全文获取类型
收费全文 | 24725篇 |
免费 | 1130篇 |
国内免费 | 4713篇 |
专业分类
化学 | 28234篇 |
晶体学 | 299篇 |
力学 | 52篇 |
综合类 | 231篇 |
数学 | 17篇 |
物理学 | 1735篇 |
出版年
2024年 | 29篇 |
2023年 | 235篇 |
2022年 | 604篇 |
2021年 | 731篇 |
2020年 | 732篇 |
2019年 | 749篇 |
2018年 | 641篇 |
2017年 | 793篇 |
2016年 | 940篇 |
2015年 | 880篇 |
2014年 | 1024篇 |
2013年 | 2251篇 |
2012年 | 1768篇 |
2011年 | 1384篇 |
2010年 | 1207篇 |
2009年 | 1438篇 |
2008年 | 1516篇 |
2007年 | 1666篇 |
2006年 | 1575篇 |
2005年 | 1469篇 |
2004年 | 1336篇 |
2003年 | 1068篇 |
2002年 | 929篇 |
2001年 | 679篇 |
2000年 | 668篇 |
1999年 | 542篇 |
1998年 | 439篇 |
1997年 | 466篇 |
1996年 | 422篇 |
1995年 | 387篇 |
1994年 | 335篇 |
1993年 | 287篇 |
1992年 | 279篇 |
1991年 | 203篇 |
1990年 | 158篇 |
1989年 | 172篇 |
1988年 | 122篇 |
1987年 | 84篇 |
1986年 | 59篇 |
1985年 | 48篇 |
1984年 | 56篇 |
1983年 | 29篇 |
1982年 | 42篇 |
1981年 | 28篇 |
1980年 | 22篇 |
1979年 | 20篇 |
1978年 | 22篇 |
1977年 | 5篇 |
1973年 | 5篇 |
1968年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
961.
962.
Zi-Qiang GuMin Li 《Tetrahedron letters》2003,44(15):3203-3205
A concise, multi-gram scale method for producing the bioactive and enantiomerically pure epimers, (2S,4R)- and (2S,4S)-glutamic acids, in a single synthetic scheme is described. 相似文献
963.
Iron interference in the spectrophotometric catalytic determination of molybdenum based on the iodide-hydrogen peroxide reaction can be corrected by using sulphosalicylic acid as masking and color-forming reagent. The catalytic influence of iron ions is circumvented to the extent of about 90% and correction of any remaining iron ions is possible by monitoring the colored iron(III)-salicylate complex at 490 nm. In this way, iron is also determined. With the proposed system, molybdenum can be determined in plant and food digests within the 0–100 μg Mo 1−1 range in the presence of up to 25 mg Fe 1−1, at a sampling rate of about 50 determinations h−1. The relative standard deviation of 10 consecutive measurements was estimated as < 2%. Results for samples were comparable with those obtained by graphite furnace atomic absorption spectrometry. In addition, recoveries within the range 94–100% were calculated. 相似文献
964.
The effect of pH on the formation and stability of phospholipid coatings in fused-silica capillaries in electrophoresis was investigated. A liposome solution consisting of 3 mM of 80:20 mol% phosphatidylcholine/phosphatidylserine (PC/PS) in N-(2-hydroxyethyl)piperazine-N'-(2-ethanesulfonic acid) (HEPES) buffer was used as coating material. The coating was prepared by a method described earlier and five steroids were used as neutral model analytes. First, the effect of pH of the coating solution on the formation and stability of phospholipid coatings was studied at pH 6.5-8.5. The pH of the background electrolyte (BGE) solution (HEPES) was either kept constant at pH 7.4 or made similar to the pH of the liposome coating solution. Results showed that attachment of the coating on the fused-silica wall mostly depends on the protonation of amines of the phospholipids and HEPES. The ability of the phospholipid coating to withstand changes in pH was then investigated by coating at pH 7.5 and separating steroids with acetic acid, 3-(cyclohexylamino)-1-propanesulfonic acid (CAPS), HEPES, or glycine BGE, adjusted to pH between 4.5 and 10.8. The results showed that with use of BGE solution at pH 10.8, the separation of steroids was not successful and the electroosmotic flow was high because of leakage of the phospholipid coating during preconditioning of the capillary with BGE solution. There was no phospholipid leakage with a BGE solution of pH 4.5, indicating that the protonated form of the functional groups of PS and HEPES participating in the attachment of the phospholipid coating to the capillary play an essential role in the success of the coating. 相似文献
965.
Marine de Person Aude Sevestre P. Chaimbault Laurent Perrot Francis Duchiron Claire Elfakir 《Analytica chimica acta》2004,520(1-2):149-158
This paper reports the use of an on-line LC–ESI–MS/MS method for the identification and quantification of di- and tripeptides in champagne wine without laborious sample pretreatment. The identification of these compounds, in their underivatised form, is based on identical retention times and ESI–MS spectra to those of reference standards. The presence of nine dipeptides (Arg–Ile, Ile–Arg, Ile–Val, Lys–Phe, Lys–Tyr, Phe–Lys, Tyr–Gln, Tyr–Lys, Val–Ile) and the absence of two tripeptides (Phe–Arg–Arg and Lys–Met–Asn) have been evidenced in the matrix. Calibration curves for each analyte were established using Phe–Arg as internal standard. The calibration curves were linear in the concentration range 0.1–10 mg L−1 with a determination coefficient, r2, better than 0.992. The accuracy for the calibration standard was estimated at between 92 and 102%. This method allows high recovery and satisfies the necessary requirements with respect to accuracy, repeatability and sensitivity. The first application of this analytical method to the measurement of di- and tri-peptides in different vintages of champagne wine is reported. Compositional changes in the peptides occurred depending on the vintage. 相似文献
966.
The interaction of Amido black 10B (AB) with DNA in basic medium was studied in the presence of cetyltrimethylammonium bromide (CTMAB) based on the measurements of resonance light scattering (RLS), UV–vis, CD spectra, and RLS imaging. The interaction has been proved to give a ternary complex of CTMAB–DNA–AB in Britton–Robinson buffer of pH 11.55, which exhibits strong negative Cotton effect at 233.3 nm and 642.8 nm, and strong RLS signals characterized at 469 nm. Experiments showed that the enhanced RLS intensities (ΔIRLS) against the mixture of AB and CTMAB are proportional to the concentration of fish sperm DNA (fsDNA) and calf thymus DNA (ctDNA), respectively over the range of 0.03–1.0 and 0.05–1.5 μg ml−1, with the limits of determination (3σ) of 7.3 ng ml−1 for fsDNA and 7.0 ng ml−1 for ctDNA. 相似文献
967.
R. A. Manzhos B. I. Podlovchenko Yu. M. Maksimov 《Russian Journal of Electrochemistry》2006,42(6):658-664
Transients of the open-circuit potential, which are observed when formic acid is interacting wit adsorbed oxygen (Oads) preliminarily accumulated on polycrystalline “smooth” platinum (pcPt), are measure in an aqueous solution of sulfuric acid. It is shown that, as with platinized platinum (Pt/Pt), at large coverage by adsorbed oxygen (θO = 1?0.8), adsorbed oxygen interacts directly with molecules of formic acid from solution. In the region of medium coverages (θO = 0.8?0.2), on the other hand, a mechanism of “conjugated reactions” is realized. It is established that, in the case of pcPt, the direct interaction of Oads with molecules of HCOOH from solution proceeds slower by nearly three times and the interaction via the mechanism of “conjugated reactions,” faster by about three times, as compared with Pt/Pt. 相似文献
968.
A new melamine based polymeric sequestering resin was prepared for preconcentration and separation of hexavalent chromium from water, and its sequestering action was investigated. The water-insoluble, cross-linked sequestering resin was formed by reaction with bromosuccinic acid and cross-linking of melamine. The active sequestering group on the resin is NH-(Succinic acid) or salt thereof. The resulting chelating resin was characterized by infrared spectra. The newly prepared resin quantitatively retained Cr(VI) at pH 2.0-4.0 when the flow rate was maintained between 1 and 5 ml min−1. The retained Cr(VI) was instantaneously eluted with 25 ml of 0.1 M NaOH. The chromium species were determined by a flame atomic absorption spectrometer. The limits of detection for Cr(VI) and Cr(III) were found to be 5.3 and 4.2 μg l−1, respectively. The precision and accuracy of the proposed procedure was checked by the use synthetic and reference steel samples. The established preconcentration method was successfully applied to the determination and selective separation of Cr(VI) in electroplating industry wastewater. Total concentrations determined by the spectrophotometric method (110.3±0.6 g l−1 Cr(VI) and 1.2±0.3 g l−1 Cr(III)) are compared with those found by FAAS and the obtained results (110.4±1.8 g l−1 Cr(VI) and 1.4±0.5 g l−1 Cr(III)) show good agreement. 相似文献
969.
Ab initio UMP2 and UQCISD(T) calculations, with 6-311G** basis sets, were performed for the titled reactions. The results show that
the reactions have two product channels: NH2+ HNCO?NH3+NCO (1) and NH2+HNCO?N2H3+CO (2), where reaction (1) is a hydrogen abstraction reaction via an H-bonded complex (HBC), lowering the energy by 32.48
kJ/mol relative to reactants. The calculated QCISD(T)//MP2(full) energy barrier is 29.04 kJ/mol, which is in excellent accordance
with the experimental value of 29.09 kJ/mol. In the range of reaction temperature 2300–2700 K, transition theory rate constant
for reaction (1) is 1.68×1011–3.29×1011 mL·mol-1·s-1, which is close to the experimental one of 5.0×1011mL·mol-1·s-1or less. However, reaction (2) is a stepwise reaction proceeding via two orientation modes,cis andtrans, and the energy barriers for the rate-control step at our best calculations are 92.79 kJ/mol (forcis-mode) and 147.43 kJ/mol (fortrans-mode), respectively, which is much higher than reaction (1). So reaction (1) is the main channel for the titled reaction. 相似文献
970.
A PVC membrane electrode for lead ions based on 5,5′-dithiobis-(2-nitrobenzoic acid) as membrane carrier was prepared. The electrode exhibits a Nernstian response for Pb2+ over a wide concentration range (1.0×10−2–4.0×10−6 M). It has a relatively fast response time and can be used for at least 3 months without any divergence in potentials. The proposed electrode revealed good selectivities for Pb2+ over a wide variety of other metal ions and could be used in a pH range of 2.0–7.0. It was used as an indicator electrode in potentiometric titration of lead ions and in direct determination of lead in water samples. 相似文献