全文获取类型
收费全文 | 32719篇 |
免费 | 208篇 |
国内免费 | 294篇 |
专业分类
化学 | 13071篇 |
晶体学 | 290篇 |
力学 | 1466篇 |
综合类 | 12篇 |
数学 | 9468篇 |
物理学 | 8914篇 |
出版年
2021年 | 52篇 |
2020年 | 67篇 |
2019年 | 63篇 |
2018年 | 1228篇 |
2017年 | 1470篇 |
2016年 | 768篇 |
2015年 | 628篇 |
2014年 | 536篇 |
2013年 | 812篇 |
2012年 | 3342篇 |
2011年 | 2602篇 |
2010年 | 1926篇 |
2009年 | 1618篇 |
2008年 | 793篇 |
2007年 | 813篇 |
2006年 | 832篇 |
2005年 | 4640篇 |
2004年 | 4078篇 |
2003年 | 2464篇 |
2002年 | 644篇 |
2001年 | 352篇 |
2000年 | 161篇 |
1999年 | 231篇 |
1998年 | 159篇 |
1997年 | 109篇 |
1996年 | 99篇 |
1995年 | 85篇 |
1994年 | 81篇 |
1993年 | 68篇 |
1992年 | 208篇 |
1991年 | 195篇 |
1990年 | 164篇 |
1989年 | 137篇 |
1988年 | 133篇 |
1987年 | 90篇 |
1986年 | 82篇 |
1985年 | 90篇 |
1984年 | 84篇 |
1983年 | 64篇 |
1982年 | 64篇 |
1981年 | 52篇 |
1980年 | 52篇 |
1979年 | 67篇 |
1978年 | 66篇 |
1977年 | 51篇 |
1976年 | 109篇 |
1975年 | 69篇 |
1974年 | 73篇 |
1973年 | 76篇 |
1972年 | 54篇 |
排序方式: 共有10000条查询结果,搜索用时 500 毫秒
991.
Karlsson NG Schulz BL Packer NH 《Journal of the American Society for Mass Spectrometry》2004,15(5):659-672
Neutral O-linked oligosaccharides released from the salivary mucin MUC5B were separated and detected by negative ion LC-MS and LC-MS(2). The resolution of the chromatography and the information obtained from collision induced dissociation of detected [M - H](-) ions were usually sufficient to identify the sequence of individual oligosaccharides, illustrated by the fact that 50 different oligosaccharides ranging from disaccharides to nonasaccharides could be assigned from the sample. Fragmentation was shown to yield mostly reducing end sequence fragments (Z(i) and Y(i)), enabling primary sequence assignment. Specific fragmentation pathways or patterns were also detected giving specific linkage information. The reducing end core (Gal/GlcNAcbeta1-3GalNAcol or Gal/GlcNAcbeta1-3(GlcNAcbeta1-6)GalNAcol) could be deduced from the pronounced glycosidic C-3 cleavage and A(i) type cleavages of the reducing end GalNAcol, together with the non reducing end fragment from the loss of a single substituted GalNAcol. Substitution patterns on GlcNAc residues were also found, indicative for C-4 substitution ((0,2)A(i) - H(2)O cleavage) and disubstitution of C-3 and C-4 (Z(i)/Z(i) cleavages). This kind of fragmentation can be used for assigning the mode of chain elongation (Galbeta1-3/4GlcNAcbeta1-) and identification of Lewis type antigens like Lewis a/x and Lewis b/y on O-linked oligosaccharides. In essence, negative ion LC-MS(2) was able to generate extensive data for understanding the overall glycosylation pattern of a sample, especially when only a limited amount of material is available. 相似文献
992.
Danielson JW Zuroski KE Twohy C Thompson RD Bell E McClure F 《Journal of AOAC International》2000,83(1):145-155
Sporicidal test results obtained from carriers inoculated with 4 types of defined Bacillus subtilis spore preparations were compared with the standard AOAC sporicidal test using soil extract nutrient broth (SENB) B. subtilis 19659 spores. Recoveries of spores inoculated on penicylinders from B. subtilis clean spores (washed and suspended in water) and B. subtilis 19659 spores inoculated from culture filtrates according to the AOAC method were compared. Spores were exposed to 6 concentrations (0.5-3.0% w/v) of glutaraldehyde in phosphate buffer (pH 7.5) for 10 h. Concentrations were established by titrimetry and liquid chromatography. Recoveries of surviving spores were determined for 3 types of clean B. subtilis var. niger preparations, one clean B. subtilis 19659 preparation, and the SENB B. subtilis 19659 filtrates. Spore carriers, inoculated by the standard AOAC protocol, resulted in as much as a 2-log number difference in runs 1-12, but not more than 0.5 log number for each clean spore preparation. The SENB spores varied most in resistance to glutaraldehyde, with no growth in recovery media from 3 different batches of 1, 1.5, and 2% glutaraldehyde. Separate batches of SENB preparations of B. subtilis 19659 were resistant and destroyed by 1.0% glutaraldehyde, with 3.98 and 6.0 log numbers of spores on penicylinders, respectively. Clean spore preparations of B. subtilis 19659 on porcelain penicylinders were more resistant to glutaraldehyde than were SENB spores. Nutrient agar/Mg/Ca and nutrient agar/Mg spore preparations of B. subtilis var. niger showed the most uniform resistance to glutaraldehyde. Spores with calcium added showed increased resistance to glutaraldehyde. B. subtilis 19659 spores from the Columbia broth spore preparation were the most resistant and were recovered after exposure to 3.0% glutaraldehyde. 相似文献
993.
Investigation of sulfur release in ETV-ICP-AES and its application for the determination of sulfates 总被引:3,自引:0,他引:3
Antje Mroczek Gerhard Werner R. Wennrich Werner Schr?n 《Fresenius' Journal of Analytical Chemistry》1998,361(1):34-42
Electrothermal vaporization inductively coupled plasma atomic emission spectrometry was applied to the determination of sulfur
species in aqueous solutions. The sensitivity for sulfur as sulfate was found to be depending on the cations in the sample.
For understanding this phenomenon the thermal behavior of sulfuric acid, ammonium sulfate and the sulfates of sodium, zinc,
magnesium and silver was studied. There were significant differences in the thermal release of sulfur from these sulfates.
To explain these phenomena different reaction mechanisms were calculated using thermodynamic data. Pd(NO3)2 and Ge in KOH were successfully applied as modifiers for the stabilization of the sulfates during the thermal pre-treatment
step and to establish a uniform thermal behavior of different sulfates. The stabilization of sulfur using Ge and Pd as modifiers
is based on the reduction of the sulfates in presence of carbon, resulting in the formation of GeS and PdS, respectively.
This explanation has been supported by comparing the experimental results with thermodynamic calculations considering different
reactions for the thermal decomposition of the sulfates. Applying Ge (in KOH) as modifier the absolute detection limit was
300 pg sulfur (e.g. LOD 30 ng mL–1). The significant influence of phosphates on the determination of sulfur could be essentially reduced by Pd as modifier.
Received: 11 November 1997 / Revised: 14 January 1998 / Accepted: 18 January 1998 相似文献
994.
A case study is presented for the establishment of traceability for ammonium nitrogen determination in wastewater in a routine laboratory in order to fulfil the requirements of ISO/IEC standard 17025. The necessary relevant information was obtained from the method validation data, the quality control data and equipment calibration certificates. The method of measurement is described together with the measurement equation, selected traceable reference standards and the associated measurement uncertainty. The major sources of uncertainty of the result of measurement were identified and the combined uncertainty was calculated. Identification of the main uncertainty sources represents the basis for target operations for reducing the measurement uncertainty of this determination. 相似文献
995.
?zdemir ümmühan Karacan Nurcan ?entürk Ozan Sanlι Sert Sema U?ur Fadime 《Transition Metal Chemistry》2003,28(4):443-446
Five new complexes, [M(CO)5(apmsh)] [M = Cr; (1), Mo; (2), W; (3)], [Re(CO)4Br(apmsh)] (4) and [Mn(CO)3(apmsh)] (5) have been synthesized by the photochemical reaction of metal carbonyls [M(CO)6] (M = Cr, Mo and W), [Re(CO)5Br], and [Mn(CO)3Cp] with 2-hydroxyacetophenone methanesulfonylhydrazone (apmsh). The complexes have been characterized by elemental analysis, mass spectrometry, f.t.-i.r. and 1H spectroscopy. Spectroscopic studies show that apmsh behaves as a monodentate ligand coordinating via the imine N donor atom in [M(CO)5(apmsh)] (1–4) and as a tridentate ligand in (5). 相似文献
996.
A method is developed whereby spherical and other particles can be derivatised with electroactive species on their surface and then immobilised on the surface of an electrode. The chronoamperometric and voltammetric responses in the limit of reversible electrode kinetics are modelled using a theory of charge movement over the surface of the spheres where this movement is considered as a diffusional process. The model is extended to include different distributions of sphere radii and to model the scenario of truncated spheres resting on the electrode surface. It is found that a good estimation of the truncation angle can be found by fitting the experimental data with theoretical predictions. 相似文献
997.
Liu JM Hu SR He XM Li XL Zhan FP Zeng LQ Li LD Zhu GH Huang XM 《Analytical and bioanalytical chemistry》2005,382(7):1507-1512
Silicon dioxide nano-particles, diameter 50 nm, containing morin (morin–SiO2) have been synthesized by the sol–gel method. They emit strong and stable room-temperature phosphorescence (SS-RTP) on filter paper as substrate, and bismuth can quench the intensity of the SS-RTP. On this basis a new morin–SiO2 solid-substrate room-temperature phosphorescence-quenching method has been established for determination of traces of bismuth. Reduction of phosphorescence intensity (Ip) is directly proportional to the concentration of bismuth in the working range 0.16–14.4 ag spot–1 (sample volume 0.40 L spot–1, corresponding to the concentration range 0.40–36.0 fg mL–1). The regression equation of the working curve is Ip=14.86+5.279×[Bi3+] (ag spot–1) (n=6, r=0.9982). The detection limit of this method is 0.026 ag spot–1 (corresponding to a concentration of 6.5×10–17 g mL–1).This sensitive, reproducible and accurate method has been used for successful analysis of real samples. 相似文献
998.
We present a detailed study of the photophysical properties of a tetraphenoxy-substituted perylene bisimide derivative. The probe molecules were immobilized in a Shpol'skii matrix of hexadecane and investigated by single-molecule spectroscopy at cryogenic temperatures. By using single-molecule spectroscopic techniques we reveal the triplet substate kinetics and the fluorescence quantum yield, and we provide an estimate for the S1-S0 transition dipole moment. 相似文献
999.
Chakravarthi Simhadri Liting Bi Mathieu L. Lepage Mahdi Takaffoli Zhipeng Pei Stefania F. Musolino Abbas S. Milani Gino A. DiLabio Jeremy E. Wulff 《Chemical science》2021,12(11):4147
Motivated by a desire to develop flexible covalent adhesives that afford some of the same malleability in the adhesive layer as traditional polymer-based adhesives, we designed and synthesized two flexible, highly fluorinated bis-diazirines. Both molecules are shown to function as effective crosslinkers for polymer materials, and to act as strong adhesives when painted between two polymer objects of low surface energy, prior to thermal activation. Data obtained from lap-shear experiments suggests that greater molecular flexibility is correlated with improved mechanical compliance in the adhesive layer.Flexible, highly fluorinated covalent adhesives are synthesized, and are shown to afford comparable C–H insertion efficiency and adhesion strength relative to a rigid analogue, while providing improved mechanical compliance in the adhesion layer. 相似文献
1000.
A flow injection–capillary electrophoresis system with contactless conductivity detection and hydrostatic-pressure-generated flow was used for the fast and sensitive speciation of Se(IV) and Se(VI). The sample throughput was 25 samples per hour using a background electrolyte solution containing 8.75 mM l-histidine (His) adjusted to pH 4.00 with acetic acid. The repeatability of peak areas (n=8) was better than 1.41% and the limits of detection were 190 g L–1 and 7.5 g L–1 for Se(IV) and Se(VI), respectively. The interference from carbonate, typically present in water samples, was eliminated by using a low-pH electrolyte in which carbonate is uncharged and migrates at the EOF front. The method was applied to the analysis of Se(IV) and Se(VI) in soil samples that were spiked with both selenium species and the results for recovery of both selenium species were in good agreement with their introduced concentrations. 相似文献