全文获取类型
收费全文 | 6529篇 |
免费 | 161篇 |
国内免费 | 19篇 |
专业分类
化学 | 3647篇 |
晶体学 | 150篇 |
力学 | 294篇 |
数学 | 770篇 |
物理学 | 1848篇 |
出版年
2022年 | 75篇 |
2021年 | 107篇 |
2020年 | 111篇 |
2019年 | 149篇 |
2018年 | 99篇 |
2017年 | 117篇 |
2016年 | 184篇 |
2015年 | 133篇 |
2014年 | 172篇 |
2013年 | 482篇 |
2012年 | 310篇 |
2011年 | 407篇 |
2010年 | 238篇 |
2009年 | 203篇 |
2008年 | 259篇 |
2007年 | 280篇 |
2006年 | 225篇 |
2005年 | 215篇 |
2004年 | 186篇 |
2003年 | 131篇 |
2002年 | 136篇 |
2001年 | 90篇 |
2000年 | 75篇 |
1999年 | 63篇 |
1998年 | 58篇 |
1996年 | 69篇 |
1995年 | 58篇 |
1994年 | 69篇 |
1993年 | 86篇 |
1992年 | 78篇 |
1991年 | 53篇 |
1990年 | 62篇 |
1989年 | 59篇 |
1988年 | 79篇 |
1987年 | 68篇 |
1986年 | 41篇 |
1985年 | 90篇 |
1984年 | 105篇 |
1983年 | 70篇 |
1982年 | 70篇 |
1981年 | 77篇 |
1980年 | 88篇 |
1979年 | 83篇 |
1978年 | 81篇 |
1977年 | 70篇 |
1976年 | 66篇 |
1975年 | 52篇 |
1974年 | 52篇 |
1973年 | 59篇 |
1962年 | 52篇 |
排序方式: 共有6709条查询结果,搜索用时 31 毫秒
61.
Isocytosine (ICH) exists in solution as two major tautomers, the keto form with N1 carrying a proton (1a) and the keto form with N3 being protonated (1b). In water, 1a and 1b exist in equilibrium with almost equal amounts of both forms present. Reactions with a series of Pd(II) and Pt(II) am(m)ine species such as (dien)Pd(II), (dien)Pt(II), and trans-(NH(3))(2)Pt(II) reveal, however, a distinct preference of these metals for the N3 site, as determined by (1)H NMR spectroscopy. Individual species have been identified by the pD dependence of the ICH resonances. pK(a) values (calculated for H(2)O) for deprotonation of the individual tautomers complexes are 6.5 and 6.4 for the N3 linkage isomers of dienPd(II) and dienPt(II), respectively, as well as 6.2 and 6.0 for the N1 linkage isomers. The dimetalated species [(dienM)(2)(IC-N1,N3)](3+) (M = Pd(II) or Pt(II)) are insensitive over a wide range of pD. The crystal structure analysis of [(dien)Pd(ICH-N3)](NO(3))(2) is reported. Ab initio calculations have been performed for tautomer compounds of composition [(NH(3))(3)Pt(ICH)](2+), cis- and trans-[(NH(3))(2)PtCl(ICH)](+), as well as trans-[(NH(3))(2)Pt(ICH)(2)](2+). Without exception, N3 linkage isomers are more stable, in agreement with experimental findings. As to the reasons for this binding preference, an NBO (natural bond orbital) analysis for [(NH(3))(3)Pt(ICH-N3)](2+)strongly suggests that intramolecular hydrogen bonding between trans-positioned NH(3) ligands and the two exocyclic groups of the ICH is of prime importance. The calculations furthermore show a marked pyramidalization of the NH(2) group of ICH in the complex once the heterocyclic ligand forms a dihedral angle <90 degrees with the Pt coordination plane. 相似文献
62.
NMR spectroscopic studies reveal that binding of Na(+) by tris(2-methoxyphenyl)amine (3) brings two of these tripod ethers together about the metal ion; the related double-tripod-ether ionophore 1,2-bis[2-(bis(2-methoxyphenyl)amino)phenoxy]ethane (4), in which two triarylamines are covalently attached, binds LiI, LiBPh(4), NaI, NaBPh(4), and KB(4-ClPh)(4). Dynamic NMR puts lower limits on binding free energies of 4 for Na(+) (71.8 kJ mol(-)(1)) and K(+) (66.8 kJ mol(-)(1)) ions. X-ray studies of 3(2).NaBPh(4), 4.NaBPh(4), 4.NaB(4-ClPh)(4), and 4.KB(4-ClPh)(4).CH(3)NO(2) show eight-coordinate M(+) ions bound between crystallographically independent, homochiral triarylamine tripod ethers in structures reminiscent of alkali metal [2.2.2] cryptates. Complexes crystallize as follows: 3(2).NaBPh(4), monoclinic, P2(1)/c, Z = 4, a = 10.701(3) ?, b = 37.593(3) ?, c = 13.774(2) ?, and beta = 98.24(2) degrees; 4.NaBPh(4), triclinic, P&onemacr;, Z = 2, a = 12.157(1) ?, b = 14.811(1) ?, c = 15.860(2) ?, alpha = 105.400(8) degrees, beta = 91.594(9) degrees, and gamma = 95.354(8) degrees; 4.NaB(4-ClPh)(4), monoclinic, P2(1)/n, Z = 4, a = 13.652(5) ?, b = 18.75(1) ?, c = 22.805(5) ?, and beta = 92.21(5) degrees; 4.KB(4-ClPh)(4).CH(3)NO(2), monoclinic, Pn, Z = 2, a = 13.663(4) ?, b = 12.228(3) ?, c = 18.712(8) ?, and beta = 91.45(3) degrees. They show variable N-M-N angles; 3(2).NaBPh(4) is surprisingly bent ( angleN-Na-N = 154.5 degrees ), while the 4.M(+) complexes are normal: nearly linear for Na(+) ( angleN-Na-N = 178.6, 178.1 degrees ) and again bent with the larger K(+) ( angleN-K-N = 164.5 degrees ). Finally, free 4 is structurally similar to 3; it crystallizes in the triclinic space group P&onemacr;, with Z = 2, a = 8.068(1) ?, b = 14.599(2) ?, c = 16.475(3) ?, alpha = 115.43(1) degrees, beta = 92.51(1) degrees, and gamma = 90.40(1) degrees. 相似文献
63.
N-methylaminoalkoxides of titanium of the type Ti(OR)4?n(O · CHR′ · CH2 · NR″R?)n where R = Et and Pr1; n = 1–4; and R′ = R″ = H, R? = Me; R′ = H, R″ = R? = Me; R′ = R″ = R? = Me, synthesized by the reactions of titanium alkoxides with aminoalcohols, show interesting variations in their properties like physical state, volatility and molecular complexity. I.r. and p.m.r. spectra of these derivatives have been recorded. A few interchange reactions with methanol and tert-butanol have also been carried out. These aminoalkoxides get cleaved with acetyl chloride and undergo insertion reactions with phenylisocyanate, thus providing the first examples of insertion reactions in such derivatives. 相似文献
64.
Summary A study of thermal analysis of some lanthanide polyphosphates has been reported. The DTA curves of Ce, Pr and Sm polyphosphates were of similar nature. They exhibited a sharp exothermic peak indicating crystallization temperature (T
c) around 520 °C. However, no peak indicatingT
m
was observed upto 800 °C. TG curves of Ce, La, Pr, Sm, Y polyphosphates indicated weight loss occurring in three stages. The integral procedural decomposition thermal analysis (ipdt) indicated that these materials had refractory nature.With 4 figures and 2 tables 相似文献
65.
Kinetics of oxidation of lactose, maltose, cellobiose and melibiose has been studied by hexacyanoferrate(III) in the presence of ammonia. A general mechanism involving the formation of intermediate enodiol anion has been suggested. The effects of dielectric constant and salts have been studied in detail. The oxidation products have been characterised by descending paper chromatography. Compensation effects have been observed. 相似文献
66.
Optical and structural properties of coumarin-4 dye-doped SiO2-PDMS xerogels synthesized by acid catalyzed (one-step) and acid-base catalyzed (two-step) sol-gel routes with varying pH (0.6 to 7) and dye content ( 5 × 10–4 to 5 × 10–2 mole) are reported. Spectroscopic methods such as photo-luminescence, FT-IR and FT-Raman were used for characterizations. The acid catalyzed xerogels prepared with pH < 2.5 exhibited two fluorescence peaks, I at 390 nm and II at 480 nm. The acid-base catalyzed xerogels synthesized with pH < 2.5 also exhibited two peaks, I at 400 nm and II at 475 nm. Peak II was not observed for the samples with pH 2.5. This phenomenon was attributed to the existence of pH dependent different forms of coumarin-4 molecule. The concentration-quenching phenomenon was observed for the acid catalyzed xerogels prepared with different dye concentration. TheFT-IR spectra indicated the existence of hydrogen bonds between the carbonyl groups of dye molecules and the silanol groups of gel matrix. The hydrogen bonding was the highest for the samples with the extremity pH, 0.6 and 7, resulting in the highest dye/gel matrix interactions, hence, the highest fluorescence peaks. The Raman studies indicated that the samples prepared with pH < 2.5 possessed relatively more number of 3-membered siloxane rings than 4-membered siloxane rings. The ring statistics was reversed for the samples with pH > 2.5. The number of silanol groups was higher for the samples with pH > 2.5. 相似文献
67.
Summary Heterobimetallic complexes of the types [Cp2Ti(-EAr)2-M(dppe)] (ClO4)2 [(1)–(4); M, E = Ni, Te (1); Ni, Se (2); Pt, Te (3); Pt, Se (4); Ar = Ph (a), C6H4-4-Me (b), C6H4-4-OMe (c), C6H4-4-OEt (d)] and [Cp2Ti(-TeAr)2-MCl 2] [M = Pd (5), Pt (6)] were obtained by the reactions of Cp2Ti(EAr)2 with M(dppe)(ClO4)2 and M(PhCN)2Cl2, respectively. While (1), (5) and (6) are stable in the solid state as well as in solution, (2)–(4) undergo dissociation to M(dppe)(EAr)2 and Cp2Ti(ClO4)2 in solution, as shown by multinuclear (31P{1H},195Pt{1H}, 125Te{1H}) n.m.r. studies. The reaction of Cp2Ti(SeAr)2 with M(PhCN)2Cl2, however, leads to the formation of Cp2TiCl2 and a polymeric material [M(SeAr)2]
n
. 相似文献
68.
Devendra Kumar Uday Razdan Alka D. Gupta 《Journal of polymer science. Part A, Polymer chemistry》1992,30(7):1477-1487
Various melt-polymerizable bisimido-bisphthalonitrile polymer precursors were synthesized by the reaction of 4-aminophthalonitrile (4-APN) with bis(3,4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), 4,4′-hexafluoroisopropylidene diphthalic anhydride (6FDA), bis(3,4-dicarboxyphenyl)ether dianhydride (ODPA), and 3,3′, 4,4′-tetracarboxylichenzophen+ne dianhydride (BTDA) in an aprotic solvent. The synthesized monomers showed crystalline melting at 269 and 271°C. Elemental analysis, differential thermal analysis (DTA), infrared (IR), nuclear magnetic resonance (1H-NMR) and mass spectral studies were carried out to characterize the synthesized monomers. Thermogravimetric analysis (TGA) of the synthesized monomers showed their thermal stability at 410–400°C. A detailed study and NMR investigation of the first step of condensation reaction was carried out and indicated the formation of a transient charge transfer complex. Thermal cyclization of the formed intermediate, however, gave the required monomers. A preliminary study demonstrated that melt-polymerization of the synthesized monomers gave thermallystable, tough polymers. 相似文献
69.
V. K. Ahluwalia K. Bhat Chandra Prakash Manjula Khanna 《Monatshefte für Chemie / Chemical Monthly》1981,112(1):119-124
A convenient synthesis of linear pyranocoumarins, viz., 8,8-dimethyl-2H,8H-benzo[1,2-b; 5,4-b]dipyran-2-one (xanthyletin,1) and 8,8-dimethyl-3-phenyl-2H,8H-benzo[1,2-b; 5,4-b]dipyran-2-one (3-phenylxanthyletin,2) is described. The key steps are blocking the 8-position of appropriate 7-hydroxy-2H-1-benzopyran-2-one derivatives with iodine and 1,1-dimethyl-2-propynylation followed by cyclisation.
Ein einfacher Syntheseweg zu linearen Pyranocumarinen. Xanthyletin und 3-Phenylxanthyletin
Zusammenfassung Es wird ein vorteilhafter Weg zur Synthese von linearen Pyranocumarinen am Beispiel von Xanthyletin und 3-Phenylxanthyletin gezeigt. Das Syntheseprinzip besteht in einer Blockierung der 8-Position des entsprechenden 7-Hydroxy-2H-1-benzopyran-2-ons mit Jod und einer 1,1-Dimethyl-2-propinylierung mit nachfolgender Cyclisierung.相似文献
70.
H. Surya Prakash Rao S. Senthilkumar K. Gopu Shaik Rafi 《Chemistry of Heterocyclic Compounds》2007,43(3):292-297
The microwave-mediated reaction of 4-aryl-4-oxobutanoic acids with benzylamines furnished 1-arylmethyl-3-[(E)-1-arylmethylidene]-5-phenyl-2,3-dihydro-1H-pyrrolones.
This result is in contract to the earlier report on this reaction conducted under neat conditions. Structures for the products
were assigned on the basis of spectral data and confirmed by independent synthesis.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 368–373, March, 2007. 相似文献