate was performed ( Open in a separate windowaIsolated yields based on 1a.Various terminal alkynes was then examined ( Open in a separate windowaIsolated yield.bTwo equivalents of Tf2O were used.cThe alkyne/P–H regent/Tf2O/pyridine were used in the molar ratio of 1 : 4 : 2 : 2.Some ethynyl heterocycles, such as 2- or 3-ethynylthiophene could be employed for the reaction, affording 3la or 3ma, respectively. For 1,4-diethynylbenzene (1n), the addition was realized when 2a and Tf2O were used in double equivalents. However, the alkynes having strong EWG, such as trifluoromethyl or 3-pyridinyl, cannot react with 2a. Aliphatic terminal alkynes, such as 1-octyne, also did not afford the product.The mechanism of the reaction was studied via in situ NMR experiments, and was proposed in Scheme 1. 2a and Tf2O formed triflate 4 of phosphite via an equilibrium.12b,15 Meanwhile, triflic acid was generated (step 1). The addition of triflic acid to 1a formed 1-phenylvinyl triflate 5 as an intermediate (step 2). The subsequent nucleophilic substitution of 5 with 4 formed vinyl phosphonate 3aa (step 3).Open in a separate windowScheme 1Proposed mechanism.The step 1 was confirmed by the observation of the signal of acidic proton in TfOH during the mixing of 2a with Tf2O (Fig. 1A). When 1a was added, 5 was detected, as seen the two doublet peaks at 5.61 and 5.38 ppm on 1H NMR spectrum (step 2 and Fig. 1B). When the mixture was heated at 60 °C, the signals of 3aa at 6.16–6.37 ppm emerged. The peaks were increased with prolonged heating, accompanied with the decreasing of the signals of 5 (step 3, Fig. 1C and D). Similar results were observed when Tf2O was initially mixed with 1a (Fig. 1E–H). After heating at 60 °C for 8 h, the signals of 1a, respected by the peak of terminal alkyne at 3.07 ppm, were disappeared (Fig. 1H).Open in a separate windowFig. 1The results of in situ NMR experiments of the reaction of 1a with 2a in the presence of triflic anhydride.The addition of triflic acid to 1a probably formed α-carbon ion as intermediate, which could be stabilized by phenyl and be converted to Markovnikov-product 5. Although the nucleophilic substitution on vinyl carbon was difficulty, the strong leaving activity of trifluoromethanesulfonyloxy on 5 enabled step 3 occurred. Miura proposed a cyclic phosphirenium intermediate for the addition and cyclization,13 which could be probably stabilized by the alkyl groups of inner-alkynes and secondary phosphine oxides. In our case, the electron-withdrawing alkoxyl on phosphorus of 2a was not favorable for the formation of the phosphirenium, thus the reaction proceeded via α-carbon ion and addition–substitution occurred.TfOH was necessary to the formation of 5 from 2a (step 2). However, triflic acid cannot sole promote the reaction, as seen in entry 9 of iii) species 4 by triflic anhydride, the lone electron pair on phosphorus of 4 could attack 5 to form the product. It was not sure the small quartet peak at 4.62 ppm belonged to 4 (Fig. 1F). On 31P NMR spectrum, the peak of 2a at 17.0 ppm obviously became broad in poor resolution when mixed with triflic anhydride (as seen in ESI). The results also supported the equilibrium between 2a and 4 (step 1).  相似文献   
59.
绞股蓝提取物制备工艺研究     
钟娜娜  吴思平  吴凌凤  梁香 《中国民族民间医药杂志》2020,(3):47-51
目的:研究出绞股蓝提取物,为绞股蓝产品研发提供实验数据。方法:建立绞股蓝提取物的化学评价方法;优化绞股蓝提取物的提取工艺,用化学评价方法分别对绞股蓝的乙醇浓度、料液比、提取时间、提取次数4个单因素进行考察,以L 9(34)正交表设计优化工艺,筛选出最佳提取工艺。结果:经单因素考察和正交优化得到绞股蓝提取物制备工艺为料液比为1∶8的70%乙醇,加热回流提取3次,每次45 min,绞股蓝总皂苷含量为0.1025 mg/mL,提取率为10.25%。结论:建立的化学评价方法可评价绞股蓝提取物;制备工艺能为绞股蓝产品研发提供依据。  相似文献   
60.
A retrospective study on the diagnosis and treatment of dementia in patients referred to the Sagamihara Municipal Medical Center for Dementia for consultation     
Yoshitaka Kyou  Satoru Oishi  Takeya Takizawa  Ryutaro Suzuki  Nana Nakamura  Hisatoshi Arai  Hitoshi Miyaoka 《Psychogeriatrics》2020,20(3):247-253
  相似文献   
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