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121.
Although the feasibility of affinity ultrafiltration was demonstrated more than 20 years ago, commercial applications have not developed due to the high cost and practical limitations of the large macroligands needed for highly selective separations. The objective of this study was to examine the use of small charged affinity ligands for protein purification by exploiting electrostatic interactions between the charged complex and an electrically-charged membrane. Experiments were performed using bovine serum albumin and ovalbumin with Cibacron Blue as the affinity ligand. Negatively charged versions of a composite regenerated cellulose membrane were generated by covalent attachment of a sulfonic acid functionality. Binding experiments were used to identify appropriate conditions for protein separations. The selectivity for the separation of BSA and ovalbumin was a function of the solution conditions, Cibacron Blue concentration, and membrane charge, with the addition of Cibacron Blue causing a 30-fold increase in selectivity. A diafiltration process was performed at the optimal conditions, giving a BSA product with a purification factor of more than 90-fold and a yield greater than 90%. These results clearly demonstrate the potential of using a small charged affinity ligand for high resolution protein separations.  相似文献   
122.
The performance of single-drop microextraction (SDME), coupled with gas chromatography/mass spectrometry, was assessed for the determination of tributyltin compounds in water and solid samples. Experimental parameters impacting the performance of SDME, such as microextraction solvent and sampling and stirring time, were investigated. Analytical results obtained by SDME were compared with those generated by conventional solid phase microextraction (SPME) and liquid-liquid extraction (LLE) for the determination of TBT in PACS-2 sediment certified reference material (CRM).  相似文献   
123.
We have developed a high-throughput purification system to purify combinatorial libraries at a 50-100-mg scale with a throughput of 250 samples/instrument/day. We applied an accelerated retention window method to shorten the purification time and targeted one fraction per injection to simplify data tracking, lower QC workload, and simplify the postpurification processing. First, we determined the accurate retention time and peak height for all compounds using an eight-channel parallel LC/UV/MS system, and calculated the specific preparative HPLC conditions for individual compounds. The preparative HPLC conditions include the compound-specific gradient segment for individual compounds with a fixed gradient slope and the compound-specific UV or ELSD threshold for triggering a fraction collection device. A unique solvent composition or solvent strength was programmed for each compound in the preparative HPLC in order to elute all compounds at the same target time. Considering the possible deviation of the predicted retention time, a 1-min window around the target time was set to collect peaks above a threshold based on UV or ELSD detection. Dual column preparative instruments were used to maximize throughput. We have purified more than 500 000 druglike compounds using this system in the past 3 years. We report various components of this high-throughput purification system and some of our purification results.  相似文献   
124.
The formation of the compound RSnX(acac)2 (acac = 2,4-pentanedionato) by reaction of bis(2,4-pentanedionato)tin(II) on a halide RX with R = CH3, C2H5, C4H9, C6H5, CH2I, (C6H5)3SnCH2, (C2H5)3SnCH2 and X = I, Br has been studied by polarography. At 25°C, it is in fact an equilibrium whose constant has been measured. The intermediate formation of the ion-pair [RSn(acac)2+X?] has allowed us to explain the experimental results.  相似文献   
125.
Two homoleptic Re(I) complexes of ortho and para-carborane isocyanide ligands were prepared as the first examples of a new class of metal-based BNCT and BNCS agents. The target compounds were prepared in low yield through the reaction of [Re2(O2CPh)4Cl2] and [Re2(OAc)4Cl2] with 3-isocyano-1,2-dicarba-closo-dodecaborane and a para-carborane azetidine derivative respectively. The desired product from the latter reaction was characterized crystallographically and is only the second reported molecular structure of a homoleptic Re(I) isonitrile complex.  相似文献   
126.
The protocol and various matrices were examined for quantification of biomolecules in both the low ca. 1200 amu and mid mass 6000-12000 amu ranges using an internal standard. Comparative studies of different matrices of MALDI quantitative analysis showed that the best accuracy and standard curve linearity were obtained for two matrices: (a) 2,5-dihydroxybenzoic acid (DHB) combined with a comatrix of fucose and 5-methoxysalicylic acid (MSA) and (b) ferulic acid/fucose. In the low mass range, the quantitative limit was in the 30 fmol range and in the mid mass range the quantitative limit was in the 250 fmol range. Linear response was observed over 2-3 decades of analyte concentration. The relative error of the standard curve slope was 1.3-1.8% with correlation coefficients of 0.996-0.998.The main problem for quantitative measurement was suppression of the signal of the less concentrated component (analyte or internal standard) by the more concentrated component. The effect was identified with saturation of the matrix by the analyte. The threshold of matrix saturation was found to be in the range of 1/(3000-5000) analyte/matrix molar ratio. To avoid matrix saturation the (analyte+internal standard) to matrix molar ratio should be below this threshold. Thus the internal standard concentration should be as low as possible.DHB/MSA/fucose and ferulic acid/fucose matrices demonstrated good accuracy and linearity for standard curves even when the internal standard had chemical properties different from the analyte. However, use of an internal standard with different chemical properties requires highly stable instrumental parameters as well as constant (analyte+internal standard)/matrix molar ratio for all samples.  相似文献   
127.
128.
A combination of two techniques, PIXE (particle induced x-ray emission) and RBS (Rutherford backscattering), is proposed as an analytical tool to measure uranium and thorium in environmental and biological samples and in the study of the micro-distribution of uranium is low Z matrices such as biological tissue.Work supported by U.S. Department of Energy Contracts DE-AC02-76CH-00116 (MC, KWJ) and DE-AC02-76EV-00119 (NPS, MEW). One of us (ASP) is grateful to FINEP (Financiadora de Estudos e Projetos) and CNPq (Conselho Nacional de Desenvolvimento Cientifico e Technológico).  相似文献   
129.
Two hydrated uranyl arsenates, Cs2(UO2)[(UO2)(AsO4)]4(H2O)2 (CsUAs) and Rb2(UO2)[(UO2)(AsO4)]4(H2O)4.5 (RbUAs), were synthesized by hydrothermal methods. Intensity data were collected at room temperature using MoKα radiation and a CCD-based area detector. The crystal structure of RbUAs was solved by direct methods, whereas the structure model of the phosphate Cs2(UO2)[(UO2)(PO4)]4(H2O)2 was used for CsUAs; both were refined by full-matrix least-squares techniques on the basis of F2 to agreement indices (CsUAs, RbUAs) wR2=0.061,0.041, for all data, and R1=0.032,0.021, calculated for 5098, 4991 unique observed reflections (|Fo|>4σF), respectively. The compound CsUAs is orthorhombic, space group Cmc21, Z=4, a=15.157(2), b=14.079(2), c=13.439(2) Å, V=2867.9(1) Å3. RbUAs is monoclinic, space group C2/m, Z=4, a=13.4619(4), b=15.8463(5), c=14.0068(4) Å, β=92.311(1)°, V=2985.52(2) Å3. The structures consist of sheets of arsenate tetrahedra and uranyl pentagonal bipyramids, with composition [(UO2)(AsO4)], that are topologically identical to the uranyl silicate sheets in uranophane-beta. These sheets are connected by a uranyl pentagonal bipyramid in the interlayer that shares corners with two arsenate tetrahedra on each of two adjacent sheets and whose fifth equatorial vertex is an H2O group, resulting in an open framework with alkali metal cations in the larger cavities of the structures. CsUAs is isostructural with its phosphate analogue, and has two Cs atoms and a H2O group in its structural cavities. RbUAs is not isostructural with its phosphate analogue, although it has a homeotypic framework. Its structural cavities are occupied by three Rb atoms and four H2O groups; one Rb position and three of the interstitial H2O groups are half-occupied. The partial occupancies of these positions probably result from the accommodation of the larger As atoms (relative to P) in the framework and resultant larger cavities.  相似文献   
130.
Pyrolysis of homoadamant-3-ene (5), generated from 1-adamantylcarbene (7), leads to the same three olefins (2, 3, and 4) that are produced from pyrolysis of 3-homoadamantyl acetate (1).  相似文献   
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