全文获取类型
收费全文 | 8631篇 |
免费 | 178篇 |
国内免费 | 14篇 |
专业分类
化学 | 4848篇 |
晶体学 | 198篇 |
力学 | 196篇 |
数学 | 1410篇 |
物理学 | 2171篇 |
出版年
2022年 | 154篇 |
2021年 | 173篇 |
2020年 | 120篇 |
2019年 | 153篇 |
2018年 | 167篇 |
2017年 | 153篇 |
2016年 | 279篇 |
2015年 | 212篇 |
2014年 | 294篇 |
2013年 | 665篇 |
2012年 | 432篇 |
2011年 | 487篇 |
2010年 | 394篇 |
2009年 | 354篇 |
2008年 | 403篇 |
2007年 | 387篇 |
2006年 | 328篇 |
2005年 | 287篇 |
2004年 | 271篇 |
2003年 | 262篇 |
2002年 | 218篇 |
2001年 | 167篇 |
2000年 | 150篇 |
1999年 | 116篇 |
1998年 | 120篇 |
1997年 | 95篇 |
1996年 | 96篇 |
1995年 | 120篇 |
1994年 | 75篇 |
1993年 | 60篇 |
1992年 | 80篇 |
1991年 | 54篇 |
1990年 | 76篇 |
1989年 | 72篇 |
1988年 | 72篇 |
1987年 | 62篇 |
1986年 | 70篇 |
1985年 | 106篇 |
1984年 | 121篇 |
1983年 | 70篇 |
1982年 | 71篇 |
1981年 | 80篇 |
1980年 | 86篇 |
1979年 | 58篇 |
1978年 | 66篇 |
1977年 | 72篇 |
1976年 | 64篇 |
1975年 | 59篇 |
1974年 | 50篇 |
1973年 | 43篇 |
排序方式: 共有8823条查询结果,搜索用时 15 毫秒
951.
B. Machura A. ?witlicka D. Tabak J. Polański 《Journal of organometallic chemistry》2011,696(3):731-738
The molecular structure of 7-acetamido-2-methyl-quinoline-5,8-dione has been determined and the reactivity of 7-acetamido-2-methyl-quinoline-5,8-dione (1) and 6-acetamido-2-methyl-quinoline-5,8-dione (2) towards Re(CO)5Cl has been examined. Two novel tricarbonyl rhenium complexes, fac-[Re(CO)3(7-acetamido-2-methyl-quinoline-5,8-dione)Cl]·CHCl3 (3·CHCl3) and fac-[Re(CO)3(6-acetamido-2-methyl-quinoline-5,8-dione)Cl]2·CHCl3 (4·CHCl3), have been synthesized and characterized spectroscopically and structurally. The electronic spectrum of 3 was investigated at the TDDFT level employing B3LYP functional in combination with LANL2DZ. 相似文献
952.
Stanis?aw Krompiec Mateusz Penkala Ewelina Kowalska Robert Penczek Piotr Bujak Witold Danikiewicz Grzegorz Spólnik Andrzej Kita Iwona Grudzka 《Monatshefte für Chemie / Chemical Monthly》2011,33(7):1241-1247
Abstract
Ru-catalyzed synthesis of mixed alkyl–alkyl acetals via addition of primary alcohols to allyl ethers has been extended to include long-chain and/or functionalized substrates. The catalytic systems for these reactions were generated from RuCl2(PPh3)3 and [RuCl2(1,5-COD)]x and phosphines [PPh3 or P(p-chlorophenyl)3] or SbPh3. Of particular importance is the almost quantitative elimination of transacetalization. The addition proceeds through allyl complexes, not via isomerization of allyl ethers––subsequent addition of ROH to vinyl ethers. 相似文献953.
Pawe? Niedzia?kowski Tadeusz Ossowski Rados?aw Majewski Zdzis?awa Nowakowska Grzegorz Schroeder 《Monatshefte für Chemie / Chemical Monthly》2011,89(3):1121-1129
Abstract
In this work, the synthesis of various thiol-functionalized anthraquinone compounds is presented. The studied compounds were characterized by mass spectrometry and the main fragmentation pathways are discussed. The compounds studied formed stable self-assembled monolayers (SAMs) in the gold surface. The parameters for the reduction processes in the gold surface of the studied new anthraquinones were determined by cyclic voltamperometry tests. 相似文献954.
A new multiresidue method for the efficient screening, identification and quantification of over 160 pesticides belonging to different chemical classes in red, rose and white wines have been developed. The analysis was based on gas chromatographic-tandem quadrupole mass spectrometric determination (GC-QqQ-MS/MS). An optimization strategy involved the selection of buffering conditions and sorbents for dispersive-solid phase extraction (dispersive-SPE) in order to achieve acceptably high recoveries and reduce co-extractives in the final extracts. As a result, the optimized procedure allowed us to obtain consistent recoveries of the target pesticides including problematic ones such as captan, chlorothalonil, dichlofluanid, folpet and tolylfluanid. The attained recoveries were typically between 80 and 110% (89% on average) with RSD values typically lower than 10% (8% on average) at three spiking levels of 0.01, 0.05 and 0.2 mg kg−1. Linearity was studied in the range between 0.005 and 0.2 mg kg−1 using pesticide standards prepared both in pure solvent and in the presence of matrix, showing coefficients of determination (R2) higher than 0.99 for all the pesticides except for desmedipham, thiabendazole and thiamethoxam in pure solvent. The study of the ratio of the slopes obtained in solvent and in matrix provided information about the matrix effects, which was <10%, 10-20% and >20% for 33, 36 and 31% of the studied pesticides, respectively. To improve accuracy, matrix matched standards were always used for calculation of the quantification results. The expanded uncertainties were estimated by using a “top-down” approach as being 17% on average (coverage factor k = 2, confidence level 95%). Finally, the method was used with success to detect and quantify pesticide residues in commercial wines. 相似文献
955.
A series of salts, with the 9-aminoacridinium cation (9-AA) and aromatic carboxylic acid: benzoate (1), ortho-phthalate (2), and salicylate (3) anions have been synthesized and characterized using X-ray diffraction. In the crystal packing, the ions are linked via N-H?O, O-H?O, and C-H?O hydrogen bonds. Analysis of the hydrogen bonds in the crystal lattices of the title compounds shows that the cations and anions form tetramers. The ions in these tetramers are linked via N(amino)-H?O(carboxy) hydrogen bonds forming R22(8) (1 and 3) or R24(15) (2) hydrogen bond ring motifs. The cations interact through π-π interactions in the ABBA (1), AB (2) or ABA (3) arrangement to form columns (1 and 2) or chains (3). 相似文献
956.
Anticonvulsant neuropeptides are best known for their ability to suppress seizures and modulate pain pathways. Galanin, neuropeptide Y, somatostatin, neurotensin, dynorphin, among others, have been validated as potential first-in-class anti-epileptic or/and analgesic compounds in animal models of epilepsy and pain, but their therapeutic potential extends to other neurological indications, including neurodegenerative and psychatric disorders. Disease-modifying properties of neuropeptides make them even more attractive templates for developing new-generation neurotherapeutics. Arguably, efforts to transform this class of neuropeptides into drugs have been limited compared to those for other bioactive peptides. Key challenges in developing neuropeptide-based anticonvulsants are: to engineer optimal receptor-subtype selectivity, to improve metabolic stability and to enhance their bioavailability, including penetration across the blood–brain barrier (BBB). Here, we summarize advances toward developing systemically active and CNS-penetrant neuropeptide analogs. Two main objectives of this review are: (1) to provide an overview of structural and pharmacological properties for selected anticonvulsant neuropeptides and their analogs and (2) to encourage broader efforts to convert these endogenous natural products into drug leads for pain, epilepsy and other neurological diseases. 相似文献
957.
W. SzczepanikP. M?ynarz P. StefanowiczM. Kucharczyk-Klamińska N. D’AmelioA. Olbert-Majkut A. StaszewskaM. Ratajska Z. SzewczukM. Je?owska-Bojczuk 《Polyhedron》2011,30(1):9-15
The coordination properties of the novel conjugate towards copper ions were investigated. The performed studies exhibited the unusual binding properties of the ligand molecule having two potential strong coordination sites, namely dipeptidic chain and pyridyl nitrogens. On the basis of potentiometric and spectroscopic studies the binding at the low pH values to the aromatic entity is suggested, while the rise of pH (including physiological one) yielded the dimeric head-to-tail complex formation. This stable species possesses three nitrogen donors involved in Cu(II) chelation: N(pirydyl), NH2 and N−(amide). 相似文献
958.
959.
A strategy for selection of reference materials in stable oxygen isotope analyses of solid materials
The propagation of uncertainties associated with the stable oxygen isotope reference materials through a multi-point normalisation procedure was evaluated in this study using Monte Carlo (MC) simulation. We quantified the normalisation error for a particular selection of reference materials and their number of replicates, when the choice of standards is restricted to either nitrates, sulphates or organic reference materials alone, and in comparison with when this restriction was relaxed. A lower uncertainty in stable oxygen isotope analyses of solid materials performed using High-Temperature Pyrolysis (HTP) can be readily achieved through an optimal selection of reference materials. Among the currently available certified reference materials the best performing pairs minimising the normalisation errors are USGS35 and USGS34 for nitrates; IAEA-SO-6 and IAEA-SO-5 for sulphates; and IAEA-601 and IAEA-602 for organic materials. The normalisation error can be reduced further--by approximately half--if each of these two analysed reference materials is replicated four times. The overall optimal selection among all nine considered reference materials is the IAEA-602 and IAEA-SO-6 pair. If each of these two reference materials is replicated four times the maximum predicted normalisation error will equal 0.22‰, the minimum normalisation error 0.12‰, and the mean normalisation error 0.15‰ over the natural range of δ(18)O variability. We argue that the proposed approach provides useful insights into reference material selection and in assessing the propagation of analytical error through normalisation procedures in stable oxygen isotope studies. 相似文献
960.