全文获取类型
收费全文 | 16180篇 |
免费 | 742篇 |
国内免费 | 141篇 |
专业分类
化学 | 10985篇 |
晶体学 | 103篇 |
力学 | 452篇 |
数学 | 2781篇 |
物理学 | 2742篇 |
出版年
2023年 | 140篇 |
2022年 | 256篇 |
2021年 | 332篇 |
2020年 | 404篇 |
2019年 | 390篇 |
2018年 | 260篇 |
2017年 | 226篇 |
2016年 | 610篇 |
2015年 | 480篇 |
2014年 | 570篇 |
2013年 | 880篇 |
2012年 | 1132篇 |
2011年 | 1327篇 |
2010年 | 683篇 |
2009年 | 593篇 |
2008年 | 992篇 |
2007年 | 951篇 |
2006年 | 947篇 |
2005年 | 844篇 |
2004年 | 733篇 |
2003年 | 513篇 |
2002年 | 529篇 |
2001年 | 181篇 |
2000年 | 151篇 |
1999年 | 155篇 |
1998年 | 123篇 |
1997年 | 131篇 |
1996年 | 173篇 |
1995年 | 109篇 |
1994年 | 116篇 |
1993年 | 122篇 |
1992年 | 90篇 |
1991年 | 97篇 |
1990年 | 72篇 |
1989年 | 72篇 |
1988年 | 84篇 |
1987年 | 74篇 |
1986年 | 69篇 |
1985年 | 104篇 |
1984年 | 113篇 |
1982年 | 120篇 |
1981年 | 125篇 |
1980年 | 99篇 |
1979年 | 92篇 |
1978年 | 119篇 |
1977年 | 98篇 |
1976年 | 78篇 |
1975年 | 74篇 |
1974年 | 72篇 |
1973年 | 73篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
141.
Jürg K. Schneider Peter Hofstetter Ern Pretsch Daniel Ammann Wilhelm Simon 《Helvetica chimica acta》1980,63(1):217-224
N,N,N′,N′-Tetrabutyl-3,6-dioxaoctane-dithioamide, an Ionophore with Selectivity for Cd2+ The dioxa-dithioamide 3 behaves as a highly selective ionophore for Cd2+ in solvent polymeric membranes. It induces cation-permselectivity in these membranes with a transference number of 1 for Cd(NO3)2- and of 2 for CdCl2-solutions. In the presence of a proton carrier, 3 may be used to selectively pump Cd2+ through membranes by coupling with a pH gradient. 相似文献
142.
During electrolysis of molten KF-2HF, strongly adherent fluorine bubbles are generated at the surface of carbon anode. The current was passing even if the horizontal anode was fully covered with gas film. The formation and growth of gas bubbles were studied by transient electrochemical techniques. It was observed that the fluorine bubbles do not have the spherical cap shape predicted by the classical theory. The curvature radius of the interface profile is not constant, the edge of the bubble being flat with a contact angle close to zero. The results are interpreted in the frame of a model which takes into account the predominant role of the interfacial properties. 相似文献
143.
Gérald Perron Jean-François Côté Daniel Lambert Johanne Pageau Jacques E. Desnoyers 《Journal of solution chemistry》1994,23(2):121-133
Blends of immiscible polymers are often stabilized by block copolymers which can form non-aqueous micelles and microemulsions in the liquid polymers. The phase diagrans, apparent volumes and apparent heat capacities of model non-aqueous binary and ternary systems were studied in order to investigate the conditions under which such self-assembly systems could form. 1,2-Hexanediol, which can cosolubilize hexane and ethyleneglycol, forms inverse micelles in hexane and weak microaggregates in ethyleneglycol. Genapol X-060, a commercial alcoholic surfactant containing on the average an aliphatic chain of 13 carbons and 6 oxyethylenes (C13E6), forms microaggregates in poly(ethyleneglycol) 400. These self-assembly systems are strengthen in the presence of a third component which has an affinity for the inner phase.Presented at the Symposium, 76th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65th birthday. 相似文献
144.
Daniel William Tholen 《Accreditation and quality assurance》1998,3(9):362-366
There are three stages to evaluating a laboratory's results in an interlaboratory proficiency test: establishing the correct
result for the test item, determining an evaluation statistic for the particular result, and establishing an acceptable range.
There are a wide variety of procedures for accomplishing these three stages and a correspondingly wide variety of statistical
techniques in use. Currently in North America the largest number of laboratory proficiency test programs are in the clinical
laboratory field, followed by programs for environmental laboratories that test drinking water and waste water. Proficiency
testing in both of these fields is under the jurisdiction of the federal government and other regulatory and accreditation
agencies. Many of the statistical procedures are specified in the regulations, to assure comparability of different programs
and a fair evaluation of performance. In this article statistical procedures recommended in International Organization for
Standardization Guide 43, Part 1, are discussed and compared with current practices in North America.
Received: 22 April 1998 · Accepted: 12 May 1998 相似文献
145.
Kramer RM Li C Carter DC Stone MO Naik RR 《Journal of the American Chemical Society》2004,126(41):13282-13286
Self-assembled particles of genetically engineered human L subunit ferritin expressing a silver-binding peptide were used as nanocontainers for the synthesis of silver nanoparticles. The inner cavity of the self-assembled protein cage displays a dodecapeptide that is capable of reducing silver ions to metallic silver. This chimeric protein cage when incubated in the presence of silver nitrate exhibits the growth of a silver nanocrystal within its cavity. Our studies indicate that it is possible to design chimeric cages, using specific peptide templates, for the growth of other inorganic nanoparticles. 相似文献
146.
Daniel Sherman 《Tetrahedron letters》2005,46(29):4901-4903
A new method for one-pot chemoselective heterobifunctional cross-linking of organic molecules is described. The method is based on tert-butyldiphenylsilyl malonate and involves two sequential carbodiimide couplings with two different molecules possessing a hydroxy or an amino functionality with one intermediate one-pot fluoride deprotection. 相似文献
147.
Role of elemental fluorine in nuclear field 总被引:1,自引:0,他引:1
The preparation of fluorine gas by Henri Moissan by electrolysis of molten fluorides can be considered as one of the most important discoveries during the last centuries. Indeed, in addition to its use in many industrial fields (microelectronic, surface cleaning, pharmacology, medicine, …), fluorine gas is strongly involved in nuclear field for the preparation of UF6. The latter allows the natural uranium enrichment via the gaseous diffusion process. Due to the increase of the energy demand in industrialised and emergent countries, the production of UF6 and consequently of F2 should increase drastically during the next decades. The aim of this paper is to summarise the evolution of the process to produce fluorine from its discovery to the present process. Few aspects on the researches done for a better understanding of the fluorine evolution reaction are presented. The use of fluorine in the nuclear field is also discussed. 相似文献
148.
Photodynamic therapy (PDT) relies on three main ingredients, oxygen, light and photoactivating compounds, although the PDT response is definitively contingent on the site and level of reactive oxygen species (ROS) generation. This study describes the development of a novel, fluorescent-based actinometer microsphere system as a means of discerning spatially resolved dosimetry of total fluence and ROS production. Providing a high resolution, localized, in situ measurement of fluence and ROS generation is critical for developing in vivo PDT protocols. Alginate-poly-L-lysine-alginate microspheres were produced using ionotropic gelation of sodium alginate droplets, ranging from 80 to 200 microm in diameter, incorporating two dyes, ADS680WS (ADS) and Rhodophyta-phycoerythrin (RPE), attached to the spheres' inside and outside layers, respectively. To test the responsivity and dynamic range of RPE for ROS detection, the production of ROS was initiated either chemically using increasing concentrations of potassium perchromate or photochemically using aluminum tetrasulphonated phthalocyanine. The generation of singlet oxygen was confirmed by phosphorescence at 1270 nm. The resulting photodegradation and decrease in fluorescence of RPE was found to correlate with increased perchromate or PDT treatment fluence, respectively. This effect was independent of pH (6.5-8) and could be inhibited using sodium azide. RPE was not susceptible to photobleaching with light alone (670 nm; 150 Jcm(-2)). ADS, which absorbs light between 600 and 750 nm, showed a direct correlation between radiant exposure (670 nm; 0-100 Jcm(-2)) and diminished fluorescence. Photobleaching was independent of irradiance (10-40 mW cm(-2)). We propose that actinometer microspheres may provide a means for obtaining high spatial resolution information regarding delivered PDT dose within model systems during investigational PDT development and dosimetric information for clinical extracorporeal PDT as in the case of ex vivo bone marrow purging. 相似文献
149.
Rhodopsin is the dim light photosensitive pigment of animals. In this work, we undertook to study the structure of rhodopsin from swine and compare it with bovine and rat rhodopsin. Porcine rhodopsin was analyzed using methodology developed previously for mass spectrometric analysis of integral membrane proteins. Combining efficient protein cleavage and high performance liquid chromatography separation with the sensitivity of mass spectrometry (MS), this technique allows the observation of the full protein map and the posttranslational modifications of the protein in a single experiment. The rhodopsin protein from a single porcine eye was sequenced completely, with the exception of two single-amino acid fragments and one two-amino acid fragment, and the gene sequence reported previously was confirmed. The posttranslational modifications, similar to the ones reported previously for bovine and rat rhodopsin, were also identified. Although porcine rhodopsin has a high degree of homology to bovine and rat rhodopsins and most of their posttranslational modifications are identical, the glycosylation and phosphorylation patterns observed were different. These results show that rhodopsin from a single porcine eye can be characterized completely by MS. This technology opens the possibility of rhodopsin structural and functional studies aided by powerful mass spectrometric analysis, using the fellow eye as an internal control. 相似文献
150.
Carmona D Lahoz FJ Atencio R Edwards AJ Oro LA Lamata MP Esteban M Trofimenko S 《Inorganic chemistry》1996,35(9):2549-2557
Treatment of the metallo ligands [ML(pz)(2)(Hpz)] (pz = pyrazolate; L = C(5)Me(5), M = Ir (1); L = mesitylene, M = Ru (3)) with [M'Cl{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (4), Ni (5)) yields heterodinuclear complexes of formula [LM(&mgr;-pz)(2)(&mgr;-Cl)M'{HB(3-i-Pr-4-Br-pz)(3)}] (L = C(5)Me(5); M = Ir; M' = Co (6), Ni (7). L = mesitylene; M = Ru; M' = Co (8)). The related complex [Ru(eta(6)-p-cymene)(pz)(2)(Hpz)] (2) reacts with equimolar amounts of 4 or 5 to give mixtures of the corresponding bis(&mgr;-pyrazolato) &mgr;-chloro complexes [(eta(6)-p-cymene)Ru(&mgr;-pz)(2)(&mgr;-Cl)M'{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (9), Ni (10)) and the triply pyrazolato-bridged complexes [(eta(6)-p-cymene)Ru(&mgr;-pz)(3)M'{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (11), Ni (12)). Complex 1 reacts with 5 in the presence of KOH to give the IrNi complex [(eta(5)-C(5)Me(5))Ir(&mgr;-pz)(3)Ni{HB(3-i-Pr-4-Br-pz)(3)}] (13) whereas its reaction with 4 and KOH rendered the bis(&mgr;-pyrazolato) &mgr;-hydroxo complex [(eta(5)-C(5)Me(5))Ir(&mgr;-pz)(2)(&mgr;-OH)Co{HB(3-i-Pr-4-Br-pz)(3)}] (14). The molecular structure of the heterobridged IrCo complex (6) and those of the homobridged RuNi (12) and IrNi (13) complexes have been determined by X-ray analyses. Compound 6 crystallizes in the monoclinic space group P2(1)/n, with a = 10.146(5) ?, b = 18.435(4) ?, c = 22.187(13) ?, beta = 97.28(4) degrees, and Z = 4. Complex 12 is monoclinic, space group P2(1), with a = 10.1169(7) ?, b = 21.692(2) ?, c = 11.419(1) ?, beta = 112.179(7) degrees, and Z = 2. Compound 13 crystallizes in the monoclinic space group Cc, with a = 13.695(2) ?, b = 27.929(6) ?, c = 13.329(2) ?, beta = 94.11(4) degrees, and Z = 4. All the neutral complexes 6, 12, and 13 consist of linear M.M'.B backbones with two (6) or three (12, 13) pyrazolate ligands bridging the dimetallic M.M' units and three substituted 3-i-Pr-4-Br-pz groups joining M' to the boron atoms. The presence in the proximity of the first-row metal M' of the three space-demanding isopropyl substituents of the pyrazolate groups induces a significant trigonal distortion of the octahedral symmetry, yielding clearly different M'-N bond distances on both sides of the ideal octahedral coordination sphere of these metals. 相似文献