全文获取类型
收费全文 | 3834篇 |
免费 | 220篇 |
国内免费 | 142篇 |
专业分类
化学 | 807篇 |
晶体学 | 86篇 |
力学 | 421篇 |
综合类 | 25篇 |
数学 | 88篇 |
物理学 | 400篇 |
综合类 | 2369篇 |
出版年
2024年 | 18篇 |
2023年 | 42篇 |
2022年 | 63篇 |
2021年 | 66篇 |
2020年 | 77篇 |
2019年 | 67篇 |
2018年 | 69篇 |
2017年 | 89篇 |
2016年 | 96篇 |
2015年 | 107篇 |
2014年 | 183篇 |
2013年 | 195篇 |
2012年 | 226篇 |
2011年 | 215篇 |
2010年 | 157篇 |
2009年 | 187篇 |
2008年 | 196篇 |
2007年 | 197篇 |
2006年 | 202篇 |
2005年 | 196篇 |
2004年 | 170篇 |
2003年 | 155篇 |
2002年 | 126篇 |
2001年 | 128篇 |
2000年 | 105篇 |
1999年 | 99篇 |
1998年 | 89篇 |
1997年 | 108篇 |
1996年 | 89篇 |
1995年 | 83篇 |
1994年 | 75篇 |
1993年 | 44篇 |
1992年 | 50篇 |
1991年 | 56篇 |
1990年 | 49篇 |
1989年 | 41篇 |
1988年 | 39篇 |
1987年 | 19篇 |
1986年 | 10篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1959年 | 1篇 |
1957年 | 2篇 |
1955年 | 1篇 |
排序方式: 共有4196条查询结果,搜索用时 15 毫秒
71.
A method of quickly determining ascorbic acid and sorbic acid by capillary zone electrophoresis with ultraviolet detection was developed. The choice of background electrolyte, wavelength, injection time and applied voltage were discussed. Ascorbic acid and sorbic acid were well separated in 80 mmol L−1 boric acid-5 mmol L−1borax (pH = 8.0) in 5 min at the detecting wavelength of 270 nm. Under the optimum condition, the method has linear ranges of 2.54-352.00 mg L−1 for ascorbic acid and 1.08-336.39 mg L−1 for sorbic acid with the detection limit of 1.70 mg L−1 for ascorbic acid and 0.54 mg L−1 for sorbic acid, respectively. Other organic acids in fruit juices have no effect on the detection. This method is very feasible and simple and can be used to detect ascorbic acid and sorbic acid in fruit juices. 相似文献
72.
The current achievements in magnetic transmission soft X-ray microscopy will be reviewed. The magnetic contrast is given by X-ray magnetic circular dichroism (X-MCD), i.e., the dependence of the absorption coefficient of circularly polarized X rays on the projection of the magnetization in a ferromagnetic system onto the photon propagation direction. X-MCD contrast can reach, e.g., at L2,3 edges in transition metals, large values up to 50%. Combined with a soft X-ray microscope where Fresnel zone plates acting as optical elements provide a lateral resolution down at 25 nm, it allows for imaging magnetic microstructures. Specific features of this photon-based technique are the recording of images in varying external magnetic fields, an inherent chemical specificity, a high sensitivity to thin magnetic layers, due to the large contrast, and the possibility to distinguish between in-plane and out-of plane contributions. In this report, recent results obtained with the XM-1 microscope at the ALS (Berkeley/CA) demonstrate the broad applicability of this novel experimental technique to both fundamental and technological relevant issues in nanomagnetism. The future potential will be briefly outlined. 相似文献
73.
The present study uses an unique capillary electrophoresis (CE) approach, that we have termed ion-interaction capillary zone electrophoresis (II-CZE), for the separation of diastereomeric peptide pairs where a single site in the centre of the non-polar face of an 18-residue amphipathic alpha-helical peptide is substituted by the 19 L- or D-amino acids. Through the addition of perfluorinated acids at very high concentrations (up to 400 mM), such concentration levels not having been used previously in chromatography or CE, to the background electrolyte (pH 2.0), we have been able to achieve baseline resolution of all 19 diastereomeric peptide pairs with an uncoated capillary. Since each diastereomeric peptide pair has the same sequence, identical mass-to-charge ratio and identical intrinsic hydrophobicity, such a separation by CZE has previously been considered theoretically impossible. Excellent resolution was achieved due to maximum advantage being taken of even subtle disruption of peptide structure/conformation (due to the presence of D-amino acids) of the non-polar face of the amphipathic alpha-helix and its interaction with the hydrophobic anionic ion-pairing reagents. In addition, due to the excellent resolution of diastereomeric peptide pairs by this novel CZE approach, we have also been able to separate a mixture of these closely-related alpha-helical peptides. 相似文献
74.
Phosphinic pseudopeptides (i.e., peptide isosteres with one peptide bond replaced by a phosphinic acid moiety) were analyzed and physicochemically characterized by capillary zone electrophoresis in the pH range of 1.1-3.2, employing phosphoric, phosphinic, oxalic and dichloroacetic acids as background electrolyte (BGE) constituents. The acid dissociation constant (pK(a)) of phosphinate group in phosphinic pseudopeptides and ionic mobilities of these analytes were determined from the pH dependence of their effective electrophoretic mobilities corrected to standard temperature and constant ionic strength of the BGEs. It was shown that these corrections are necessary whenever precise mobility data at very low pH are to be determined. Additionally, it was found that the ionic mobilities of the phosphinic pseudopeptides and pK(a) of their phosphinate group are affected by the BGE constituent used. The variability of migration behavior of the pseudopeptides can be attributed to their ion-pairing formation with the BGE components. 相似文献
75.
A capillary zone electrophoresis (CZE) method has been developed for simultaneous determination of eukovoside, cinnamic acid and ferulic acid in Euphrasia regelii for the first time. The electrophoresis buffer was 20 mmol/L sodium borate containing 10% (v/v) methanol (pH 8.50). The effects of concentration of borate and electrolyte pH on electrophoretic behavior and separation were studied. Regression equations revealed linear relationships (correlation coefficients 0.9995-0.9998) between the peak area of each analyte and the concentration. The levels of analytes in the different parts of Euphrasia regelii were easily determined with recoveries ranging from 95.5 to 104.2%. 相似文献
76.
《Journal of separation science》2003,26(5):425-428
This paper describes a method for analysing some acids of milk whey by Capillary Zone Electrophoresis. After eliminating the whey proteins by ultrafiltration, the whey underwent electrophoretic separation in the presence of anodic electroosmotic flow. The following analytes were detected: citric, orotic, uric, and hippuric acids. A procedure is described for sample preparation and the operating conditions for electrophoretic capillary separation established. Finally, orotic acid is quantitatively determined. 相似文献
77.
A capillary zone electrophoresis (CZE) method for the analyses of kaempferol in Centella asiatica and Rosa hybrids and rutin in Chromolaena odorata was developed. The optimization was performed on analyses of flavonoids (e.g., rutin, kaempferol, quercetin, myricetin, and apigenin) and organic carboxylic acids (e.g., ethacrynic acid and xanthene-9-carboxylic acid) by investigation of the effects of types and amounts of organic modifiers, background electrolyte concentrations, temperature, and voltage. Baseline separation (R(s) = 2.83) of the compounds was achieved within 10 min in 20 mM NaH2PO4 - Na2HPO4 (pH 8.0) containing 10% v/v ACN and 6% v/v MeOH using a voltage of 25 kV, a temperature of 30 degrees C, and a detection wavelength set at 220 nm. The application of the corrected migration time (t(c)), using ethacrynic acid as the single marker, was efficient to improve the precision of flavonoid identification (% relative standard deviation (RSD) = 0.65%). The method linearity was excellent (r2 > 0.999) over 50-150 microg/mL. Precision (%RSD < 1.66%) and recoveries were good (> 96% and %RSDs < 1.70%) with detection and quantitation limits of 2.23 and 7.14 microg/mL, respectively. Kaempferol in C. asiatica and R. hybrids was 0.014 g/100 g (%RSD = 0.59%) and 0.044 g/100 g (%RSD = 1.04%), respectively, and rutin in C. odorata was 0.088 g/100 g (%RSD = 0.06%). 相似文献
78.
Three standardised, capillary zone electrophoresis-electrospray ionisation mass spectrometry (CZE-ESI-MS) methods were developed for the analysis of six drug candidates and their respective process-related impurities comprising a total of 22 analytes with a range of functional groups and lipophilicities. The selected background electrolyte conditions were found to be: 60/40 v/v 10 mM ammonium formate pH 3.5/organic, 60/40 v/v 10 mM ammonium acetate pH 7.0/organic and 10 mM piperidine, pH 10.5, where the organic solvent is 50/50 v/v methanol/acetonitrile. The coaxial sheath flow consisted of either 0.1% v/v formic acid in 50/50 v/v methanol/water, or 10 mM ammonium acetate in 50/50 v/v methanol/water, depending on the mixture being analysed. Factor analysis and informational theory were used to quantify the orthogonality of the methods and predict their complementarities. The three selected CZE-ESI-MS methods allowed the identification of 21 out of 22 of all the drug candidates and their process-related impurities and provided orthogonality with four established high-performance liquid chromatography-mass spectrometry (HPLC-MS) methods. These methodologies therefore form the basis of a generic approach to impurity profiling of pharmaceutical drug candidates and can be applied with little or no analytical method development, thereby offering significant resource and time savings. 相似文献
79.
设置扇形边界死区的电压型PWM整流器直接功率控制 总被引:9,自引:2,他引:9
利用电压型PWM整流器的数学模型分析了PWM整流器直接功率控制(DPC)的原理,讨论了功率滞环比较器环宽对PWM整流器的影响.为了降低开关频率和减少开关损失,增加功率滞环比较器环宽则引起瞬时有功功率和直流电压波动现象;提出了设置扇形边界死区的控制策略,减少扇形边界误选开关量现象,使瞬时有功功率和直流电压波形趋于平稳.通过Simulink环境下仿真模型的仿真,证明了该策略的可行性. 相似文献
80.
借助专门的能够控制吸力的四联式非饱和土直剪仪,对清江水布垭坝区古树包滑坡滑带土的重塑样进行了一系列抗剪强度试验,验证了F red lud提出的非饱和土抗剪强度公式对滑带土的适用性,求出了该滑带非饱和土的强度参数;通过在一定基质吸力条件下量测含水率-固结压力之间的关系,指出土-水特征曲线与固结压力相关的特性。 相似文献