全文获取类型
收费全文 | 3213篇 |
免费 | 44篇 |
国内免费 | 12篇 |
专业分类
化学 | 2124篇 |
晶体学 | 25篇 |
力学 | 94篇 |
数学 | 387篇 |
物理学 | 639篇 |
出版年
2022年 | 22篇 |
2021年 | 32篇 |
2019年 | 25篇 |
2016年 | 35篇 |
2015年 | 31篇 |
2014年 | 43篇 |
2013年 | 144篇 |
2012年 | 117篇 |
2011年 | 145篇 |
2010年 | 57篇 |
2009年 | 66篇 |
2008年 | 142篇 |
2007年 | 161篇 |
2006年 | 138篇 |
2005年 | 129篇 |
2004年 | 134篇 |
2003年 | 134篇 |
2002年 | 132篇 |
2001年 | 93篇 |
2000年 | 72篇 |
1999年 | 40篇 |
1998年 | 45篇 |
1997年 | 46篇 |
1996年 | 51篇 |
1995年 | 61篇 |
1994年 | 49篇 |
1993年 | 55篇 |
1992年 | 43篇 |
1991年 | 59篇 |
1990年 | 53篇 |
1989年 | 27篇 |
1988年 | 33篇 |
1987年 | 28篇 |
1986年 | 28篇 |
1985年 | 42篇 |
1984年 | 53篇 |
1983年 | 33篇 |
1982年 | 42篇 |
1981年 | 46篇 |
1980年 | 37篇 |
1979年 | 37篇 |
1978年 | 53篇 |
1977年 | 45篇 |
1976年 | 36篇 |
1975年 | 34篇 |
1974年 | 27篇 |
1973年 | 49篇 |
1972年 | 30篇 |
1971年 | 24篇 |
1969年 | 20篇 |
排序方式: 共有3269条查询结果,搜索用时 15 毫秒
81.
Hales M Barner-Kowollik C Davis TP Stenzel MH 《Langmuir : the ACS journal of surfaces and colloids》2004,20(25):10809-10817
A polylactide (D,L-PLA) macroRAFT agent was prepared by utilizing a hydroxyl-functional trithiocarbonate as a coinitiator for the ring-opening polymerization. The length of the resultant polymer was controlled by the concentration of the coinitiator leading to the formation of two PLA polymers with M(n) = 12500 g mol(-)(1) (PDI = 1.46) and M(n) = 20500 g mol(-)(1) (PDI = 1.38) each with omega-trithiocarbonate functionality. Chain extension of PLA via the RAFT (free radical) polymerization of N-isopropyl acrylamide (NIPAAm) resulted in the formation of amphiphilic block copolymers with the PNIPAAm block increasing in size with conversion. TEM measurements of the aggregates obtained by self-organization of the block copolymers in aqueous solutions indicated the formation of vesicles. The sizes of these aggregates were influenced by the ratio of both blocks and the molecular weight of each block. The lower critical solution temperature (LCST) of the block copolymer was largely unaffected by the size of each block. UV turbidity measurements indicated a higher LCST for the block copolymers than for the corresponding PNIPAAm homopolymers. Stabilization of the vesicles was attained by a cross-linking chain extension of the PNIPAAm block using hexamethylene diacrylate. As the trithiocarbonate group was located between the PLA and PNIPAAm blocks, the chain extension resulted in a cross-linked layer between the core and corona of the vesicles. 相似文献
82.
Nithyanandhan J Jayaraman N Davis R Das S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):689-698
A series of azobenzene-functionalized poly(alkyl aryl ether) dendrimers have been synthesized and their photochemical and photophysical properties in solution and as thin films have been investigated. Although the photochemical behavior of the azodendrimers in solution indicated that the azobenzene units behave independently, very similar to the constituent monomer azobenzene unit, the properties of thin solid films of the dendrimers were distinctly different. The azodendrimers, AzoG1, AzoG2, and AzoG3 were observed to form stable supercooled glasses, which showed long-wavelength absorption and red emission characteristics of J-aggregates of the azobenzene chromophores. Reversible photoinduced isomerization of the azodendrimers in the glassy state is described. 相似文献
83.
The development and validation of a rapid liquid chromatography (LC)-tandem mass spectrometry (MS-MS) method for determination of nicotine and cotinine in smokers' serum is described. The method is based on solid-phase extraction in a 96-well plate format and requires only 100 microL of serum. Using normal-phase chromatography, both analytes elute in less than 1 min, which permits high sample throughput applications. The calibrated range is 2-100 ng/mL nicotine and 20-1,000 ng/mL cotinine. For known samples, recovery is 95-116% for nicotine and 93-94% for cotinine. The method is extended to rat serum and human saliva (cotinine only) using partial validation techniques. When compared with an existing radioimmunoassay method in our laboratory, the LC-MS-MS method gives improved accuracy, precision, and sample throughput. 相似文献
84.
Kanibolotsky A Roquet S Cariou M Leriche P Turrin CO de Bettignies R Caminade AM Majoral JP Khodorkovsky V Gorgues A 《Organic letters》2004,6(13):2109-2112
[structure: see text] In four new dendrimers terminated by 12 electroactive tetrathiafulvalenyl substituents, the tridimensional character of the inter- and intradendrimeric charge and electron transfer, and hence of the electroconductivity, is evidenced by examination of the electronic spectra of their corresponding neutral state and cation radical, dication, and mixed-valence salts, including a closed-shell anion. 相似文献
85.
The first synthesis of the fungal natural product (−)-xylariamide A 1 is reported. N,O-Bis(trimethylsilyl)acetamide induced coupling of d-tyrosine with (E)-but-2-enedioic acid 2,5-dioxo-pyrrolidin-1-yl ester methyl ester 5 produced the dechloro natural product 6, which was subsequently monochlorinated using oxone and KCl to yield synthetic 1. (−)-Xylariamide A 1, (+)-xylariamide A 2 and (−)-dechloroxylariamide A 6 displayed no cytotoxic or antimicrobial activity. 相似文献
86.
A study of the fragmentation of the \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{\left({{\rm C}_{\rm 6} {\rm H}_{\rm 6} {\rm O}} \right){\rm Fe}} \right]_{}^{_.^ + } $\end{document} ion formed from two different precursors suggests that the ions adopt different structures over that part of the energy distribution giving rise to decomposition in the ion source. 相似文献
87.
Artificial red cells with crosslinked hemoglobin membranes 总被引:1,自引:0,他引:1
Thomas A. Davis William J. Asher Herbert W. Wallace 《Applied biochemistry and biotechnology》1984,10(1-3):123-132
Artificial cells containing concentrated hemoglobin (Hb) solution were prepared by interfacial polymerization of Hb with glutaraldehyde
(GA) in liquid membrane capsules (LMC). A solution containing 30% of Hb was emulsified in mineral oil as red cell-size microdroplets,
and this emulsion was dispersed in an aqueous phase containing glutaraldehyde to form LMC. The LMC were semipermeable templates
that held the microdroplets of Hb in suspension while GA diffused through the oil to the microdroplet surfaces. The GA crosslinked
Hb at the surface of each microdroplet to form an artificial red-cell membrane encapsulating Hb solution. A water-soluble
surfactant was used to eject the cells from the LMC and suspend them in saline.
Several surfactants were evaluated. Cell size was controlled by agitation speed during preparation of the original emulsion.
Cells of 2.52 = ±1.69 μm were prepared. The encapsulated Hb retained capacity to bind and release O2. The cells had aP
50 of 8.9 torr (1200 Pa) and a capacity of 0.55 cc O2/g of total Hb, indicating that the crosslinked portion of the Hb did not contribute to O2 transport. 相似文献
88.
The reduction of ammonium pertechnetate with bis(diphenylphosphino)methane (dppm), and with diphenyl-2-pyridyl phosphine (Ph(2)Ppy), has been investigated. The neutral Tc(II) complex, trans-TcCl(2)(dppm)(2) (1), has been isolated from the reaction of (NH(4))[TcO(4)] with excess dppm in refluxing EtOH/HCl. Chemical oxidation with ferricinium hexafluorophosphate results in formation of the cationic Tc(III) analogue, trans-[TcCl(2)(dppm)(2)](PF(6)) (2). The dppm ligands adopt the chelating bonding mode in both complexes, resulting in strained four member metallocycles. With excess PhPpy, the reduction of (NH(4))[TcO(4)] in refluxing EtOH/HCl yields a complex with one chelating Ph(2)Ppy ligand and one unidentate Ph(2)Ppy ligand, mer-TcCl(3)(Ph(2)Ppy-P,N)(Ph(2)Ppy-P) (3). The cationic Tc(III) complexes, trans-[TcCl(2)(Ph(2)P(O)py-N,O)(2)](PF(6)) (4) and trans-[TcCl(2)(dppmO-P,O)(2)](PF(6)) (5) (Ph(2)P(O)py = diphenyl-2-pyridyl phosphine monoxide and dppmO = bis(diphenylphosphino)methane monoxide), have been isolated as byproducts from the reactions of (NH(4))[TcO(4)] with the corresponding phosphine. The products have been characterized in the solid state and in solution via a combination of single-crystal X-ray crystallography and spectroscopic techniques. The solution state spectroscopic results are consistent with the retention of the bonding modes revealed in the crystal structures. 相似文献
89.
Palladium supported on amorphous silica, mercapto-functionalized silica, amine functionalized silica, and zeolite Y has been studied as a catalyst in the Heck reaction of iodobenzene with butyl acrylate in the presence of triethylamine base and dimethylformamide solvent. Trapping of soluble Pd with poly(4-vinylpyridine), hot filtration tests during the batchwise Heck reaction, and reaction tests of effluents from a fixed bed continuous reactor support the conclusion that leached Pd is the active phase in the Heck reaction for all of the catalysts tested. Two different paths of Pd leaching that depend on the chemical state of the Pd were elucidated in this study. Oxidative addition of aryl halide to reduced Pd caused leaching of samples containing metallic particles. However, for a zeolite Y sample containing unreduced cationic Pd, the presence of triethylamine base was required to leach Pd into solution. These two paths of Pd leaching are consistent with the generally accepted mechanism of the Heck reaction. 相似文献
90.
The use of electrolytically generated silver(II) as a coulometric titrant has been studied. Difficulties arising from the current efficiency for generation of silver (II) at a platinum or gold electrode and from the reduction of silver(II) by water, have been overcome. The precautions necessary for accurate titrations of oxalic acid, cerium(III), arsenic(III) and vanadium(IV) by amperometric or potentiometric methods are detailed. Manganese and chromium could not be determined directly. Substances which reduce nitric acid could be determined if care was taken. 相似文献