全文获取类型
收费全文 | 37504篇 |
免费 | 6492篇 |
国内免费 | 4309篇 |
专业分类
化学 | 25864篇 |
晶体学 | 519篇 |
力学 | 2455篇 |
综合类 | 286篇 |
数学 | 4461篇 |
物理学 | 14720篇 |
出版年
2024年 | 91篇 |
2023年 | 764篇 |
2022年 | 985篇 |
2021年 | 1215篇 |
2020年 | 1474篇 |
2019年 | 1390篇 |
2018年 | 1230篇 |
2017年 | 1141篇 |
2016年 | 1732篇 |
2015年 | 1693篇 |
2014年 | 2075篇 |
2013年 | 2630篇 |
2012年 | 3228篇 |
2011年 | 3424篇 |
2010年 | 2335篇 |
2009年 | 2300篇 |
2008年 | 2496篇 |
2007年 | 2253篇 |
2006年 | 2153篇 |
2005年 | 1661篇 |
2004年 | 1339篇 |
2003年 | 1119篇 |
2002年 | 1039篇 |
2001年 | 838篇 |
2000年 | 872篇 |
1999年 | 827篇 |
1998年 | 739篇 |
1997年 | 688篇 |
1996年 | 691篇 |
1995年 | 621篇 |
1994年 | 542篇 |
1993年 | 430篇 |
1992年 | 428篇 |
1991年 | 331篇 |
1990年 | 303篇 |
1989年 | 241篇 |
1988年 | 205篇 |
1987年 | 172篇 |
1986年 | 153篇 |
1985年 | 152篇 |
1984年 | 104篇 |
1983年 | 72篇 |
1982年 | 60篇 |
1981年 | 36篇 |
1980年 | 16篇 |
1979年 | 10篇 |
1977年 | 2篇 |
1971年 | 1篇 |
1959年 | 1篇 |
1957年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Ai‐Hua Zhao Yan Zhang Zhao‐Hui Xu Jian‐Wen Liu Wei Jia 《Helvetica chimica acta》2004,87(12):3160-3166
Three new enmein‐type ent‐kaurenoids, i.e., the two pairs 1 and 2 of 20‐epimers and the (20R)‐isomer 3 , besides the seven known diterpenoids 4 – 10 , were isolated from the aerial parts of Isodon serra. Their structures were elucidated by spectroscopic techniques and X‐ray diffraction. The immunosuppressive effect for T‐lymphocytes proliferation induced by Con A in BALB/c mouse was evaluated for the isolates 1 – 10 . They all displayed a remarkable inhibitory effect, with multi‐glycosides of Tripterygium wilfordii as positive reference substance (Table 3). 相似文献
942.
Poly(acrylp-aminobenzenesulfonamideamidine-p-aminobenzenesulfonylamide) chelating fiber containing "S", "N", and "O" elements was synthesized from polyacrylonitrile fiber and p-aminobenzene sulfonamide and used to enrich and separate trace Bi(III), Hg(III), Au(III), and Pd(IV) ions from wastewater and ore sample solution. The enrichment acidity, flow rate, elution conditions, reuse, interference ions, saturated adsorption capacity, constant of adsorption rate, analytical accuracy, and actual samples on chelating fiber were investigated by means of inductively coupled plasma optical emission spectrometry (ICP-OES) with satisfactory results. Solutions of 100 ng mL–1 of Bi(III), Hg(III), Au(III), and Pd(IV) ions can be enriched quantitatively by this chelating fiber at a rate of 1.0 mL min–1 at pH 4 and desorbed quantitatively with 20 mL of 0.25 M HCl and 2% CS(NH2)2 solution at 50 °C (with recovery 97%). When the chelating fiber was reused for 20 times, the recoveries of the analyzed ions enriched by the fiber were still over 95% (except for Hg(III)). One thousand-fold excesses of Mn2+, Ca2+, Zn2+, Mg2+, Fe3+, Cu2+, Ni2+, Al3+, and Ba2+ ions and thousands-fold excesses of Na+ and K+ cause little interference in the pre-concentration and determination of the analyzed ions. The saturated adsorption capacity of Bi(III), Hg(III), Au(III), and Pd(IV) was 4.850×10–4, 3.235×10–4, 2.807×10–4, and 3.386×10–4 mol g–1, respectively. The constants of adsorption rate were 0.409 min–1 for Bi, 0.122 min–1 for Hg, 0.039 min–1 for Au, and 0.080 min–1 for Pd. The relative standard deviations (RSDs) for the enrichment and determination of 10 ng mL–1 Bi(III), Hg(III), Au(III), and Pd(IV) were lower than 2.3%. The results obtained for these ions in actual samples by this method were basically in agreement with the given values with average errors of less than 1.0%. FT-IR spectra shows that the existence of –SO2–Ar, –H2N–Ar, O=C–NH–, HN=C–NH–, and –HN–SO2 functional groups are verified in the chelating fiber. From the FT-IR spectroscopy, we can see that Hg(III), Au(III), and Pd(IV) are mainly combined with nitrogen and sulfur (or oxygen), and Bi(III) is mainly combined with nitrogen (or oxygen) of the groups to form a chelating complex. 相似文献
943.
Brousmiche DW Xu M Lukeman M Wan P 《Journal of the American Chemical Society》2003,125(42):12961-12970
Evidence is presented for the photochemical generation of novel biphenyl quinone methide (BQM)-type intermediates on photolysis of hydroxybiphenyl alkenes 7 and 8 and hydroxybiphenyl alcohols 9 and 10. Mechanistic investigations utilizing product, fluorescence, and nanosecond laser flash photolysis (LFP) studies indicate two distinct pathways for the formation of these BQMs depending upon the functional groups of the progenitor. Formal excited-state intramolecular proton transfer (ESIPT) between the phenol and the alkene led to BQMs upon irradiation of the hydroxybiphenyl alkenes 7 and 8, while excited-state proton transfer (ESPT) to solvent followed by dehydroxylation was responsible for BQM formation from the hydroxybiphenyl alcohols 9 and 10. Photolysis of 7 and 8 in aqueous CH(3)CN gave photohydration products via attack of water on the respective BQMs, while photolysis of the analogous methyl ethers (of the phenolic moiety) gave only carbocation intermediates. Hydroxybiphenyl alcohols 9 and 10 yielded the corresponding photomethanolysis products in aqueous methanol, through attack of CH(3)OH on the respective BQMs. Although no evidence was found for BQM formation in LFP studies of 8 and 10, due to its suspected short lifetime, the respective diaryl carbocation (lambda(max) 420 nm, tau = 8.5 micros) has been observed upon irradiation of 8 in 2,2,2-trifluoroethanol. A BQM (lambda(max) 580 nm) was observed for 9 but not for 10, the latter having more complex chemistry on laser excitation, resulting in a transient that appears to mask any BQM absorption. Significant quenching of fluorescence from the hydroxybiphenyl alkenes at low water content implies that H(2)O is directly involved in reaction from the singlet excited state. The decrease in fluorescence intensity of 8 was found to depend on [H(2)O](3); however, the distance required for ESIPT in these systems is too large to be bridged by a water trimer. The nonlinear quenching has been attributed to deprotonation of the phenol by two water molecules, with concerted protonation at the alkene by another molecule of water. Fluorescence quenching of the hydroxybiphenyl alcohols required much higher water content, implying a different mechanism of reaction, consistent with the proposal of ESPT (to solvent water) followed by dehydroxylation. 相似文献
944.
The reactions of the cationic, diiron-bridging carbyne complexes [Fe(2)(mu-CAr)(CO)(4)(eta(8)-C(8)H(8))]BF(4) (1, Ar=C(6)H(5); 2, Ar=p-CH(3)C(6)H(4); 3, Ar=p-CF(3)C(6)H(4)) with LiN(C(6)H(5))(2) in THF at low temperature gave novel N-nucleophilic-addition products, namely, the neutral, diiron-bridging carbyne complexes [Fe(2)(mu-CAr)(CO)(4)(eta(7)-C(8)H(8)N(C(6)H(5))(2))] (4, Ar=C(6)H(5); 5, Ar=p-CH(3)C(6)H(4); 6, Ar=p-CF(3)C(6)H(4))). Cationic bridging carbyne complexes 1-3 react with (C(2)H(5))(2)NH, (iC(3)H(7))(2)NH, and (C(6)H(11))(2)NH under the same conditions with ring cleavage of the COT ligand to produce the novel diiron-bridging carbene inner salts [Fe(2)[mu-C(Ar)C(8)H(8)NR(2)](CO)(4)] (7, Ar=C(6)H(5), R=C(2)H(5); 8, Ar=p-CH(3)C(6)H(4), R=C(2)H(5); 9, Ar=p-CF(3)C(6)H(4), R=C(2)H(5); 10, Ar=C(6)H(5), R=iC(3)H(7); 11, Ar=p-CH(3)C(6)H(4), R=iC(3)H(7); 12, Ar=p-CF(3)C(6)H(4), R=iC(3)H(7); 13, Ar=C(6)H(5), R=C(6)H(11); 14, Ar=p-CH(3)C(6)H(4), R=C(6)H(11), 15, Ar=p-CF(3)C(6)H(4), R=C(6)H(11)). Piperidine reacts similarly with cationic carbyne complex 3 to afford the corresponding bridging carbene inner salt [Fe(2)[mu-C(Ar)C(8)H(8)N(CH(2))(5)](CO)(4)] (16). Compound 9 was transformed into a new diiron-bridging carbene inner salt 17, the trans isomer of 9, by heating in benzene. Unexpectedly, the reaction of C(6)H(5)NH(2) with 2 gave a novel COT iron-carbene complex [Fe(2)[=C(C(6)H(4)CH(3)-p)NHC(6)H(5)](mu-CO)(CO)(3)(eta(8)-C(8)H(8))] (18). However, the analogous reactions of 2-naphthylamine with 2 and of p-CF(3)C(6)H(4)NH(2) with 3 produce novel chelated iron-carbene complexes [Fe(2)[=C(C(6)H(4)CH(3)-p)NC(10)H(7)](CO)(4)(eta(2):eta(3):eta(2)-C(8)H(9))] (19) and [Fe(2)[=C(C(6)H(4)CF(3)-p)NC(6)H(4)CF(3)-p](CO)(4)(eta(2):eta(3):eta(2)-C(8)H(9))] (20), respectively. Compound 18 can also be transformed into the analogous chelated iron-carbene complex [Fe(2)[=C(C(6)H(4)CH(3)-p)NC(6)H(5)](CO)(4)(eta(2):eta(3):eta(2)-C(8)H(9))] (21). The structures of complexes 6, 9, 15, 17, 18, and 21 have been established by X-ray diffraction studies. 相似文献
945.
二氧化硅填料与硅橡胶在热老化时的作用 总被引:2,自引:0,他引:2
本文研究了三种表面性质不同的二氧化硅填料与二甲基硅橡胶在热老化时的作用。使混炼胶和硫化胶分别在甲苯和甲苯-氨中溶胀,测定了结合胶及溶胀度的变化。证明在老化时填料和橡胶之间有数量可观的化学键生成,并且发生氢键向化学键的转化。填料表面经过化学处理或加结构化控制剂,对它和橡胶之间的氢键结合,化学反应均有一定的抑制作用。 相似文献
946.
Adsorption of NH3 onto activated carbon prepared from palm shells impregnated with H2SO4 总被引:3,自引:0,他引:3
Adsorption of ammonia (NH3) onto activated carbons prepared from palm shells impregnated with sulfuric acid (H2SO4) was investigated. The effects of activation temperature and acid concentration on pore surface area development were studied. The relatively large micropore surface areas of the palm-shell activated carbons prepared by H2SO4 activation suggest their potential applications in gas adsorption. Adsorption experiments at a fixed temperature showed that the amounts of NH3 adsorbed onto the chemically activated carbons, unlike those prepared by CO2 thermal activation, were not solely dependent on the specific pore surface areas of the adsorbents. Further adsorption tests for a wide range of temperatures suggested combined physisorption and chemisorption of NH3. Desorption tests at the same temperature as adsorption and at an elevated temperature were carried out to confirm the occurrence of chemisorption due to the interaction between NH3 and some oxygen functional groups via hydrogen bonding. The surface functional groups on the adsorbent surface were detected by Fourier transform infrared spectroscopy. The amounts of NH3 adsorbed by chemisorption were correlated with the contents of elemental oxygen present in the adsorbents. Mechanisms for chemical activation and adsorption processes are proposed based on the observed phenomena. 相似文献
947.
Three unusual compounds based on polyoxometalate building blocks, [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2][Ag2IMo6O24(H2O)4] x 6.25H2O (1), [(H2O)4Na2(C6NO2H5)6Ag3][IMo6O24] x 6H2O (2), and (C6NO2H6)2[(C6NO2H5)2Ag][Cr(OH)6Mo6O18] x 4H2O (3), have been synthesized and characterized by elemental analysis; IR, XPS, and ESR spectroscopy; TG analysis; and single-crystal X-ray diffraction. Compound 1 is constructed from the cationic two-dimensional (2D) coordination polymer sheets which are constituted of [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2]3+ and anionic [Ag2IMo6O24(H2O)4]3- chains as pillars, forming a three-dimensional (3D) supramolecular framework via weak Ag-O interactions. Compound 2 is composed of the well-defined [IMo6O24]5- building blocks, which are linked through trinuclear Ag-pyridine-3-carboxylic acid, [(C6NO2H5)6Ag3]3+, fragments into a one-dimensional (1D) hybrid chain; adjacent chains are further connected by sodium cations to yield a novel 2D network. Compound 3 has a 1D chainlike structure constructed from [Cr(OH)6Mo6O18]3- building blocks and Ag-pyridine-4-carboxylic acid coordination units. The crystal data for these compounds are the following: 1, triclinic, P1, a = 13.280(3) A, b = 13.641(3) A, c = 16.356(3) A, alpha = 89.68(3) degrees, beta = 88.31(3) degrees, gamma = 75.87(3) degrees, Z = 2; 2, triclinic, P1, a = 11.978(2) A, b = 12.008(2) A, c = 13.607(3) A, alpha = 116.14(3) degrees, beta = 108.85(3) degrees, gamma = 93.86(3) degrees, Z = 1; 3, triclinic, P1, a = 10.458(2) A, b = 10.644(2) A, c = 12.295(3) A, alpha = 97.40(3) degrees, beta = 112.38(3) degrees, gamma = 113.59(3) degrees, Z = 1. 相似文献
948.
[chemical reaction: see text]. Direct addition of Grignard reagents to acid chlorides in the presence of bis[2-(N,N-dimethylamino)ethyl] ether proceeds selectively to provide aryl ketones in high yields. A possible tridentate interaction between Grignard reagents and bis[2-(N,N-dimethylamino)ethyl] ether moderates the reactivity of Grignard reagents, preventing the newly formed ketones from nucleophilic addition by Grignard reagents. 相似文献
949.
Changmei Sun Rongjun Qu Qiang Xu Chunnuan Ji Yanzhi Sun 《European Polymer Journal》2007,43(4):1501-1509
Two novel chelating resins were prepared by anchoring ethylenediamine to crosslinked polystyrene via a spacer containing sulfide. Their structures were characterized by Fourier transform-infrared spectra (FTIR) and scanning electron microscopy (SEM). Porous structure parameters of the resins were measured by ASAP 2020 using BET and BJH methods. Their adsorption capacities for several heavy metal ions especially Hg2+ were investigated. The results showed that for the two resins, the more N contents did not mean the better adsorption capacity and the saturated adsorption capacity of poly(2-ethylenediamidomercaptomethylstyrene) (PSM-EDA) for Hg2+ could reach to 3.0 mmol/g at room temperature. Isothermal adsorptions of the resins for Hg2+ could be described by Langmuir formula. The adsorption mechanism of the resins for Hg2+, Cu2+ and Ag+ was confirmed by X-ray photoelectron spectroscopy (XPS) and FTIR. 相似文献
950.
Zhiyong Wu Duanjun Xu Jingyun Wu Michael Y. Chiang 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):m374-m376
The title compound, [CuCl(CH4N2S)2]·2C11H6N2O·H2O, consists of molecules of a CuI–thiourea complex, free 4,5‐diazafluoren‐9‐one (dafone) and crystalline water. The planar complex molecule has trigonal coordination geometry around the CuI atom. The dafone and water molecules, which are hydrogen bonded to the CuI complex, are approximately coplanar with this complex. The crystal displays a sheet structure and π–π stacking is observed between neighbouring sheets. 相似文献