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981.
The main C(1) isomer of C(70)F(38) is shown by single-crystal X-ray analysis to contain four planar aromatic hexagons and four isolated C=C bonds, has two fluorines on the equator, and is related to C(2) C(70)F(38) by means of three 1,3-fluorine shifts. The C(1) and C(2) isomers thus parallel the T and C(3)/C(1) isomers of C(60)F(36) in containing three and four aromatic rings, respectively, and in the fluorine shift relationship.  相似文献   
982.
983.
The behaviour of glucosinolates and desulphoglucosinolates under fast atom bombardment conditions has been investigated. Relatively little fragmentation was noted in the mass spectra of these compounds. The positive ion fast atom bombardment mass spectra of glucosinolates exhibited abundant cationized and protonated molecula ions, thus complementing the previously reported electron impact and chemical ionization mass spectra of these compounds. Desulphoglucosinolates yield only the protonated molecular ion. Under negative ion conditions the spectra of glucosinolates were dominated by the molecular anion and this has been used as a means of analysing a crude plant extract containing a complex mixture of glucosinolates.  相似文献   
984.
The transition metal catalyzed ethylene polymerization in aqueous emulsion has been increasingly successful in the last couple of years. Water however adversely affects the polymerization process by (a) competing with ethylene for the binding site at the metal and (b) hydrolyzing the growing chain. Neutral salicylaldiminato and cationic diimine complexes of Ni and Pd with different substituent patterns are studied here by density functional theory to determine their propensity toward water complexation and hydrolysis of the growing chain. Experimental NMR studies have also been carried out on the protonolysis of the Ni(II)-based Grubbs catalyst. It is found that in general that (a) ethylene coordination is preferred over water coordination for both Ni and Pd catalysts and (b) hydrolysis of the metal alkyl bond is competitive to ethylene insertion.  相似文献   
985.
A mixture of the Z and E isomers of 2-(3-pentenyl)pyridine has been separated with baseline resolution by capillary electrophoresis. Using molecular modelling it was proposed that the smaller more rapidly migrating peak would be the Z isomer. This agreed with a 38:62 (Z/E) composition by nuclear magnetic resonance spectroscopy. The sample was also investigated by gas chromatography coupled to mass spectrometry.  相似文献   
986.
The solvent effect on the acidic dissociation of the protonated base tris(hydroxymethyl)aminomethane (Tris) has been studied in aqueous mixtures of several organic constituents with qualitatively similar results. The dissociation constant of protonated 2-amino-2-methyl-1,3-propanediol (Bis), the analog of Tris with two hydroxy groups, has now been determined in 50 mass % methanol by emf measurements of cells without liquid junction in the temperature range 10 to 40°C. The conventional treatment of the data indicated abnormally low values for the activity coefficient of BisHCl, but an alternate method of calculation with allowance for ion pairing provided no advantage. The pKa in the range from T=283.15 to 313.15 K is given by $$pK_a = 3755.63/T - 24.5127 + 3.56855 In T$$ with a standard deviation of 0.0006 at the seven temperatures. Thermodynamic quantities for the dissociation process and corresponding quantities for the transfer from water to 50 mass % methanol were derived. The implications of the results in terms of selective solute-solvent stabilization are discussed.  相似文献   
987.
The convergent synthesis of the C1-C15 AB-spiroacetal subunit of altohyrtin A/spongistatin 1 is described. This highly stereocontrolled synthesis relies on matched boron aldol reactions of chiral methyl ketones, under Ipc(2)BCl mediation, to establish the C5, C9 and C11 stereocentres, and formation of the desired thermodynamic spiroacetal under acidic conditions. The scalable synthetic sequence developed provided access to multi-gram quantities of , thus enabling the successful completion of the total synthesis of altohyrtin A/spongistatin 1, as reported in Part 4.  相似文献   
988.
Bacteriohopanepolyols (BHPs) fragment via characteristic pathways during atmospheric pressure chemical ionisation liquid chromatography/ion trap mass spectrometry (APCI-LC/MS(n)). Comparison of the MS(2) spectra of bacteriohopane-32,33,34,35-tetrol (BHT) and 2 beta-methylbacteriohopane-32,33,34,35-tetrol has confirmed the previously proposed ring-C cleavage occurring between C-9 and 11 and C-8 and 14. This fragmentation, diagnostic of all hopanoids, also occurs in BHPs containing an amino group (-NH(2)) at C-35 although the higher relative stability of the ion limits this fragmentation to a minor process after protonation of the basic nitrogen function. Studies of a number of cell cultures including a prochlorophyte (Prochlorothrix hollandica) and a cyanobacterium (Chlorogloeopsis LA) demonstrate the power of this technique to detect composite BHPs with a complex biological functionality at C-35. We also report the first observation of intact pentafunctionalised bacteriohopanepolyols using this method.  相似文献   
989.
Smith MR  Jee RD  Moffat AC  Rees DR  Broad NW 《The Analyst》2003,128(11):1312-1319
A novel optimisation algorithm is presented for full spectrum calibration models in near-infrared (NIR) spectroscopy. The algorithm is used to investigate the affect of removing continuous spectral regions on parameters critical to the validity of the model (e.g. explained variance, bias etc.) and ultimately identify and remove problem areas of the spectrum. As an example of its application, this paper shows how to optimise partial least squares regression (PLSR) calibration models for predicting moisture content within an intact pharmaceutical product and how problems due to changes in the nature of samples since setting up the original model may be eliminated. On application of two validated calibration models to a new set of samples unacceptable results were obtained for bias (-0.26 and -0.21% m/m moisture content) between the NIR predicted values and the true values (Karl Fischer analysis). The optimisation algorithm identified small regions of the spectrum, which if included in development of the models contributed significant bias to the final prediction. On removal of these problem regions the calibration models were found to be equally accurate and precise, but with the added advantage of robustness to a variable region of the sample spectrum (bias reduced to -0.05 and -0.09% m/m).  相似文献   
990.
Bashir S  Mutter R  Derrick PJ 《The Analyst》2003,128(12):1452-1457
Dihydroxybenzoic acid was modified to three analogues (M2, M4 and M6). The analogues exhibited specific properties that resulted in enhancement of analyte signal intensity with or without addition of iodine compared to the underivatized parent. Addition of iodine to M2, an ester of dihydroxybenzoic acid that had a terminal double bond in the alkyl chain, resulted in peak intensities comparable to the parent, indicating that iodine interaction across the double bond resulted in enhancement although the exact mechanism is not fully understood. No enhancement on addition of iodine was observed for M4, which had a long alkyl chain that contained no double bonds. The alkyl chain allowed micelle formation in solution, which in turn allowed more uniform analyte-to-matrix mixing. The final analogue combined the long alkyl chain of M4 with the double bond of M2 and exhibited either similar peak intensities to that of dihydroxybenzoic acid or better. Micelle formation in solution was examined using spectroscopy and in the solid by reflective microscopy. The standard deviation from spot to spot was considerably lower relative to dihydroxybenzoic acid (RSD 3.4%vs. 14.2%). Unlike dihydroxybenzoic acid, the novel matrix M6 was able to yield characteristic peaks for analytes such as ubiquitin.  相似文献   
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