全文获取类型
收费全文 | 1408篇 |
免费 | 34篇 |
国内免费 | 242篇 |
专业分类
化学 | 1536篇 |
晶体学 | 12篇 |
力学 | 2篇 |
综合类 | 7篇 |
数学 | 1篇 |
物理学 | 126篇 |
出版年
2024年 | 2篇 |
2023年 | 7篇 |
2022年 | 23篇 |
2021年 | 20篇 |
2020年 | 27篇 |
2019年 | 31篇 |
2018年 | 33篇 |
2017年 | 21篇 |
2016年 | 23篇 |
2015年 | 20篇 |
2014年 | 49篇 |
2013年 | 155篇 |
2012年 | 83篇 |
2011年 | 80篇 |
2010年 | 59篇 |
2009年 | 74篇 |
2008年 | 85篇 |
2007年 | 102篇 |
2006年 | 98篇 |
2005年 | 85篇 |
2004年 | 70篇 |
2003年 | 68篇 |
2002年 | 49篇 |
2001年 | 54篇 |
2000年 | 35篇 |
1999年 | 49篇 |
1998年 | 35篇 |
1997年 | 28篇 |
1996年 | 25篇 |
1995年 | 24篇 |
1994年 | 21篇 |
1993年 | 21篇 |
1992年 | 18篇 |
1991年 | 15篇 |
1990年 | 13篇 |
1989年 | 17篇 |
1988年 | 11篇 |
1987年 | 16篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 6篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1972年 | 2篇 |
排序方式: 共有1684条查询结果,搜索用时 15 毫秒
991.
Antiseptic agent carbethopendecinium bromide (septonex) was determined by capillary electrophoresis with capacitively coupled contactless conductivity detection. Optimal separation of this quaternary ammonium ion was achieved in BGE of pH 7.0 containing 30 mM 2-(N-morpholino)ethanesulfonic acid, 12.5 mg/mL of 2-hydroxypropyl-β-cyclodextrin and 20% v/v of acetonitrile. The separation was performed at 25°C in an uncoated fused silica capillary (50 μm id; total length, 60.5 cm; effective length, 50 cm) at 30 kV. Samples were injected hydrodynamically at 50 mbar for 6 s. For quantitative analysis, L-arginine (500 μg/mL) was used as internal standard. The calibration curve was rectilinear for 25-400 μg/mL of septonex (y=0.0113x-0.0063; r(2)=0.9992). The LOD was 7 μg/mL of septonex (at S/N=3). The run-to-run repeatability (n=6) was characterized by the RSDs of 0.18% for the migration time and 1.96% for the analyte/internal standard peak area ratio. Accuracy tested by recovery experiments at three concentration levels gave recoveries of 100.27-104.22% with RSD ≤2.19%. The method was successfully applied to the assay of carbethopendecinium bromide in eye drops. Quaternary ammonium ions having structure and size close to that of carbethopendecinium may not be resolved from the analyte. 相似文献
992.
993.
Qibo Liu 《Journal of fluorine chemistry》2011,132(2):78-87
(Z)-HFCCFZnI was stereoselectively synthesized from activated zinc dust and (Z)-HFCCFI that was synthesized from chlorotrifluoroethene in a sequential manner. Compared to (E)-HFCCFZnI, (Z)-HFCCFZnI was more challenging to prepare in terms of sluggish metallation and formation of by-products, and underwent slower and incomplete Negishi coupling with aryl iodides. In a modification of Negishi coupling, (E)-α,β-difluorostyrenes were stereospecifically prepared in good to excellent yields under mild conditions from aryl iodides and (Z)-HFCCFZnI with the co-catalysis of Pd(PPh3)4/Cu(I)Br. Experimental investigation and mechanistic rationalization suggested that Cu(I)Br would be a scavenger of free ligands for the facilitation of Pd(PPh3)2 formation, and a supplier of ligand for the metathesis process. Alternatively, (Z)-HFCCFSnBu3 and aryl iodides with an electron-withdrawing group underwent Stille-Liebiskind coupling to afford (E)-α,β-difluorostyrenes. 相似文献
994.
995.
A wide variety of monobrominated compounds 2a-l have been prepared in good yields from (E)-1-(2′-hydroxy-4′,6′-dimethoxyphenyl)-3-aryl-2-propen-1-ones (1a-l) through regioselective ring bromination using 1.5 equiv of bromodimethylsulfonium bromide (BDMS) at room temperature. Similarly, some of the 2′-hydroxychalcones can be converted directly into tribromides 3 or dibromides 4 by employing 4.0 equiv of BDMS under different reaction conditions which in turn can be transformed into 8-bromoflavones and 7-bromoaurones on treatment with 0.2 M ethanolic KOH solution. Mild reaction conditions, good yields and no chromatographic separation are some of the salient features of the present protocol. 相似文献
996.
IntroductionRecently ,theBaylis Hillmanreactionhasbecomeaveryhotfieldforsyntheticchemists ,1 12 witharecentexampleofacatalyticasymmetricversion .13 IthasbeendisclosedthatthecombinationofaLewisbasesuchaschalcogenides ,amines ,phosphinesorquaternaryammo niumhali… 相似文献
997.
In this work, a very sensitive and simple electrochemical sensor for chlorophenols (CPs) based on a nanocomposite of cetyltrimethylammonium bromide (CTAB) and ZnSe quantum dots (ZnSe–CTAB) through electrostatic self-assembly technology was built for the first time. The composite of ZnSe–CTAB introduced a favorable access for the electron transfer and gave superior electrocatalytic activity for the oxidation of CPs than ZnSe QDs and CTAB alone. Differential pulse voltammetry (DPV) was used for the quantitative determination of the CPs including 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP). Under the optimum conditions, the peak currents of the CPs were proportional to their concentrations in the range from 0.02 to 10.0 μM for 2-CP, 0.006 to 9.0 μM for 2,4-DCP, and 0.06 to 8.0 for PCP. The detection limits were 0.008 μM for 2-CP, 0.002 μM for 2,4-DCP, and 0.01 μM for PCP, respectively. The method was successfully applied for the determination of CPs in waste water with satisfactory recoveries. This ZnSe–CTAB electrode system provides operational access to design environment-friendly CPs sensors. 相似文献
998.
The studies on the ZnBr2-mediated synthesis of axially chiral aryl-substituted allenes from terminal alkynes, aromatic aldehydes, and commercially available chiral amine (S)-α,α-diphenylprolinol were conducted. Axially chiral aryl-substituted allenes can be obtained in moderate yields with up to 96% ee. 相似文献
999.
研究了阴离子染料荧光桃红B(PB)对鱼精脱氧核糖核酸(fsDNA)和阳离子表面活性剂溴化十六烷基三甲铵(CTMAB)的共振光散射光谱有协同增强作用,建立了一种定量测定fsDNA的灵敏度高、操作简便的共振光散射(RLS)方法。在pH 5.33和离子强度低于0.03 mol/L的条件下,fsDNA与CTMAB和PB共同作用产生最大散射波长为340 nm的特征共振光散射增强(RLSE)信号。在优化条件下,测定fsDNA的线性范围为0.01~3.0 mg/L,检出限(3δ)为1.4μg/L。方法成功应用于合成样中DNA的测定。 相似文献
1000.
采用自制的相平衡研究装置, 测定了RbBr-CH3OH/C2H5OH-H2O和CsBr-CH3OH/C2H5OH-H2O四个三元体系在25、35、45 ℃三个温度下的平衡溶解度;同时得到了四个三元体系饱和溶液中不同盐浓度下的折光率数据. 实验结果表明,在所有的体系中, 随着甲醇或乙醇质量分数的增加, RbBr和CsBr 在水中的溶解度逐渐降低; 并且折光率也逐渐减小. 用经验关联方程对溶解度进行了拟合, 同时给出了CH3OH 和C2H5OH 分别对RbBr和CsBr的盐析率曲线. 相似文献