全文获取类型
收费全文 | 2623篇 |
免费 | 57篇 |
国内免费 | 6篇 |
专业分类
化学 | 1640篇 |
晶体学 | 10篇 |
力学 | 44篇 |
数学 | 547篇 |
物理学 | 445篇 |
出版年
2020年 | 26篇 |
2019年 | 21篇 |
2016年 | 35篇 |
2015年 | 43篇 |
2014年 | 36篇 |
2013年 | 68篇 |
2012年 | 49篇 |
2011年 | 64篇 |
2010年 | 43篇 |
2009年 | 47篇 |
2008年 | 67篇 |
2007年 | 63篇 |
2006年 | 63篇 |
2005年 | 52篇 |
2004年 | 41篇 |
2003年 | 49篇 |
2002年 | 36篇 |
2001年 | 31篇 |
2000年 | 39篇 |
1999年 | 32篇 |
1998年 | 31篇 |
1997年 | 34篇 |
1996年 | 34篇 |
1995年 | 31篇 |
1994年 | 30篇 |
1993年 | 30篇 |
1992年 | 26篇 |
1991年 | 42篇 |
1990年 | 39篇 |
1989年 | 32篇 |
1988年 | 35篇 |
1987年 | 28篇 |
1986年 | 25篇 |
1985年 | 34篇 |
1984年 | 36篇 |
1983年 | 27篇 |
1982年 | 42篇 |
1981年 | 45篇 |
1980年 | 44篇 |
1979年 | 46篇 |
1978年 | 42篇 |
1977年 | 28篇 |
1976年 | 23篇 |
1975年 | 30篇 |
1973年 | 25篇 |
1970年 | 23篇 |
1933年 | 22篇 |
1929年 | 28篇 |
1928年 | 21篇 |
1927年 | 21篇 |
排序方式: 共有2686条查询结果,搜索用时 859 毫秒
101.
102.
Dr. Miguel Cortijo Dr. Ángela Valentín-Pérez Dr. Andrei Rogalev Dr. Fabrice Wilhelm Dr. Philippe Sainctavit Dr. Patrick Rosa Dr. Elizabeth A. Hillard 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(59):13363-13366
An original method for determining the handedness of individual non-centrosymmetric crystals in a mixture using a tightly-focused, circularly polarized X-ray beam is presented. The X-ray natural circular dichroism (XNCD) spectra recorded at the metal K-edge on selected crystals of [Δ-M(en)3](NO3)2 and [Λ-M(en)3](NO3)2 (M=CoII, NiII) show extrema at the metal pre-edge (7712 eV for Co, 8335 eV for Ni). A mapping of a collection of some 220 crystals was performed at the respective energies by using left and right circular polarizations. The difference in absorption for the two polarizations, being either negative or positive, directly yielded the handedness of the crystal volume probed by the beam. By using this technique, it was found that the addition of l -ascorbic acid during the synthesis of [Co(en)3](NO3)2 resulted in an enantiomeric enrichment of the Λ-isomer of 67±13 %, whereas the Ni analogue was similarly, but conversely, enriched in the Δ-isomer (65±22 %). 相似文献
103.
104.
105.
Reassessment of the NH4NO3 thermal decomposition technique for calibration of the N2O isotopic composition 下载免费PDF全文
106.
107.
108.
Andreas Thomas Matthias Vogel Thomas Piper Oliver Krug Simon Beuck Wilhelm Schänzer Mario Thevis 《Analytical and bioanalytical chemistry》2013,405(30):9703-9709
AICAR (5-amino-4-imidazolecarboxyamide ribonucleoside) arguably provides performance-enhancing properties even in the absence of physical exercise and, therefore, the substance is banned in elite sports since 2009. Due to the natural presence of AICAR in human blood and urine, uncovering the misuse by direct qualitative analysis is not possible. Entering the circulation, the riboside is immediately incorporated into red blood cells (RBCs) and transformed into the corresponding ribotide (5′-monophosphate) form. Within the present study, an analytical method was developed to determine AICAR-ribotide concentrations in RBC concentrates by means of liquid chromatography-tandem mass spectrometry. The method was validated enabling quantitative result interpretation considering the parameters specificity, precision (intra- and interday), linearity, recovery, accuracy (LOD/LOQ), stability and ion suppression. By analysing 99 RBC samples of young athletes, normal physiological levels of AICAR-ribotide were determined (10–500 ng/mL), and individual levels were found to be stable for several days. Employing in vitro incubation experiments with AICAR riboside in fresh whole blood samples, the ribotide concentrations were observed to increase significantly within 30 min from baseline to 1–10 μg/mL. These levels are considered conserved for the lifetime of the erythrocyte and, thus, the results of the in vitro model strongly support the hypothesis that measuring abnormally high AICAR-ribotide concentrations in RBC of elite athletes has the potential to uncover the misuse of this substance for a long period of time. 相似文献
109.
Mario?ThevisEmail author Andreas?Thomas Wilhelm?Sch?nzer 《Analytical and bioanalytical chemistry》2013,405(30):9655-9667
Urine samples have been the predominant matrix for doping controls for several decades. However, owing to the complementary information provided by blood (as well as serum or plasma and dried blood spots (DBS)), the benefits of its analysis have resulted in continuously increasing appreciation by anti-doping authorities. On the one hand, blood samples allow for the detection of various different methods of blood doping and the abuse of erythropoiesis-stimulating agents (ESAs) via the Athlete Biological Passport; on the other hand, targeted and non-targeted drug detection by means of chromatographic–mass spectrometric methods represents an important tool to increase doping control frequencies out-of-competition and to determine drug concentrations particularly in in-competition scenarios. Moreover, blood analysis seldom requires in-depth knowledge of drug metabolism, and the intact substance rather than potentially unknown or assumed metabolic products can be targeted. In this review, the recent developments in human sports drug testing concerning mass spectrometry-based techniques for qualitative and quantitative analyses of therapeutics and emerging drug candidates are summarized and reviewed. The analytical methods include both low and high molecular mass compounds (e.g., anabolic agents, stimulants, metabolic modulators, peptide hormones, and small interfering RNA (siRNA)) determined from serum, plasma, and DBS using state-of-the-art instrumentation such as liquid chromatography (LC)–high resolution/high accuracy (tandem) mass spectrometry (LC-HRMS), LC–low resolution tandem mass spectrometry (LC-MS/MS), and gas chromatography–mass spectrometry (GC-MS). 相似文献
110.
Iulius I. E. Markovits Dr. Wilhelm A. Eger Dr. Shuang Yue Dr. Mirza Cokoja Christian J. Münchmeyer Bo Zhang Dr. Ming‐Dong Zhou Dr. Alexander Genest Prof. Dr. János Mink Prof. Dr. Shu‐Liang Zang Prof. Dr. Notker Rösch Prof. Dr. Fritz E. Kühn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(19):5972-5979
Imidazolium‐based ionic liquids that contain perrhenate anions are very efficient reaction media for the epoxidation of olefins with H2O2 as an oxidant, thus affording cyclooctene in almost quantitative yields. The mechanism of this reaction does not follow the usual pathway through peroxo complexes, as is the case with long‐known molecular transition‐metal catalysts. By using in situ Raman, FTIR, and NMR spectroscopy and DFT calculations, we have shown that the formation of hydrogen bonds between the oxidant and perrhenate activates the oxidant, thereby leading to the transfer of an oxygen atom onto the olefin demonstrating the special features of an ionic liquid as a reaction environment. The influence of the imidazolium cation and the oxidant (aqueous H2O2, urea hydrogen peroxide, and tert‐butyl hydrogen peroxide) on the efficiency of the epoxidation of cis‐cyclooctene were examined. Other olefinic substrates were also used in this study and they exhibited good yields of the corresponding epoxides. This report shows the potential of using simple complexes or salts for the activation of hydrogen peroxide, owing to the interactions between the solvent medium and the active complex. 相似文献