全文获取类型
收费全文 | 932篇 |
免费 | 23篇 |
国内免费 | 1篇 |
专业分类
化学 | 758篇 |
晶体学 | 2篇 |
力学 | 21篇 |
数学 | 49篇 |
物理学 | 126篇 |
出版年
2023年 | 6篇 |
2021年 | 9篇 |
2020年 | 4篇 |
2019年 | 13篇 |
2018年 | 4篇 |
2017年 | 7篇 |
2016年 | 15篇 |
2015年 | 12篇 |
2014年 | 10篇 |
2013年 | 30篇 |
2012年 | 58篇 |
2011年 | 59篇 |
2010年 | 21篇 |
2009年 | 17篇 |
2008年 | 43篇 |
2007年 | 49篇 |
2006年 | 46篇 |
2005年 | 44篇 |
2004年 | 40篇 |
2003年 | 32篇 |
2002年 | 76篇 |
2001年 | 20篇 |
2000年 | 7篇 |
1999年 | 11篇 |
1998年 | 12篇 |
1997年 | 21篇 |
1996年 | 15篇 |
1995年 | 18篇 |
1994年 | 13篇 |
1993年 | 11篇 |
1992年 | 11篇 |
1991年 | 15篇 |
1990年 | 8篇 |
1989年 | 16篇 |
1988年 | 18篇 |
1987年 | 11篇 |
1986年 | 7篇 |
1985年 | 17篇 |
1984年 | 15篇 |
1983年 | 5篇 |
1982年 | 4篇 |
1981年 | 10篇 |
1980年 | 12篇 |
1979年 | 15篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 10篇 |
1975年 | 12篇 |
1974年 | 13篇 |
1973年 | 6篇 |
排序方式: 共有956条查询结果,搜索用时 15 毫秒
71.
The setting of analytical quality specifications in laboratory medicine has attracted attention for many years. Over time,
many strategies were advocated and all had advantages and disadvantages. In the final decade of the last millennium, considerable
confusion existed on how to define analytical quality specifications correctly and how to apply them in everyday practice.
This led to wide professional interest. In 1999, a consensus conference sponsored by IUPAC, IFCC and WHO was held in Stockholm
on “Strategies to Set Global Analytical Quality Specifications in Laboratory Medicine”. The consensus set useful and well-documented
strategies for the setting of analytical quality specifications into a hierarchy with the best strategy at the highest level,
namely, (1) Evaluation of the effect of analytical performance on clinical outcomes in specific clinical situations, (2) Evaluation
of the effect of analytical performance on clinical decisions in general, (3) Published professional recommendations, (4)
Performance goals set by regulatory bodies and EQAS organisers, and (5) Goals based on the current state of the art. Much success has been achieved since the promulgation of the statement with the approach being adopted by many in laboratory
medicine for a very wide variety of purposes, particularly in quality management. However, there is a requirement for additional
investigation of, inter alia, quality specifications for examinations done on measurements performed on ordinal and nominal scales, pre-analytical factors
and matrix effects, examinations done as POCT, target values of control materials, and ways in which analytical quality specifications
can be used both to set what is the optimum performance and as a tool for assessment of everyday practice. 相似文献
72.
Jones AK Lamle SE Pershad HR Vincent KA Albracht SP Armstrong FA 《Journal of the American Chemical Society》2003,125(28):8505-8514
The cycling between active and inactive states of the catalytic center of [NiFe]-hydrogenase from Allochromatium vinosum has been investigated by dynamic electrochemical techniques. Adsorbed on a rotating disk pyrolytic graphite "edge" electrode, the enzyme is highly electroactive: this allows precise manipulations of the complex redox chemistry and facilitates quantitative measurements of the interconversions between active catalytic states and the inactive oxidized form Ni(r) (also called Ni-B or "ready") as functions of pH, H(2) partial pressure, temperature, and electrode potential. Cyclic voltammograms for catalytic H(2) oxidation (current is directly related to turnover rate) are highly asymmetric (except at pH > 8 and high temperature) due to inactivation being much slower than activation. Controlled potential-step experiments show that the rate of oxidative inactivation increases at high pH but is independent of potential, whereas the rate of reductive activation increases as the potential becomes more negative. Indeed, at 45 degrees C, activation takes just a few seconds at -288 mV. The cyclic asymmetry arises because interconversion is a two-stage reaction, as expected if the reduced inactive Ni(r)-S state is an intermediate. The rate of inactivation depends on a chemical process (rearrangement and uptake of a ligand) that is independent of potential, but sensitive to pH, while activation is driven by an electron-transfer process, Ni(III) to Ni(II), that responds directly to the driving force. The potentials at which fast activation occurs under different conditions have been analyzed to yield the potential-pH dependence and the corresponding entropies and enthalpies. The reduced (active) enzyme shows a pK of 7.6; thus, when a one-electron process is assumed, reductive activation at pH < 7 involves a net uptake of one proton (or release of one hydroxide), whereas, at pH > 8, there is no net exchange of protons with solvent. Activation is favored by a large positive entropy, consistent with the release of a ligand and/or relaxation of the structure around the active site. 相似文献
73.
Irmukhametova GS Fraser BJ Keddie JL Mun GA Khutoryanskiy VV 《Langmuir : the ACS journal of surfaces and colloids》2012,28(1):299-306
PEGylated organosilica nanoparticles have been synthesized through self-condensation of (3-mercaptopropyl)trimethoxysilane in dimethyl sulfoxide into thiolated nanoparticles with their subsequent reaction with methoxypoly(ethylene glycol) maleimide. The PEGylated nanoparticles showed excellent colloidal stability over a wide range of pH in contrast to the parent thiolated nanoparticles, which have a tendency to aggregate irreversibly under acidic conditions (pH < 3.0). Due to the presence of a poly(ethylene glycol)-based corona, the PEGylated nanoparticles are capable of forming hydrogen-bonded interpolymer complexes with poly(acrylic acid) in aqueous solutions under acidic conditions, resulting in larger aggregates. The use of hydrogen-bonding interactions allows more efficient attachment of the nanoparticles to surfaces. The alternating deposition of PEGylated nanoparticles and poly(acrylic acid) on silicon wafer surfaces in a layer-by-layer fashion leads to multilayered coatings. The self-assembly of PEGylated nanoparticles with poly(acrylic acid) in aqueous solutions and at solid surfaces was compared to the behavior of linear poly(ethylene glycol). The nanoparticle system creates thicker layers than the poly(ethylene glycol), and a thicker layer is obtained on a poly(acrylic acid) surface than on a silica surface, because of the effects of hydrogen bonding. Some implications of these hydrogen-bonding-driven interactions between PEGylated nanoparticles and poly(acrylic acid) for pharmaceutical formulations are discussed. 相似文献
74.
75.
Leung KC Aricó F Cantrill SJ Stoddart JF 《Journal of the American Chemical Society》2005,127(16):5808-5810
The versatility and efficiency of dynamic covalent chemistry (DCC) has been exploited in the convergent synthesis of mechanically interlocked dendrimers that are based upon the mutual recognition expressed between secondary dialkylammonium ions and crown ether-like macrocycles. Reversible imine bond formation is employed to clip two acyclic fragments, one of them a diformylpyridine unit bearing a dendritic side chain, and the other a complementary dianiline in the shape of the di(o-aminophenyl)ether of tetraethylene glycol, around each arm of a tritopic trisammonium ion core, thereby affording a branched [4]rotaxane. This template-directed strategy has been demonstrated to work in very high yields (>90%) with successive generations (G0-G2) of a modified Fréchet-type dendritic wedge attached to the 4-position of the diformylpyridine unit. Reduction of these dynamic dendritic systems is achieved upon treatment with borane.THF and results in kinetically stable compounds. The inherent modularity of the overall process should allow for the rapid and straightforward access to many other analogous mechanically interlocked systems in which either the branched core or the dendritic periphery can be modified to suit the needs of any given application of these molecules. Indeed, the dynamic nature of the initial thermodynamically mediated assembly could be utilized in order to amplify particular products from a potential library as a result of a selective recognition process. 相似文献
76.
Jeppesen JO Vignon SA Stoddart JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(19):4611-4625
A [2]pseudorotaxane, based on a semi-dumbbell-shaped component containing asymmetrically substituted monopyrrolotetrathiafulvalene and 1,5-dioxynaphthalene recognition sites for encirclement by cyclobis(paraquat-p-phenylene) and with a "speed bump" in the form of a thiomethyl group situated between the two recognition sites, has been self-assembled. This supramolecular entity is a mixture in solution of two slowly interconverting [2]pseudorotaxanes, one of which is on the verge of being a [2]rotaxane at room temperature, allowing it to be isolated by employing flash column chromatography. These two [2]pseudorotaxanes were both characterized in solution by UV/Vis and (1)H NMR spectroscopies (1D and 2D) and also by differential pulse voltammetry. The spectroscopic and electrochemical data reveal that one of the complexes behaves wholly as a [2]pseudorotaxane, while the other has some [2]rotaxane character to it. The kinetics of the shuttling of cyclobis(paraquat-p-phenylene) between the monopyrrolotetrathiafulvalene and the 1,5-dioxynaphthalene recognition sites have been investigated at different temperatures. The shuttling processes, which are accompanied by detectable color changes, can be monitored using UV/Vis and (1)H NMR spectroscopies; the spectroscopic data have been employed in the determination of the rate constants, free energies of activation, enthalpies of activation, and the entropies of activation for the translation of cyclobis(paraquat-p-phenylene) between the two recognition sites. 相似文献
77.
Horn M Ihringer J Glink PT Stoddart JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4046-4054
A template-directed dynamic clipping procedure has generated a library of nine [2]rotaxanes that have been formed from three dialkylammonium salts-acting as the dumbbell-shaped components-and three dynamic, imino bond-containing, [24]crown-8-like macrocycles-acting as the ring-shaped components-which are themselves assembled from three dialdehydes and one diamine. The rates of formation of these [2]rotaxanes differ dramatically, from minutes to days depending on the choice of dialkylammonium ion and dialdehyde, as do their thermodynamic stabilities. Generally, [2]rotaxanes formed by using 2,6-diformylpyridine as the dialdehyde component, or bis(3,5-bis(trifluoromethyl)benzyl)ammonium hexafluorophosphate as the dumbbell-shaped component, assembled the most rapidly. Those rotaxanes containing this particular electron-deficient dumbbell-shaped unit, or 2,5-diformylfuran units in the macroring, were the most stable thermodynamically. The relative thermodynamic stabilities of all nine of the [2]rotaxanes were determined by competition experiments that were monitored by (1)H NMR spectroscopy. 相似文献
78.
MD. Daloar Hossain Le Thi Bao Tran Jong Myung Park Kwon Taek Lim 《Journal of polymer science. Part A, Polymer chemistry》2010,48(22):4958-4964
A new, efficient method for synthesizing stable nanoparticles with poly(ethylene oxide) (PEO) functionalities on the core surface, in which the micellization and crosslinking reactions occur in one pot, has been developed. First, amphiphilic PEO‐b‐PS copolymers were synthesized by reversible addition fragmentation chain transfer (RAFT) radical polymerization of styrene using (PEO)‐based trithiocarbonate as a macro‐RAFT agent. The low molecular weight PEO‐b‐PS copolymer was dissolved in isopropyl alcohol where the block copolymer self‐assembled as core‐shell micelles, and then the core‐shell interface crosslink was performed using divinylbenzene as a crosslinking agent and 2,2′‐azobisisobutyronitrile as an initiator. The design of the amphiphilic RAFT agent is critical for the successful preparation of core‐shell interface crosslinked micellar nanoparticles, because of RAFT functional groups interconnect PEO and polystyrene blocks. The PEO functionality of the nanoparticles surface was confirmed by 1H NMR and FTIR. The size and morphology of the nanoparticles was confirmed by scanning electron microscopy, transmission electron microscopy, and dynamic laser light scattering analysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
79.
Rapeseed, soybean and sunflower seeds are used for a comparison of solvent extractions by SFE, ASE, fexIKA and Soxtherm apparatus
with the official standard method B-I 5 (87) by the DGF. The optimal extraction parameters for each method are evaluated.
The extracts are analysed regarding the composition of tocopherols, as a parameter for mild extraction conditions and the
content of free fatty acids and diglycerides, as a parameter for the recovery of more polar lipids. The obtained results for
oil content using the optimised methods agree well with the standard method. Differences occur in the results of tocopherol
composition and free fatty acid and diglyceride contents. The SFE method shows the highest recovery regarding the tocopherol
content. The extraction period by SFE is reduced to about 40 min in contrast to 4 h of the DGF standard method. The other
methods also provide considerable time reductions, but showed lower tocopherols and free fatty acid contents.
Received: 25 September 1998 / Revised: 18 January 1999 / Accepted: 21 January 1999 相似文献
80.
MD. Anwarul Hasan Carlos F. Lange Malcolm L. King 《ournal of non Newtonian Fluid Mechanics》2010,165(21-22):1431-1441
The effect of viscoelastic properties and surface tension of artificial mucus simulant samples on the size distribution and volume concentration of bioaerosol droplets generated during simulated coughing was investigated through in vitro experiments. The mucus simulant samples had viscoelastic properties in a similar range as those of real human airway mucus. The mucus simulant gels were prepared by mixing various proportions of 0.5–1.7% locust bean gum solution and 0.1 M sodium tetraborate (XLB) solution. Surface tension of one set of samples was varied by adding different amounts of SDS (sodium dodecyl sulfate) surfactant while the measurement of surface tension was performed using ADSA (axisymmetric drop shape analysis) method. The viscoelastic properties of the samples were measured using a Bohlin Gemini 200 HR (Malvern, UK) nano-rheometer with peltier plate assembly. An artificial cough machine was used to simulate human cough, generating aerosol droplets in a model trachea attached to the front of the cough machine. The size distribution and volume concentration of the droplets generated through simulated cough were measured using a laser diffraction particle sizer (SprayTec, Malvern, USA). The surface tension was found to have negligible effect on the characteristic of generated droplets within the range of this investigation. The experimental results showed a decrease in particle size as the samples changed from a viscous fluid type to a viscoelastic to an elastic solid type sample. The volume concentration also changed significantly as the viscoelasticity of the samples was varied. 相似文献