全文获取类型
收费全文 | 3768篇 |
免费 | 141篇 |
国内免费 | 16篇 |
专业分类
化学 | 2548篇 |
晶体学 | 79篇 |
力学 | 120篇 |
数学 | 304篇 |
物理学 | 874篇 |
出版年
2023年 | 43篇 |
2022年 | 82篇 |
2021年 | 78篇 |
2020年 | 90篇 |
2019年 | 112篇 |
2018年 | 66篇 |
2017年 | 64篇 |
2016年 | 120篇 |
2015年 | 90篇 |
2014年 | 128篇 |
2013年 | 292篇 |
2012年 | 192篇 |
2011年 | 297篇 |
2010年 | 152篇 |
2009年 | 121篇 |
2008年 | 182篇 |
2007年 | 199篇 |
2006年 | 135篇 |
2005年 | 116篇 |
2004年 | 115篇 |
2003年 | 75篇 |
2002年 | 78篇 |
2001年 | 54篇 |
2000年 | 40篇 |
1999年 | 22篇 |
1998年 | 23篇 |
1997年 | 23篇 |
1996年 | 33篇 |
1995年 | 29篇 |
1994年 | 36篇 |
1993年 | 42篇 |
1992年 | 37篇 |
1989年 | 19篇 |
1988年 | 36篇 |
1987年 | 34篇 |
1986年 | 29篇 |
1985年 | 41篇 |
1984年 | 32篇 |
1983年 | 39篇 |
1982年 | 31篇 |
1981年 | 28篇 |
1980年 | 38篇 |
1979年 | 27篇 |
1978年 | 36篇 |
1977年 | 21篇 |
1976年 | 27篇 |
1974年 | 21篇 |
1966年 | 29篇 |
1965年 | 19篇 |
1962年 | 43篇 |
排序方式: 共有3925条查询结果,搜索用时 156 毫秒
31.
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
32.
Koushik Dhara Santanu Karan Jagnyeswar Ratha Partha Roy Goutam Chandra Mario Manassero Dr. Biswanath Mallik Dr. Pradyot Banerjee Dr. 《化学:亚洲杂志》2007,2(9):1091-1100
A 2D coordination compound {[Cu2(HL)(N3)]?ClO4}∞ ( 1 ; H3L=2,6‐bis(hydroxyethyliminoethyl)‐4‐methyl phenol) was synthesized and characterized by single‐crystal X‐ray diffraction to be a polymer in the crystalline state. Each [Cu2(HL)(N3)]+ species is connected to its adjacent unit by a bridging alkoxide oxygen atom of the ligand to form a helical propagation along the crystallographic a axis. The adjacent helical frameworks are connected by a ligand alcoholic oxygen atom along the crystallographic b axis to produce pleated 2D sheets. In solution, 1 dissociates into [Cu2(HL)2(H3L)]?2H2O ( 2 ); the monomer displays high selectivity for Zn2+ and can be used in HEPES buffer (pH 7.4) as a zinc ion selective luminescent probe for biological application. The system shows a nearly 19‐fold Zn2+‐selective chelation‐enhanced fluorescence response in the working buffer. Application of 2 to cultured living cells (B16F10 mouse melanoma and A375 human melanoma) and rat hippocampal slices was also studied by fluorescence microscopy. 相似文献
33.
Birendra K. Agrawal Madhup Chandra Badri V. Agarwala Arun K. Dey 《Transition Metal Chemistry》1978,3(1):243-246
Summary Mixed ligand complexes of copper(II), zinc(II), nickel(II) and cobalt(II) ions involving 1,10-phenanthroline (phen) as primary and 3,5-dinitrosalicylic acid (dnsa), 5-nitrosalicylic acid (nsa), 5-chlorosalicylic acid (csa) and 3,5-dibromosalicylic acid (dbsa) as secondary ligands in solution have been investigated potentiometrically [25°, µ = 0.1 M [NaClO4], medium 50% v: v aqueous ethanol]. The stability order of mixed ligand complexes with respect to the metal ions obeys the natural order: cobalt(II) < nickel(II) < copper(II) > zinc(II). The stabilities of the heterometal chelates have been compared with the corresponding homometal chelates of the secondary ligands and have been interpreted in terms of metal-ligand effects and coulombic interactions between various ligand anion species present. 相似文献
34.
Summary Calmagite [1-(1-hydroxy-4-methyl-2-phenyl azo)-2-naphthol sulphonic acid], dissociates in two steps. It forms violet complexes with Al3+, Ga3+ and In3+. The stepwise proton-ligand stability constants of calmagite and stepwise metal-ligand stability constants of these complexes were evaluated by potentiometric titration technique ofBjerrum andIrving andRossotti. The order of the stabilities of complexes is In3+ > Ga3+ > > Al3+.
Zusammenfassung Camalgit [1-(1-Hydroxy-4-methyl-2-phenylazo)-2-naphtholsulfonsäure] dissoziiert in zwei Stufen und bildet violette Komplexe mit Al(III), Ga(III) und In(III). Die Konstanten der Dissoziationsstufen der freien Säure und die der Metallkomplexe wurden potentiometrisch nachBjerrum bzw.Irving undRossotti ermittelt. Die Stabilität der Komplexe nimmt in der Reihe In(III) > Ga(III) > Al(III) ab.相似文献
35.
Collisions of I2 in the E electronic state with rare gas atoms result in electronic energy transfer to the D, beta, and D' ion-pair electronic states. Rate constants for each of these channels have been measured when I2 is initially prepared in the J = 55, nu = 1 and 2 levels in the E state. The rate constants and effective hard sphere collision cross sections confirm the trends observed when nu = 0 in the E state is initially prepared: He collisions favor population of the D state, while Ar collisions favor population of the beta state. Final state vibrational level distributions are determined by spectral simulation and are found to be qualitatively consistent with the trends in the Franck-Condon factors. The experimental distributions are also compared to the recent quantum scattering calculations of Tscherbul and Buchachenko. 相似文献
36.
The o-, m-, and p-phenylene bis(1,3-dioxolanium) dications (4-6) and 2,4,6-triphenylene tris(1,3-dioxolanium) trication (7) have been prepared by the ionization of the corresponding 2-methoxyethyl benzoates in FSO(3)H or CF(3)SO(3)H at 40 and 60 degrees C, respectively. The charge delocalization in these carbocations was probed by (13)C NMR chemical shifts and substantiated by GIAO/DFT calculations. Relatively less charge is delocalized into the aromatic ring of the carbotrication 7. The rotational barrier around the C(+)-Ar bond for carbodications 4 and 5 was also estimated to be 8-10 kcal/mol. 相似文献
37.
Total synthesis of (-)-lentiginosine was achieved from D-mannitol using highly stereoselective reactions. Similarly, (+)-lentiginosine was synthesized from L-tartaric acid. 相似文献
38.
Summary Reactions of titanium(IV) isopropoxide with ethyl 1-hydroxycyclohexylacetate, ethyl 2-hydroxy-2-arylpropionate, ethyl 2-hydroxy-2-arylbutyrate and ethyl 2-hydroxy-2-arylhydrocinnamate have been studied in dry benzene in different molar ratios under strictly anhydrous conditions. The Ti(OPr-i)4-nLn type compounds, where L = hydroxy ester and n = 1 to 4, have been isolated and characterised by elemental analysis, molecular weight, i.r. and n.m.r. spectral studies. These products may be distilled unchanged under reduced pressure.Reprints of this are not available. 相似文献
39.
R. Dustan Myrex Gary M. Gray Young-Jin Wright Prakash C. Bharara Keith E. Branham 《European Polymer Journal》2003,39(6):1105-1115
Polymeric phosphonate esters are an interesting class of organophosphorus polymers because both the polymer backbone and phosphorus substituents can be modified. These polymers have been prepared by ring-opening polymerizations of cyclic phosphites, stoichiometric polycondensations of dimethyl phosphonate with diols in conjunction with diazomethane treatment and by transesterification of polyphosphonate oligomers. Our initial attempts to prepare high molecular weight polymeric phosphonate esters by the transesterification methods were unsuccessful. Results indicate that the reactions of dimethyl phosphonate with diols to form polyphosphonate oligomers with only methyl phosphonate end groups are plagued by a serious side reaction that forms phosphonic acid end groups. These end groups do not participate in the transesterification reaction and limit the molecular weights of the polymers that can be obtained. The phosphonic acid end groups can be converted into reactive methyl phosphonate end groups by treatment with diazomethane, however diazomethane is explosive and the polymerization is slow. An alternative route for the production of high molecular weight polymers is the transesterification of the 1,12-bis(methyl phosphonato)dodecane, formed by the reaction of excess dimethyl phosphonate and 1,12-dodecanediol, with a Na2CO3 promoter. This allows polymers with molecular weights of up to 4.5×104 to be prepared, and no phosphonic acid end groups are observed in these polymers. Thermal analyses of the poly(1,12-dodecamethylene phosphonate) have shown that this polymer has reasonable thermal stability (onset of thermal decomposition at 273 °C). This polymer also undergoes a cold crystallization process at 15 °C similar to that which has been observed in some polyesters, polyamides and elastomers. 相似文献
40.
Prakash O Kaur H Batra H Rani N Singh SP Moriarty RM 《The Journal of organic chemistry》2001,66(6):2019-2023
The combination reagent (dichloroiodo)benzene and lead(II) thiocyanate in dichloromethane effects oxidation of various enol silyl ethers, ketene silyl acetals, and beta-dicarbonyl compounds, thereby providing an efficient and convenient method for alpha-thiocyanation of carbonyl and beta-dicarbonyl compounds. 相似文献