全文获取类型
收费全文 | 10930篇 |
免费 | 189篇 |
国内免费 | 28篇 |
专业分类
化学 | 7040篇 |
晶体学 | 103篇 |
力学 | 215篇 |
数学 | 1680篇 |
物理学 | 2109篇 |
出版年
2020年 | 97篇 |
2016年 | 200篇 |
2015年 | 162篇 |
2014年 | 150篇 |
2013年 | 370篇 |
2012年 | 342篇 |
2011年 | 381篇 |
2010年 | 244篇 |
2009年 | 270篇 |
2008年 | 356篇 |
2007年 | 356篇 |
2006年 | 358篇 |
2005年 | 338篇 |
2004年 | 265篇 |
2003年 | 267篇 |
2002年 | 258篇 |
2001年 | 199篇 |
2000年 | 212篇 |
1999年 | 159篇 |
1998年 | 150篇 |
1997年 | 154篇 |
1996年 | 182篇 |
1995年 | 184篇 |
1994年 | 143篇 |
1993年 | 170篇 |
1992年 | 184篇 |
1991年 | 177篇 |
1990年 | 137篇 |
1989年 | 152篇 |
1988年 | 145篇 |
1987年 | 140篇 |
1986年 | 137篇 |
1985年 | 201篇 |
1984年 | 188篇 |
1983年 | 164篇 |
1982年 | 174篇 |
1981年 | 198篇 |
1980年 | 117篇 |
1979年 | 161篇 |
1978年 | 149篇 |
1977年 | 174篇 |
1976年 | 138篇 |
1975年 | 158篇 |
1974年 | 138篇 |
1973年 | 137篇 |
1972年 | 94篇 |
1971年 | 99篇 |
1968年 | 113篇 |
1967年 | 130篇 |
1966年 | 127篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
Markus Gallei Bernhard V. K. J. Schmidt Roland Klein Matthias Rehahn 《Macromolecular rapid communications》2009,30(17):1463-1469
Ferrocenylmethyl methacrylate (FMMA) is one of the very few metallocene‐based monomers that are promising candidates for truly living anionic polymerization. Nevertheless, FMMA homopolymers with a narrow polydispersity, or block copolymerization studies that result in satisfying blocking efficiencies, are unknown so far. Here we describe a procedure that leads to highly regular FMMA‐based polymers for the first time, characterized by polydispersity indices (PDI) of less that 1.05 and very high blocking efficiencies (>95%) in sequential copolymerization with styrene. Some of the obtained poly[styrene‐block‐(ferrocenylmethyl methacrylate)]s show unusual microphase morphologies, presumably the consequence of high Tgs causing ‘frustrated’ non‐equilibrium states.
972.
Polymerizable vinylimidazolium ionic liquids (ILs) that contain mesogenic coumarin and biphenyl units, respectively, have been synthesized. The N‐alkylation of N‐vinylimidazole with bromoalkylated mesogenic units 7‐(6‐bromohexyloxy)coumarin ( 1 ) and 4,4′‐bis(6‐bromohexyloxy)biphenyl ( 2 ) was then carried out. The thermal behavior of the obtained ILs 3 and 4 was investigated by differential scanning calorimetry and polarizing optical microscopy. These measurements showed that the attached mesogenic units induce the self‐assembly of ILs and, therefore, the occurrence of liquid crystalline phases. Subsequently, the ionic liquid crystals (ILCs) 3 and 4 were polymerized by a free‐radical mechanism.
973.
Summary : Pulp reactivity is a kinetic term and is always connected with a certain derivatization process. The quality and hence the market value of the pulp is determined by such characteristics as α- cellulose content, solubility, brightness, ash content, as well as the amount of soluble material in dichloromethane. However, solubility data, especially S18 and S10 values do not characterise dissolving pulp reactivity. These are indicative of pulp solubility and provide some information regarding losses of material during pulp processing. One way by which the pulp reactivity for viscose making can be characterised is the investigation of the mercerisation step. Following the mercerisation kinetics by help of the molecular weight distribution of cellulose II the behaviour especially of the high molecular weight cellulose gives information regarding the accessibility and therefore, about the reactivity of the pulp aside from losses in low molecular weight cellulose. This behaviour will be shown on different pulps and the physicochemical background will be discussed in relation to results obtained from wide angle X-ray scattering and Raman investigations. The influence of the behaviour of the pulp during mercerising on the viscose process, and the molecular weight distribution of the viscose including the distribution of the xanthogenate groups along the chain was investigated and will also be discussed. 相似文献
974.
Anne‐Christine Schmidt Benjamin Fahlbusch Matthias Otto 《Journal of mass spectrometry : JMS》2009,44(6):898-910
Arsenic‐binding proteins are of toxicological importance since enzymatic activities can be blocked by arsenic interactions. In the present work, a novel methodology based on size exclusion chromatography coupled to electrospray ionization mass spectrometry (SEC‐ESI‐MS) was developed with special emphasis to preserve the intact proteins and their arsenic bindings. The eluent composition of 25 mM Tris/HCl, pH 7.5, with the addition of 100‐mM NaCl optimized for SEC with UV detection provided the highest SEC separation efficiency, but was not compatible with the ESI‐MS because of the non‐volatility of the buffer substance and of the salt additive. In order to find the best compromise between chromatographic separation and ionization of the arsenic‐binding proteins, buffer type and concentration, pH value, portion of organic solvent in the SEC eluent as well as the flow rate were varied. In the optimized procedure five different arsenic‐binding peptides and proteins (glutathione, oxytocin, aprotinin, α‐lactalbumin, thioredoxin) covering a molar mass range of 0.3–14 kDa could be analyzed using 75% 10‐mM ammonium formate, pH 5.0/25% acetonitrile (v : v) as eluent and a turbo ion spray source operated at 300 °C and 5.5 kV. A complete differentiation of all peptides and proteins involved in the arsenic‐binding studies as well as of their arsenic‐bound forms has become feasible by means of the extracted ion chromatograms (XIC) of the mass spectrometric detection. The new method offered the possibility to estimate equilibrium constants for the reaction of phenylarsine oxide with different thiol‐containing biomolecules by means of the XIC peak areas of reactants and products. Limits of detection in the range of 2–10 µM were obtained by SEC‐ESI‐MS for the individual proteins. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
975.
Bruno Bulic Dr. Marcus Pickhardt Dr. Boris Schmidt Prof. Eva‐Maria Mandelkow Dr. Herbert Waldmann Prof. Eckhard Mandelkow Prof. 《Angewandte Chemie (International ed. in English)》2009,48(10):1740-1752
Small molecules against Alzheimer's : The pathological aggregation of the tau protein is a major hallmark of neurodegenerative diseases such as Alzheimer's disease. The inhibition or reversal of tau aggregation is a potential therapeutic strategy that is currently undergoing clinical trials. The image shows pathological fibers assembled from tau protein, which are the main components of the neurofibrillary tangles of Alzheimer's disease.
976.
Andrew R. Shaffer Joseph A. R. Schmidt Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(11):2662-2673
Phorteen phine phosphines : Fourteen new α,β‐unsaturated β‐chloroimines were synthesized from inexpensive ketones by using the Vilsmeier–Haack reagent followed by Schiff‐base condensation. Each imine was subsequently converted to an α,β‐unsaturated 3‐iminophosphine through either late‐metal‐catalyzed phosphorus–carbon cross‐coupling or through an addition–elimination sequence (see scheme). This high‐yield protocol serves as a general means to produce α,β‐unsaturated 3‐iminophosphines.
977.
Christof Schmitz Ahmed Mourran Helmut Keul Martin Möller Martina Keerl Walter Richtering 《Colloid and polymer science》2009,287(10):1183-1193
The effect of microstructure on the aggregation behaviour of symmetrical di- and triblock copolymers P(BMA)-b-P(MAA) and P(BMA)-b-P(BMA-co-MAA)-b-P(MAA) with a molecular weight of 40,000 g/mol was studied. The critical micelle concentration, hydrodynamic radius and morphology
of the micelles were determined by fluorescence spectroscopy, dynamic light scattering and scanning force microscopy (SFM).
Whereas no effect of the microstructure on the critical micelle concentration could be detected, the hydrodynamic radius decreased
from di- to triblock copolymer from 53 to 36 nm. The decrease of about 32% corresponds to the length of the random middle
block within the triblock copolymer so that the reduction in hydrodynamic radius was caused by a complete orientation of the
random middle block at the core corona interface. Finally, the SFM investigation showed that dehydration of micelles on a
substrate is accompanied by formation of a physisorbed monolayer with a thickness of 2 nm on which the micelles are deposited. 相似文献
978.
Martin Egginger Siegfried Bauer Reinhard Schw?diauer Helmut Neugebauer Niyazi Serdar Sariciftci 《Monatshefte für Chemie / Chemical Monthly》2009,95(1):735-750
Abstract
Research into organic field effect transistors (OFETs) has made significant advances—both scientifically and technologically—during the last decade, and the first products will soon enter the market. Printed electronic circuits using organic resistors, diodes and transistors may become cheap alternatives to silicon-based systems, especially in large-area applications. A key parameter for device operation, besides long term stability, is the reproducibility of the current–voltage behavior, which may be affected by hysteresis phenomena. Hysteresis effects are often observed in organic transistors during sweeps of the gate voltage (V GS). This hysteresis can originate in various ways, but comparative scientific investigations are rare and a comprehensive picture of “hysteresis phenomena” in OFETs is still missing. This review provides an overview of the physical effects that cause hysteresis and discusses the importance of such effects in OFETs in a comparative manner. 相似文献979.
Boris A. Trofimov Elena Yu. Schmidt Igor A. Ushakov Elena Yu. Senotrusova Grigorii G. Aleksandrov 《Tetrahedron letters》2009,50(26):3314-3775
A new three-component reaction between alkyl aryl(hetaryl)ketoximes, acetylene, and aliphatic ketones in the superbasic systems KOH/DMSO and LiOH/CsF/DMSO (70-90 °C, initial acetylene pressure 13-15 atm, 5-60 min) affords novel 4-methylene-3-oxa-1-azabicyclo[3.1.0]hexanes in yields of up to 75%. Using KOH/DMSO, the side products of the reaction are O-vinylketoximes and 2-aryl(hetaryl)pyrroles, while with LiOH/CsF/DMSO, the reaction proves to be selective, only minor amounts of the corresponding alkyl aryl(hetaryl) ketones being detectable. 相似文献
980.
Nico Fleck Caspar A. Heubach Tobias Hett Florian R. Haege Pawel P. Bawol Helmut Baltruschat Olav Schiemann 《Angewandte Chemie (International ed. in English)》2020,59(24):9767-9772
The understanding of biomolecular function is coupled to knowledge about the structure and dynamics of these biomolecules, preferably acquired under native conditions. In this regard, pulsed dipolar EPR spectroscopy (PDS) in conjunction with site‐directed spin labeling (SDSL) is an important method in the toolbox of biophysical chemistry. However, the currently available spin labels have diverse deficiencies for in‐cell applications, for example, low radical stability or long bioconjugation linkers. In this work, a synthesis strategy is introduced for the derivatization of trityl radicals with a maleimide‐functionalized methylene group. The resulting trityl spin label, called SLIM, yields narrow distance distributions, enables highly sensitive distance measurements down to concentrations of 90 nm , and shows high stability against reduction. Using this label, the guanine‐nucleotide dissociation inhibitor (GDI) domain of Yersinia outer protein O (YopO) is shown to change its conformation within eukaryotic cells. 相似文献