全文获取类型
收费全文 | 834篇 |
免费 | 32篇 |
国内免费 | 3篇 |
专业分类
化学 | 686篇 |
晶体学 | 12篇 |
力学 | 11篇 |
数学 | 50篇 |
物理学 | 110篇 |
出版年
2023年 | 5篇 |
2022年 | 8篇 |
2021年 | 10篇 |
2020年 | 11篇 |
2019年 | 8篇 |
2018年 | 10篇 |
2017年 | 5篇 |
2016年 | 25篇 |
2015年 | 19篇 |
2014年 | 18篇 |
2013年 | 40篇 |
2012年 | 66篇 |
2011年 | 71篇 |
2010年 | 24篇 |
2009年 | 36篇 |
2008年 | 49篇 |
2007年 | 63篇 |
2006年 | 64篇 |
2005年 | 71篇 |
2004年 | 79篇 |
2003年 | 44篇 |
2002年 | 36篇 |
2001年 | 8篇 |
2000年 | 8篇 |
1999年 | 9篇 |
1997年 | 8篇 |
1996年 | 8篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 5篇 |
1974年 | 2篇 |
1973年 | 4篇 |
1968年 | 1篇 |
1954年 | 1篇 |
1943年 | 2篇 |
1937年 | 1篇 |
1935年 | 1篇 |
1885年 | 1篇 |
排序方式: 共有869条查询结果,搜索用时 15 毫秒
1.
Amphiphilic thermoset elastomers from metal‐free,click crosslinking of PEG‐grafted silicone surfactants 下载免费PDF全文
Michael A. Brook Frances Lasowski Heather Sheardown 《Journal of polymer science. Part A, Polymer chemistry》2015,53(9):1082-1093
The hydrophobicity of silicone elastomers can compromise their utility in some biomaterials applications. Few effective processes exist to introduce hydrophilic groups onto a polysiloxane backbone and subsequently crosslink the material into elastomers. This problem can be overcome through the utilization of metal‐free click reactions between azidoalkylsilicones and alkynyl‐modified silicones and/or PEGs to both functionalize and crosslink silicone elastomers. Alkynyl‐functional PEG was clicked onto a fraction of the available azido groups of a functional polysiloxane, yielding azido reactive PDMS‐g‐PEG rake surfactants. The reactive polymers were then used to crosslink alkynyl‐terminated PDMS of different molecular weights. Using simple starting materials, this generic yet versatile method permits the preparation and characterization of a library of amphiphilic thermoset elastomers that vary in their composition, crosslink density, elasticity, hydrogel formation, and wettability. An appropriate balance of PEG length and crosslink density leads to a permanently highly wettable silicone elastomer that demonstrated very low levels of protein adsorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1082–1093 相似文献
2.
Multi-quantum well heterostructures (MQWHs) of the novel Ga(NAsP)/GaP material system have been grown, pseudomorphically strained to GaP-substrate. The crystalline perfection is verified by transmission electron microscopy (TEM). For As-concentrations in excess of about 70%, a direct band structure and adequate luminescence efficiency for laser device application is observed. Temperature-dependent photoluminescence (PL) investigations show the influence of carrier localisation and non-radiative recombination processes typical for dilute nitride materials. With rising N content in the active material, the emission wavelength shifts towards longer wavelength, leading to Ga(NAs)/GaP MQW structures with photon energies below the indirect band gap of silicon (Si). At the same time the luminescence intensity drops due to an increase in non-radiative carrier traps and/or structural degradation. 相似文献
3.
Thorsten Hamann Erin Osborne Heather L. Youngs Julie Misson Laurent Nussaume Chris Somerville 《Cellulose (London, England)》2004,11(3-4):279-286
We have used Affymetrix gene chips to measure the expression of 10 CESA and 29 CSL genes of Arabidopsis in different developmental stages or organs. These measurements reveal that many of the genes exhibit different levels of expression in the various organs. While several CESA genes are highly expressed in all the tissues examined, very few CSL genes approach such high levels of expression. This suggests that the CSL genes either encode enzymes for the synthesis of minor components of cell walls or are expressed only in specific cell types. The expression data also highlights the potential importance of the CESA genes for primary and secondary cell wall formation during different developmental stages and in the different organs examined. 相似文献
4.
Dorina Mitrea Heather Rosenblatt 《Mathematical Methods in the Applied Sciences》2006,29(12):1349-1361
We prove a rather general mean‐value formula in the theory of elasticity, which expresses the value of the displacement at the centre of a sphere in terms of certain combinations of integral averages over the sphere itself of the traction and the displacement. We also establish the corresponding converse to this mean‐value formula under minimal smoothness assumptions on the displacement. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
5.
Synthetic erythropoietic proteins: tuning biological performance by site-specific polymer attachment
Chen SY Cressman S Mao F Shao H Low DW Beilan HS Cagle EN Carnevali M Gueriguian V Keogh PJ Porter H Stratton SM Wiedeke MC Savatski L Adamson JW Bozzini CE Kung A Kent SB Bradburne JA Kochendoerfer GG 《Chemistry & biology》2005,12(3):371-383
Chemical synthesis in combination with precision polymer modification allows the systematic exploration of the effect of protein properties, such as charge and hydrodynamic radius, on potency using defined, homogeneous conjugates. A series of polymer-modified synthetic erythropoiesis proteins were constructed that had a polypeptide chain similar to the amino acid sequence of human erythropoietin but differed significantly in the number and type of attached polymers. The analogs differed in charge from +5 to -26 at neutral pH and varied in molecular weight from 30 to 54 kDa. All were active in an in vitro cell proliferation assay. However, in vivo potency was found to be strongly dependent on overall charge and size. The trends observed in this study may serve as starting points for the construction of more potent synthetic EPO analogs in the future. 相似文献
6.
Heredia KL Bontempo D Ly T Byers JT Halstenberg S Maynard HD 《Journal of the American Chemical Society》2005,127(48):16955-16960
Protein-polymer conjugates are widely used in biotechnology and medicine, and new methods to prepare the bioconjugates would be advantageous for these applications. In this report, we demonstrate that bioactive "smart" polymer conjugates can be synthesized by polymerizing from defined initiation sites on proteins, thus preparing the polymer conjugates in situ. In particular, free cysteines, Cys-34 of bovine serum albumin (BSA) and Cys-131 of T4 lysozyme V131C, were modified with initiators for atom transfer radical polymerization (ATRP) either through a reversible disulfide linkage or irreversible bond by reaction with pyridyl disulfide- and maleimide-functionalized initiators, respectively. Initiator conjugation was verified by electrospray-ionization mass spectroscopy (ESI-MS), and the location of the modification was confirmed by muLC-MSMS (tandem mass spectrometry) analysis of the trypsin-digested protein macroinitiators. Polymerization of N-isopropylacrylamide (NIPAAm) from the protein macroinitiators resulted in thermosensitive BSA-polyNIPAAm and lysozyme-polyNIPAAm in greater than 65% yield. The resultant conjugates were characterized by gel electrophoresis and size exclusion chromatography (SEC) and easily purified by preparative SEC. The identity of polymer isolated from the BSA conjugate was confirmed by (1)H NMR, and the polydispersity index was determined by gel permeation chromatography (GPC) to be as low as 1.34. Lytic activities of the lysozyme conjugates were determined by two standard assays and compared to that of the unmodified enzyme prior to polymerization; no statistical differences in bioactivity were observed. 相似文献
7.
We report here on a family of self-assembling fluorescent organic amphiphiles with a biomolecular L-lysine hydrophile and a photonically active phenylene vinylene hydrophobe. Unlike conventional amphiphiles, these segmented dendrimers feature a rigid, branched hydrophobe, and have packing characteristics controlled by the ratio of cross-sectional areas of the hydrophobe and hydrophile. In dilute solution, the amphiphiles form supramolecular aggregates, which are easily taken in by cells through an endocytic pathway, and have no discernible effect on cell proliferation or morphology. An analogous pyrene-based amphiphile was cytotoxic, suggesting that cell survival may be linked either to the self-assembling nature of the amphiphiles, or to the specific properties of the phenylene vinylene segment. The combination of photonic and biological components in these amphiphiles provides great potential for applications in sensing or delivery of molecules to intracellular targets. 相似文献
8.
1,2-Bis-(triphenylphosphorane-ylidene-amino)ethane as a Bidentate Ligand in Transition Metal Complexes The reactions of Ph3P?N? C2H4? N?PPh3 with transition metal halogenides MX2 give according to eq. (1) novel bisiminophosphorane complexes of the type M(Ph3PNC2H4 NPPh3)X2 (M ? Co, X ? Cl 1 a , Br 1 b , J 1 c ; M ? Ni, X ? Cl 2 a , Br 2 b , J 2 c , M ? Hg, X ? Cl 3 , M ? Cd, X ? Cl 4 ). The preparation, properties, magnetic moments, and structure of the new complexes are reported 相似文献
9.
Fiedler AT Halfen HL Halfen JA Brunold TC 《Journal of the American Chemical Society》2005,127(6):1675-1689
A combined synthetic/spectroscopic/computational approach has been employed to prepare and characterize a series of Fe(II)-thiolate complexes that model the square-pyramidal [Fe(II)(N(His))(4)(S(Cys))] structure of the reduced active site of superoxide reductases (SORs), a class of enzymes that detoxify superoxide in air-sensitive organisms. The high-spin (S = 2) Fe(II) complexes [(Me(4)cyclam)Fe(SC(6)H(4)-p-OMe)]OTf (2) and [FeL]PF(6) (3) (where Me(4)cyclam = 1,4,8,11-tetramethylcyclam and L is the pentadentate monoanion of 1-thioethyl-4,8,11-trimethylcyclam) were synthesized and subjected to structural, magnetic, and electrochemical characterization. X-ray crystallographic studies confirm that 2 and 3 possess an N(4)S donor set similar to that found for the SOR active site and reveal molecular geometries intermediate between square pyramidal and trigonal bipyramidal for both complexes. Electronic absorption, magnetic circular dichroism (MCD), and variable-temperature variable-field MCD (VTVH-MCD) spectroscopies were utilized, in conjunction with density functional theory (DFT) and semiemperical INDO/S-CI calculations, to probe the ground and excited states of complexes 2 and 3, as well as the previously reported Fe(II) SOR model [(L(8)py(2))Fe(SC(6)H(4)-p-Me)]BF(4) (1) (where L(8)py(2) is a tetradentate pyridyl-appended diazacyclooctane macrocycle). These studies allow for a detailed interpretation of the S-->Fe(II) charge transfer transitions observed in the absorption and MCD spectra of complexes 1-3 and provide significant insights into the nature of Fe(II)-S bonding in complexes with axial thiolate ligation. Of the three models investigated, complex 3 exhibits an absorption spectrum that is particularly similar to the one reported for the reduced SOR enzyme (SOR(red)), suggesting that this model accurately mimics key elements of the electronic structure of the enzyme active site; namely, highly covalent Fe-S pi- and sigma-interactions. These spectral similarities are shown to arise from the fact that 3 contains an alkyl thiolate tethered to the equatorial cyclam ring, resulting in a thiolate orientation that is very similar to the one adopted by the Cys residue in the SOR(red) active site. Possible implications of our results with respect to the electronic structure and reactivity of SOR(red) are discussed. 相似文献
10.
Thompson M Wilkins SJ Compton RG Viles HA 《Journal of colloid and interface science》2003,259(2):338-345
The dissolution kinetics of surface-pretreated and weathered calcite was investigated in dilute acid using a channel flow cell with microdisk detection. Two pretreatments were studied, polymaleic acid and phosphoric acid. Treatment with polymaleic acid was shown to significantly passivate calcite but to a lesser extent than the phosphoric acid and the former coating was found to be less effective for protection of calcite from acid attack. However, treatment of calcite with phosphoric acid resulted in the passivation of calcite from acid attack which strongly inhibited dissolution, an effect that was enhanced even further after exposure to the environment. 相似文献