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41.
目的分析变应性鼻炎血清变应原特异性Ig E(s Ig E)、皮肤点刺试验(SPT)、外周血嗜酸粒细胞(EOS)计数与鼻部症状积分的相关性。方法选择2011年9月至2014年5月荆州市中心医院收治的变应性鼻炎患者70例,对患者分别采用s Ig E检测、SPT、外周血EOS计数测定,并对鼻炎症状进行积分;分析各结果的相关性。结果鼻炎症状积分与s Ig E检测试验、变应原SPT、外周血EOS计数无明显相关性(r=0.058,0.021,0.031,均P>0.05);s Ig E与SPT呈明显正相关(r=0.532,P<0.05),s Ig E与EOS、SPT与EOS无明显相关性(r=0.133,0.078,均P>0.05)。结论 s Ig E与SPT均可作为诊断变应性鼻炎的方法,但是无法对患者症状的严重程度进行判断,需要结合患者的主诉、体征、病状和病史进行综合评价。  相似文献   
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目的:根据流行病学调查的方法,对艾森克个性问卷(EPQ)进行信效度检验,并建立该问卷镇江市个别正常(牙合)学生性别常模,对临床工作指导更具针对性.方法:根据学校综合实力的不同,采用随机分层整群抽样的方法,随机抽取镇江市9所学校不同年级38个班的1430学生,根据纳入和排除标准筛选出符合标准的个别正常(牙合)学生,并根据年龄分为幼年(12~15岁)组和成人(16岁以上)组,然后在相同的环境条件和相同的指导语指导下进行艾森克个性问卷测量,根据测量结果建立镇江市个别正常(牙合)学生艾森克个性问卷性别常模.结果:男性个别正常(牙合)学生在P分量表和E分量表上的评分高于女生的评分,但男女学生在E分量表上的差异没有统计学意义;男性个别正常(牙合)学生在N分量表和L分量表上的评分低于女生的评分,但幼年男女生在N分量表上的差异没有统计学意义.结论:可采用艾森克个性问卷建立镇江市个别正常(牙合)学生EPQ的性别常模,女性对错牙(牙合)畸形所致的容貌影响更为关注.  相似文献   
46.
We herein report the functionalization of α-C–H in alcohols through cross-dehydrogenative coupling reactions. Selectfluor was used as a mild oxidant. In situ-generated HF participated in the reaction and no external strong acid was necessary. A variety of heteroaryl-substituted alcohols were achieved with good yields and with good functional group tolerance.

We herein report the functionalization of α-C–H in alcohols through cross-dehydrogenative coupling reactions.

Alcohols are one of the most important types of compounds, because they exist universally in bioactive molecules and are also found in nature in the form of sugars, steroids, etc. Furthermore, alcohols can be used as versatile building blocks, and be transformed into other functional groups. The synthesis of alcohols is a classic topic in organic chemistry. Late-stage functionalization has attracted the interest of chemists because in this way complex molecules could be modified. In particular, functionalization of C–H is a very efficient way to build various structures, as pre-functionalization here is not needed. Thus, transformation of C–H in alcohols is a direct method to prepare diverse alcohols from simple molecules.During the past several decades, activations of the α sp3 C–H groups of alcohols have been achieved through radical-involved processes. In the early research, functionalizations of α C–H groups in alcohols were always initiated by light or di-tert-butyl peroxide, and the generated radicals could add to alkenes, affording alkylated alcohols.1 This reaction was developed by Duan to construct hydroxyl-containing oxindoles through a tandem addition/cyclization reaction.2 Also, amino alcohols were prepared through addition of radicals generated from alcohols to unactivated alkenes.3 Reactions catalyzed by metals such as Rh,4 Fe,5 Cu and Co6 have also been applied. In 2009, addition of such radicals to alkynes was reported. Homoallylic alcohols were prepared using simple alcohol molecules.7 The reactions of alcohols and cinnamic acids were also reported and allylic alcohols were obtained.8 However, arylations of the α C–H in alcohols have attracted much interest because such structures are present in many bioactive molecules (Fig. 1). Great efforts have been expended to the synthesis of arylated alcohols. In 2014, Liu reported the reaction of alcohol molecules and isocyanide, and various alkyl-substituted phenanthridines were achieved.9Open in a separate windowFig. 1Bioactive molecules containing alcoholic hydroxyl groups.Cross-dehydrogenative coupling reactions have been the focus of many researchers and have been shown to be powerful and convenient tools in organic synthesis.10 The activation of the C–H groups in two molecules allows application of starting materials without further functionalization. This simple process with high atomic economy provides an ideal transformation for the preparation of various target compounds. The Minisci reaction has been widely explored since the 1960s. Palmer and McIntyre first reported the hydroxymethylation of quinolone in the presence of hydroxylamine-O-sulphonic acid (HSA).11 Minisci further developed an Fe-catalyzed process that resulted in good yields.12 PdCl2 (ref. 13) and TiCl3 (ref. 14) were also shown to be efficient catalysts for the Minisci reaction. Metal-free reactions initiated by TBHP15 and M2S2O8 (M = Na, K, NH4)16 have also been developed. Very recently, as visible light-promoted processes find applications in organic synthesis, visible light-induced Minisci reactions have been reported.17 However, a strong oxidant, external acid, and complex system are always needed for these reactions. In our research, we found that Selectfluor could be used as a mild oxidant for the functionalizations of C–H groups in ethers, and the HF generated in situ could be made to participate in the reaction process.18 Herein, we report an Ag/Selectfluor-catalyzed Minisci reaction, in which Selectfluor was used as a mild oxidant and no external acid was necessary (Scheme 1).Open in a separate windowScheme 1Arylations of α sp3 C–H groups in alcohols.We chose quinaldine as the model substrate and carried out the reactions (
EntryAgNO3 (eq.)Selectfluor (eq.)Time (h)MeOH : H2ObYieldc (%)
10.50.2543 : 1Trace
20.50.543 : 17
30.5143 : 124
40.5443 :  176
51443 : 188
62443 : 189
71441 : 188
81449 : 196
91429 : 193
101469 : 193
11d1449 : 190
12e1449 : 185
Open in a separate windowaConditions: 0.2 mmol of 1a, AgNO3, Selectfluor, and 2 mL of solvent were added in a tube that was then sealed. The system was heated at the indicated temperature.bVolume ratio.cIsolated yields.dReaction temperature was 60 °C.eReaction temperature was 100 °C.With the optimal conditions in hand, we explored a series of quinaldines substituted with various groups or atoms. Hydroxymethylation of substituted substrates went smoothly with high yields. 6-Substituted quinaldines were shown to be proper starting materials. Good yields were observed for a variety of introduced substituents, such as F (3b), Br (3c), I (3d), Me (3e) and CF3 (3f). Electron-withdrawing atoms and groups were favourable for high yields. However, molecule with electron-donating group gave a low yield (3e). This result may be caused by the lower stability of the in situ-generated intermediate containing an electron-withdrawing group. 8-Substituted quinaldines could also undergo this process. However, the yields were lower than those of 6-substituted substrates. We supposed that this was the result of steric effects. The substituents present on the 8-position may have protected the heterocycles from protonation, an effect harmful for the hydroxymethylation. Here again, electron-withdrawing substituents were more efficient than electron-donating groups. 7-Chloroquinaldine reacted under the standard conditions, giving the product (3l) in 94% yield. Multifluorinated heterocycles were used, and good results were obtained (3m, 3n). Lepidine was also hydroxymethylated on the 2-position in 85% yield (3o) (Scheme 2).Open in a separate windowScheme 2Quinaldine substrate scope. Standard conditions: 1 (1 mmol), AgNO3 (1 eq.), Selectfluor (4 eq.), and 10 mL of solvent (MeOH/H2O = 9 : 1) were added into a tube that was then sealed. The system was heated at 80 °C for 4 h.Next, we examined the scope of alcohols. To our delight, ethanol reacted with substituted quinaldines smoothly. Arylation of the α sp3 C–H in ethanol occurred with good yields. Various substituents, such as F (4a, 4e), Cl (4b, 4f), Br (4c) and I (4d), were tolerated and the position of the substituent showed little influence on the yield. 1-Propanol was also tested as a starting material and arylations using this starting material proceeded with good yields, albeit slightly lower than those for ethanol (4g, 4h, 4i). This result may be caused by a steric effect, leading to lower reactivity of the generated radicals (Scheme 3).Open in a separate windowScheme 3Alcohol substrate scope. Standard conditions: 1 (1 mmol), AgNO3 (1 eq.), Selectfluor (4 eq.), and 10 mL of solvent (RCH2OH/H2O = 9 : 1) were added into a tube that was then sealed. The system was heated at 80 °C for 4 h.To explore the reaction mechanism, some control experiments were carried out. When base was added together with starting materials, no product was obtained. When TEMPO was added, also no product was observed according to liquid chromatography-mass spectrometry (LC-MS) results. However, several new species were present besides the original heterocycle and alcohol. A peak at a position corresponding to a molecular weight of 161.0548 was assigned to salt 5, which was generated by the reaction of Selectfluor and AgNO3. The peak characterized by a molecular weight of 158.1548 was attributed to compound 7. We did not, however, observe a peak corresponding to compound 6, which had been expected to result from the combination of TEMPO and hydroxymethyl radical. We supposed that 6 was a hemiacetal, which due to its instability was hydrolysed rapidly to give 7. Furthermore, a kinetic isotopic effect was observed using [2H4]methanol (KIE = 2.8), indicating that the hydrogen atom abstraction from methanol was the rate-limiting step. Based on these data, a mechanism was derived (Scheme 4). First, the Ag(i) species was oxidized to Ag(ii) by Selectfluor, generating a fluorine radical and 5. Then the α-H in the alcohol molecule was abstracted by the fluorine radical, and an alkyl radical (Int I) was generated. Meanwhile, HF was released and combined with the heterocycles, giving an intermediate cation (Int II). This cation was attacked by Int I, resulting in the radical cation Int III. Then a proton was released and the radical Int IV was oxidized by Ag(ii) to give a cation (Int V). Finally, a proton was abstracted by external base, leading to the desired product. If the base was added at the beginning of the reaction, the released HF could be trapped, and the intermediate Int II was not generated, resulting in a disturbance of the process. Our results together with the derived mechanism indicated that the in situ-generated HF played a significant role in this reaction.Open in a separate windowScheme 4Proposed mechanism.In summary, we developed an efficient method for the arylation of α sp3 C–H groups in alcohols using heterocycles through CDC catalyzed by Ag. Selectfluor was used as a mild oxidant and no external acid was needed. Instead, in situ-generated HF played an important role. Various substituents were tolerated, such as halogens, alkyl groups, CF3, etc. Multi-substituted quinaldines also underwent this reaction smoothly. Common alcohols, such as methanol, ethanol and 1-propanol were explored as materials and all the alcohols could be used without further purification. Mechanism studies showed that a radical process occurred and the hydrogen abstraction step was determined to be the rate-limiting step.  相似文献   
47.
胸锁乳突肌缝线定位联合肌间隙注水分离在经腋窝无充气腔镜甲状腺手术中的应用          下载免费PDF全文
郑向欣  杨鹏  管晓青  陈志峰  许南敢  田明明  黄超  王付超  佘欣远  王前玉  朱小朝 《中国普通外科杂志》2024,33(5):780-787
背景与目的 目前较为常用的腔镜甲状腺手术入路主要有经腋窝入路、经胸乳入路及经口入路等。经腋窝入路相较于其他术式,其利用颈部肌肉的自然间隙建腔,在颈前带状肌深面显露甲状腺并进行手术操作,对颈部功能影响较小,而且无需充CO2,对心脑血管影响较小,因此近年来越来越被临床医生所接受。经腋窝入路腔镜甲状腺手术中寻找胸锁乳突肌肌间隙是该术式的一大难点,在此步骤中较多初学者不能准确定位肌间隙,进而增加了手术时间及创伤。为此,笔者中心对经腋窝无充气腔镜甲状腺手术作了一定的改进,降低术中寻找肌间隙的难度。本研究对该改良术式的近期疗效与安全性进行评估,为其在临床中的应用提供依据。方法 回顾性分析2023年1月—2023年5月江苏省宿迁市第一人民医院甲乳外科收治的46例甲状腺癌患者的临床资料。其中,23例接受改良经腋窝入路免充气腔镜下甲状腺手术(观察组),另23例接受常规经腋窝入路免充气腔镜下甲状腺手术(对照组)。观察组患者术前超声引导下在胸锁乳突肌胸骨部与锁骨部之间的间隙内注水分离,扩大肌间隙,然后缝线定位胸锁乳突肌胸骨部后缘,准确进入肌间隙后,按照常规经腋窝入路腔镜甲状腺手术方法实施手术。结果 两组患者一般资料无明显差异(均P>0.05),具有可比性。观察组平均手术时间明显短于对照组(65.6 min vs. 87.2 min,P<0.05),而两组的术中出血量、术后引流量、中央区清扫淋巴结数及住院时间差异均无统计学意义(均P>0.05)。观察组有1例出现腋窝皮下血肿,经抽液、包扎后改善,余患者均无呼吸困难、声音嘶哑、手足麻木、饮水呛咳等并发症发生。术后3个月,两组患者颈部疼痛评分及颈部损伤指数、吞咽障碍指数比较,差异均无统计学意义(均P>0.05)。所有患者术后均口服左旋甲状腺素钠片行个体化促甲状腺激素(TSH)抑制治疗,随访期间无患者出现复发转移。结论 术前行超声引导下胸锁乳突肌缝线定位联合肌间隙注水分离操作方便、实用,便于术中寻找肌间隙,降低了经腋窝无充气腔镜甲状腺手术整体手术难度,具有较好的临床应用价值。  相似文献   
48.
HPLC-ELSD测定不同产地青蒿中青蒿素的含量     
胡向荣  佘凤华 《今日药学》2006,16(3):34-36
目的建立HPLC-ELSD同时测定不同产地青蒿中青蒿素的含量.方法采用色谱柱:LichrospherC18柱(4.6 mm×250 mm,5 μm);流动相:甲醇:水(75:25);Alltech ELSD 2000(蒸发光散射检测器)检测,气体为高纯氮气,流速2.0 L/min.结果在此色谱条件下,青蒿素与其它色谱峰完全达到基线分离(R>2.0).12批不同产地黄花蒿中青蒿素含量在0.25%~1.21%.结论用该方法进行检测,操作简单,灵敏度高.  相似文献   
49.
中医五联疗法治疗肝性脑病临床研究     
佘世锋  侯江涛  杨晓军 《安徽中医学院学报》2010,29(4):6-8
目的观察中医五联疗法治疗肝性脑病的,临床疗效。方法将肝性脑病患者65例随机分为治疗组34例与对照组31例,均予常规西药和中药汤剂口服治疗,治疗组加中药静脉滴注、中药灌肠、中药肝区热敷、中药穴位敷贴五联疗法。比较两组患者精神意识、智力及扑翼样震颤的改善情况,治疗前后总胆红素、血氨及凝血酶原时间变化情况。结果治疗组和对照组总有效率分别为76.47%、51.61%,治疗组疗效显著优于对照组(P〈0.05);两组患者治疗后总胆红素、血氨及凝血酶原时间均显著下降(P〈0.05),且治疗组在降低凝血酶原时间、血氨方面显著优于对照组(P〈0.05)。结论中医五联疗法发挥了中药综合治疗的优势,疗效显著,值得推广。  相似文献   
50.
39例早期先天性梅毒的临床分析     
佘凡凡  杨春俊  张学军 《实用皮肤病学杂志》2017,(1)
目的了解先天性梅毒的流行病学特点、临床特征及其治疗预后情况,为先天性梅毒的防治提供参考。方法对2010—2014年住院治疗的先天性梅毒患儿的病历资料进行回顾性分析。结果①共39例资料完整的先天性梅毒患儿入选;②患儿母亲正规驱梅治疗5例、非正规驱梅治疗34例;③临床和体征主要表现为皮肤黏膜损害、肝损伤、血液系统损害、骨损害、心脏损害、中枢神经系统损害、发热、脾大;④患儿均予以青霉素治疗,未见青霉素不良反应;⑤症状体征消失的有11例、症状体征好转17例、无改善3例。结论先天性梅毒中以早期先天性梅毒最常见;早期先天性梅毒可以有皮肤黏膜、肝脏、血液系统、骨骼系统、中枢神经系统及心脏损害等多器官损害;青霉素是先天性梅毒治疗的首选药物,但早期先天性梅毒的预后值得关注。  相似文献   
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