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101.
Fujiwara Y Domingo V Seiple IB Gianatassio R Del Bel M Baran PS 《Journal of the American Chemical Society》2011,133(10):3292-3295
A direct functionalization of a variety of quinones with several boronic acids has been developed. This scalable reaction proceeds readily at room temperature in an open flask using inexpensive reagents: catalytic silver(I) nitrate in the presence of a persulfate co-oxidant. The scope with respect to quinones is broad, with a variety of alkyl- and arylboronic acids undergoing efficient cross-coupling. The mechanism is presumed to proceed through a nucleophilic radical addition to the quinone with in situ reoxidation of the resulting dihydroquinone. This method has been applied to complex substrates, including a steroid derivative and a farnesyl natural product. 相似文献
102.
Patel B Carlisle J Bottle SE Hanson GR Kariuki BM Male L McMurtrie JC Spencer N Grainger RS 《Organic & biomolecular chemistry》2011,9(7):2336-2344
Acyclic bissulfonylnitroxides have never been isolated, and degrade through fragmentation. In an approach to stabilising a bissulfonylnitroxide radical, the cyclic, peri-substituted N,N-bissulfonylhydroxylamine, 2-hydroxynaphtho[1,8-de][1,3,2]dithiazine 1,1,3,3-tetraoxide (1), has been prepared by formal nitrogen insertion into the sulfur-sulfur bond of a sulfinylsulfone, naphtho[1,8-cd][1,2]dithiole 1,1,2-trioxide. The heterocyclic ring of 1 is shown to adopt a sofa conformation by X-ray crystallography, with a pseudo-axial hydroxyl group. N,N-Bissulfonylhydroxylamine 1 displays high thermal, photochemical and hydrolytic stability compared to acyclic systems. EPR analysis reveals formation of the corresponding bissulfonylnitroxide 2 upon oxidation of 1 with the Ce(IV) salts CAN and CTAN. Although 2 does not undergo fragmentation, it cannot be isolated, since hydrogen atom abstraction to reform 1 occurs in situ. The stability and reactivity of 1 and 2 are compared with the known cyclic benzo-fused N,N-bissulfonylhydroxylamine, N-hydroxy-O-benzenedisulfonimide (6), for which the X-ray data, and EPR of the corresponding nitroxide 10, are also reported for the first time. 相似文献
103.
Jeffs L Arquier D Kariuki B Bethell D Page PC Hutchings GJ 《Organic & biomolecular chemistry》2011,9(4):1079-1084
By synthesising S-2-phenyl-N-(4-nitrophenyl)aziridine from S-phenylglycinol, it has been demonstrated that the aziridination of styrene by [N-(4-nitrobenzenesulfonyl)imino]phenyliodinane (nosyliminophenyliodinane, PhINNs) in the presence of S,S-2,2'-isopropylidene-bis(4-phenyl-2-oxazoline), catalysed by copper(II) triflate in CH(3)CN solution or heterogeneously by CuHY, has predominantly an R-configuration. The enantioselectivity of the aziridination of styrene by [N-arenesulfonylimino]-phenyliodinanes catalysed by copper-exchanged zeolite Y (CuHY), in conjunction with a chiral bis-oxazoline ligand, has been re-examined. In the case of PhINNs, it is shown that the product mixture of enantiomeric aziridines, on treatment with hexane, gives rise to a solid phase of low enantiomeric excess (ee) and a solution phase of high ee. Separation of the solid phase and recrystallisation afforded a true racemate (racemic compound), which has been confirmed by X-ray crystallography. The aziridine obtained from the solution phase could be recrystallised to produce the pure enantiomer originally in excess. A consequence of the new findings is that previous reports on the enantioselectivity of copper-catalysed aziridination, both in heterogeneous and homogeneous conditions, should be regarded with caution if the analytical procedure involved HPLC with injection of the enantiomeric mixture in a hexane-rich solvent. Such a method has been used in previous work from this laboratory, but has also been used elsewhere, following the procedure developed by Evans and co-workers when the (homogeneous) copper-catalysed aziridination by PhINTs was first discovered. Evidently, the change of substituent in the benzenesulfonyl group reduces the solubility in hexane, affording a solution phase of enhanced ee. 相似文献
104.
Newman PD Cavell KJ Hallett AJ Kariuki BM 《Dalton transactions (Cambridge, England : 2003)》2011,40(35):8807-8813
A tridentate N^C^N ligand, 1, containing a bicyclic central NHC ring and two flanking pyridyl groups has been coordinated to Rh(I) and Ir(I) to give complexes of the type [M(κ(3)-1)(1,5-COD)]PF(6) (2 M = Rh; 3 M = Ir). In contrast to our earlier study with this ligand, the complexes have been shown to approximate to a trigonal bipyramidal geometry in the solid state and exist as an isomeric mixture in solution as determined by (1)H and (13)C NMR spectroscopy. Electrochemical studies revealed that both complexes undergo a 1-electron oxidation with the potential of the Rh complex 0.1 V less than that of the Ir complex in CH(2)Cl(2). Preliminary DFT studies confirm the lowest energy conformations as those seen in the solid state and show the location and energy of the HOMOs to be identical in 2 and 3. Partial charge analysis shows a greater positive charge on the Ir in 3 compared to the Rh in 2. Some preliminary studies of hydrogenation reactivity have shown the complexes to be efficient for both transfer and direct hydrogenation of prochiral ketones and alkenes at moderate temperatures but without any discernible enantioselectivity. 相似文献
105.
Dreyfuss JM Jacobs C Gindin Y Benson G Staples GO Zaia J 《Analytical and bioanalytical chemistry》2011,399(2):727-735
Hydrophilic interaction chromatography (HILIC) liquid chromatography/mass spectrometry (LC/MS) is appropriate for all native
and reductively aminated glycan classes. HILIC carries the advantage that retention times vary predictably according to oligosaccharide
composition. Chromatographic conditions are compatible with sensitive and reproducible glycomics analysis of large numbers
of samples. The data are extremely useful for quantitative profiling of glycans expressed in biological tissues. With these
analytical developments, the rate-limiting factor for widespread use of HILIC LC/MS in glycomics is the analysis of the data.
In order to eliminate this problem, a Java-based open source software tool, Manatee, was developed for targeted analysis of
HILIC LC/MS glycan datasets. This tool uses user-defined lists of compositions that specify the glycan chemical space in a
given biological context. The program accepts high-resolution LC/MS data using the public mzXML format and is capable of processing
a large data file in a few minutes on a standard desktop computer. The program allows mining of HILIC LC/MS data with an output
compatible with multivariate statistical analysis. It is envisaged that the Manatee tool will complement more computationally
intensive LC/MS processing tools based on deconvolution and deisotoping of LC/MS data. The capabilities of the tool were demonstrated
using a set of HILIC LC/MS data on organ-specific heparan sulfates. 相似文献
106.
Lee PH Mo J Kang D Eom D Park C Lee CH Jung YM Hwang H 《The Journal of organic chemistry》2011,76(1):312-315
Pd-catalyzed cross-coupling reactions of aryl iodides containing not only an electron-donating group but also an electron-withdrawing group on the aryl ring with organoindium reagents generated in situ from indium and ethyl 4-bromo-2-alkynoates produced selectively ethyl 2-aryl-2,3-alkadienoates in good yield. 相似文献
107.
A sweeping structural revision of the sarcodonin natural product family (published structures 1a-13a) is proposed after extensive studies aimed at their chemical synthesis. Key features of revised structure 1b include replacement of the N,N-dioxide moiety with an oxime, ring-opening of the central diketopiperazine, and transposition of the terphenyl wing from the 1β-2β position of 1a to the 2β-3β position of 1b. This structure revision arose from the serendipitous synthesis of a benzodioxane aminal (44) whose structure was unambiguously determined by X-ray crystallography and whose spectral properties bore considerable resemblance to the published data for the sarcodonins. A versatile new method for O-arylation of hydroxamic acids is also reported herein, as well as a manganese(III)-mediated α-oxidation of hydroxamic acids to aminals. 相似文献
108.
Pd-catalyzed multifold (2-, 3-, and 4-fold) carbon-sulfur cross-coupling reaction of indium tri(organothiolates) with polybromonated aromatic and heteroaromatic compounds was developed in a one-pot procedure. Both 2,5-dibromopyridine and 2,6-dibromopyridine reacted with indium tri(organothiolates) (0.68 equiv) in the presence of 4 mol % of Pd(OAc)(2), 4.2 mol % of Xantphos, and 1 equiv of diisopropylethylamine (DIPEA), producing disulfides in good to excellent yields. These results indicate that indium tri(organothiolates) transfer all three alkyl- or arylthio groups attached to indium metal to electrophilic coupling partners. Indium tri(organothiolates) derived from alkyl thiol having a low boiling point, such as n-propyl, isopropyl, and tert-butyl thiol, acted as good nucleophilic coupling partners. In addition, indium tri(arylthiolates) derived from aryl thiols possessing an electron-withdrawing or -donating group on the aromatic ring participated well in the Pd-catalyzed multifold carbon-sulfur cross-coupling reaction. 4,4'-Dibromo-1,1'-biphenyl, 9,10-dibromoanthracene, 2,4-dibromoanisole, 2,7-dibromo-9,9-dimethylfluorene, 3,4-dibromothiophene, 2,3-dibromothiophene, 2,2'-bithiophene, 1,3,5-tribromobenzene, and 1,2,4,5-tetrabromobenzene were converted smoothly to the corresponding di-, tri-, and tetrasulfides. 相似文献
109.
Short R Carta M Bezzu CG Fritsch D Kariuki BM McKeown NB 《Chemical communications (Cambridge, England)》2011,47(24):6822-6824
Microporous polymers derived from the 1,2- and 1,4-regioisomers of di(3',4'-dihydroxyphenyl)tetraphenylbenzene have very different properties with the former being composed predominantly of cyclic oligomers whereas the latter is of high molar mass suitable for the formation of robust solvent-cast films of high gas permeability. 相似文献
110.
We present an experimental study of a supersonic nozzle with supersonic iodine injection. This nozzle simulates Chemical Oxygen
Iodine Laser (COIL) flow conditions with non-reacting, cold flows. During the experiments, we used a laser sheet near 565 nm
to excite fluorescence in iodine, which we imaged with an intensified and gated CCD camera. We captured streamwise and semi-spanwise
(oblique-view) images, with fluorescence revealing the material injected into the flow. We identified the flow structures
in the images, and produced quantitative characterizations of the flow morphology and of the mixing between the primary and
injected flow. We considered four injection scenarios. The first scenario includes a single injector positioned downstream
of the nozzle throat. To enhance the mixing between the flows, trip jets are placed in the wake of the single jet. The sonic
trip jets, significantly smaller than the primary supersonic iodine jet, are intended to destabilize the counter-rotating
vortex pair (CRVP) of the primary jet. We compare three different trip jet configurations for their ability to enhance mixing
between the oxygen and iodine flows. 相似文献