全文获取类型
收费全文 | 7957篇 |
免费 | 354篇 |
国内免费 | 22篇 |
专业分类
化学 | 5860篇 |
晶体学 | 44篇 |
力学 | 96篇 |
数学 | 843篇 |
物理学 | 1490篇 |
出版年
2023年 | 73篇 |
2022年 | 209篇 |
2021年 | 260篇 |
2020年 | 182篇 |
2019年 | 165篇 |
2018年 | 106篇 |
2017年 | 119篇 |
2016年 | 302篇 |
2015年 | 303篇 |
2014年 | 345篇 |
2013年 | 597篇 |
2012年 | 497篇 |
2011年 | 510篇 |
2010年 | 369篇 |
2009年 | 323篇 |
2008年 | 402篇 |
2007年 | 386篇 |
2006年 | 357篇 |
2005年 | 296篇 |
2004年 | 233篇 |
2003年 | 200篇 |
2002年 | 201篇 |
2001年 | 73篇 |
2000年 | 88篇 |
1999年 | 69篇 |
1998年 | 65篇 |
1997年 | 65篇 |
1996年 | 64篇 |
1995年 | 64篇 |
1994年 | 46篇 |
1993年 | 50篇 |
1992年 | 41篇 |
1991年 | 46篇 |
1990年 | 44篇 |
1988年 | 54篇 |
1987年 | 48篇 |
1986年 | 41篇 |
1985年 | 63篇 |
1984年 | 68篇 |
1983年 | 45篇 |
1982年 | 38篇 |
1981年 | 34篇 |
1980年 | 44篇 |
1979年 | 41篇 |
1978年 | 44篇 |
1977年 | 51篇 |
1976年 | 48篇 |
1975年 | 44篇 |
1974年 | 56篇 |
1973年 | 37篇 |
排序方式: 共有8333条查询结果,搜索用时 31 毫秒
1.
Tomáš Hložek Martin Štícha Miroslava Bursová Ivan Jelínek Petr Tůma Radomír Čabala 《Electrophoresis》2020,41(18-19):1564-1567
Riociguat is novel antihypertensive drug for treatment of pulmonary hypertension. As such, it is still being tested in many clinical and pharmacokinetic trials. Existing methods that determine serum riociguat and desmethylriociguat (DMR) are based solely on liquid chromatography with mass spectrometry. Therefore, we present a novel capillary electrophoresis with mass spectrometry method (CE-MS) for their determination in human serum as alternative method for ongoing trials. Complete resolution of both analytes was achieved by means of pH optimization of ammonium formate background electrolytes that are fully compatible with ESI/MS detection. Simple liquid-liquid extraction was used as sample pretreatment. The calibration dependence of the method was linear (in the range of 10–1000 ng/mL), with adequate accuracy (90.1–114.9%) and precision (13.4%). LOD and LOQ were arbitrarily set at 10 ng/mL for both analytes. Clinical applicability was validated using serum samples from patients treated with riociguat in pharmacokinetic study and the results corresponded with reference HPLC-MS/MS values. Capillary electrophoresis proved to be sensitive and selective tool for the analysis of riociguat and DMR. 相似文献
2.
3.
4.
Functional Carbazole Liquid‐Crystal Block Codendrimers with Optical and Electronic Properties
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Ismael Gracia Beatriz Feringán Prof. José Luis Serrano Dr. Roberto Termine Dr. Attilio Golemme Dr. Ana Omenat Prof. Joaquín Barberá 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(3):1359-1369
The synthesis and characterisation of a family of block codendrimers consisting of highly versatile mesogenic and carbazole‐containing 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) dendrons are reported. The liquid‐crystal behaviour was investigated by means of differential scanning calorimetry, polarised‐light optical microscopy and X‐ray diffraction. Depending on the chemical structure of the constituent dendrons, the codendrimers show lamellar or columnar mesophases. On the basis of the experimental results, models both at the molecular level and in the mesophase are proposed. The physical properties of the block codendrimers derived from the presence of the carbazole moiety in their structure were investigated: photoluminescence in solution and in the mesophase, electrochemical behaviour and hole transport. Electrodeposition of carbazole dendrons afforded a globular supramolecular conformation in which the mesogenic molecular side plays a key role. 相似文献
5.
A protocol to correct for intra‐ and interspecific variation in tail hair growth to align isotope signatures of segmentally cut tail hair to a common time line
下载免费PDF全文
![点击此处可从《Rapid communications in mass spectrometry : RCM》网站下载免费的PDF全文](/ch/ext_images/free.gif)
6.
Dr. Liat Avram Dr. Václav Havel Ronit Shusterman-Krush Dr. Mark A. Iron Dr. Moritz Zaiss Prof. Vladimír Šindelář Dr. Amnon Bar-Shir 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1687-1690
The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF4− are mediated by the side chains on the receptor (100 s−1<kex<5000 s−1), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method. 相似文献
7.
8.
Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
9.
Palladium and molybdenum polycrystalline layers (clusters) have been deposited in a stainless steel UHV system onto a layer of alumina (Al2O3). This layer has been prepared by high temperature oxidation of an aluminium layer. The interaction of this system with nitrogen has been investigated at room temperature by an FEM technique. Under these conditions nitrogen spillover from molybdenum to palladium has been observed. 相似文献
10.
J. Kudrna I. Pelant J. Štěpánek F. Trojánek P. Malý 《Applied Physics A: Materials Science & Processing》2002,74(2):253-256
We have studied ultra-fast carrier dynamics of photo-excited carriers in hydrogenated microcrystalline silicon prepared by
a very high frequency glow-discharge technique. We report on direct observation of two types of dynamics using selective photo-excitation
in picosecond pump and probe measurements. One type of the observed dynamics has been found to be independent of the sample
preparation, while the other reflects the relative weights of crystalline and amorphous fractions. We propose a simple rate-equation
model that describes the carrier dynamics in microcrystalline silicon in terms of the composition of those in Si microcrystallites
and in the a-Si:H tissue which surrounds the microcrystallites. The model without any fitting parameters reproduces the experimental
data very well when the dynamics are scaled with relative volume fractions as obtained from Raman spectra.
Received: 23 November 2000 / Accepted: 17 March 2001 / Published online: 23 May 2001 相似文献