全文获取类型
收费全文 | 8428篇 |
免费 | 378篇 |
国内免费 | 82篇 |
专业分类
化学 | 5937篇 |
晶体学 | 26篇 |
力学 | 221篇 |
数学 | 1231篇 |
物理学 | 1473篇 |
出版年
2023年 | 59篇 |
2022年 | 176篇 |
2021年 | 247篇 |
2020年 | 176篇 |
2019年 | 173篇 |
2018年 | 169篇 |
2017年 | 131篇 |
2016年 | 313篇 |
2015年 | 283篇 |
2014年 | 302篇 |
2013年 | 511篇 |
2012年 | 509篇 |
2011年 | 628篇 |
2010年 | 401篇 |
2009年 | 310篇 |
2008年 | 560篇 |
2007年 | 503篇 |
2006年 | 513篇 |
2005年 | 433篇 |
2004年 | 367篇 |
2003年 | 298篇 |
2002年 | 262篇 |
2001年 | 119篇 |
2000年 | 150篇 |
1999年 | 90篇 |
1998年 | 92篇 |
1997年 | 81篇 |
1996年 | 90篇 |
1995年 | 60篇 |
1994年 | 66篇 |
1993年 | 68篇 |
1992年 | 64篇 |
1991年 | 60篇 |
1990年 | 34篇 |
1989年 | 36篇 |
1988年 | 29篇 |
1987年 | 25篇 |
1986年 | 28篇 |
1985年 | 46篇 |
1984年 | 51篇 |
1983年 | 29篇 |
1982年 | 34篇 |
1981年 | 34篇 |
1980年 | 31篇 |
1979年 | 27篇 |
1978年 | 28篇 |
1977年 | 24篇 |
1976年 | 22篇 |
1974年 | 13篇 |
1973年 | 22篇 |
排序方式: 共有8888条查询结果,搜索用时 15 毫秒
71.
A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results. 相似文献
72.
73.
Alberto Avenoza Jesús H Busto Carlos Cativiela Francisco Corzana Jesús M Peregrina María M Zurbano 《The Journal of organic chemistry》2002,67(2):598-601
A short and efficient asymmetric synthesis of the (6R,7S)-7-tert-butoxycarbonylamino-2-ketocarbacepham is described. The key step involves the hetero Diels-Alder reaction of the benzylimine derived from the enantiomer of Garner's aldehyde with Danishefsky's diene. 相似文献
74.
Ricardo Baggio Juan Carlos Muoz Mireille Perec 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(10):m498-m500
The title compound, [Dy2(C2H3O2)6(H2O)4]·4H2O, crystallizes in the form of dimeric units related by an inversion centre. Each cation is nine‐coordinate, binding to two water molecules and three acetate groups, two of which are bidentate and the third tridentate. This last acetate group acts as a bridge between neighbouring metal atoms, leading to an intradimer Dy?Dy separation of 4.170 (1) Å. 相似文献
75.
The rate of the Wolff-Kishner reaction of benzophenone hydrazone in butyl carbitol increases as the cation of the alkoxide base is varied in the order K>Na>Li>Mg. The replacement of butyl carbitol by 1-decanol also accelerates the reaction, and an additional increase is caused by the presence of crown ether. On the basis of changes in the activation parameters, it is concluded that the reactivity of the hydrazone anion increases as the contact ion pair becomes more fully solvated and dissociated. 相似文献
76.
A novel asymmetric, edge-sharing bioctahedral complex with formamidinato ligands (
2-DAniF)Mo(-DAniF)2(-O,Cl)MoCl2, 1, (DAniF=N,N-di-p-anisylformamidinate) has been isolated as a byproduct from the preparation of the dimolybdenum(II,III) compound Mo2(DAniF)3Cl2. An X-ray crystallographic study shows that the structure consists of edge-sharing bioctahedra, with the shared edge defined by the vector joining the: -O and -Cl ligands. Compound 1 is best formulated as a mixed-valent MoIIIMoV compound, the Mo(V) ion being that with the two terminal Cl– ligands. The cyclic voltammogram of 1 shows a reversible reduction at –0.472 V and a reversible oxidation at 1.028 V vs. the Ag/AgCl reference electrode, while the absorption spectrum of 1 reveals an intense low energy absorption at 523 nm (
max=12 500) which is attributed to an intervalence charge transfer transition. Crystallographic data for 1 are as follows: a=13.387(1) Å, b=15.500(2) Å, c=21.855(2) Å, =98.786(2)°, V=4481.8(8) Å3, P21/c, R1 (wR2)=0.082 (0.177). 相似文献
77.
Synthetic erythropoietic proteins: tuning biological performance by site-specific polymer attachment
Chen SY Cressman S Mao F Shao H Low DW Beilan HS Cagle EN Carnevali M Gueriguian V Keogh PJ Porter H Stratton SM Wiedeke MC Savatski L Adamson JW Bozzini CE Kung A Kent SB Bradburne JA Kochendoerfer GG 《Chemistry & biology》2005,12(3):371-383
Chemical synthesis in combination with precision polymer modification allows the systematic exploration of the effect of protein properties, such as charge and hydrodynamic radius, on potency using defined, homogeneous conjugates. A series of polymer-modified synthetic erythropoiesis proteins were constructed that had a polypeptide chain similar to the amino acid sequence of human erythropoietin but differed significantly in the number and type of attached polymers. The analogs differed in charge from +5 to -26 at neutral pH and varied in molecular weight from 30 to 54 kDa. All were active in an in vitro cell proliferation assay. However, in vivo potency was found to be strongly dependent on overall charge and size. The trends observed in this study may serve as starting points for the construction of more potent synthetic EPO analogs in the future. 相似文献
78.
Barriga S Fuertes P Marcos CF Rakitin OA Torroba T 《The Journal of organic chemistry》2002,67(18):6439-6448
We report the synthesis of some new polysulfur-nitrogen heterocycles by cycloaddition reactions to readily available tricyclic condensed 1,2-dithiole-3-thiones. Thus, treatment of bis[1,2]dithiolopyrrole ketothione 1 with diacyl acetylenes gave the bis-aducts 2a-d. On the other hand, cycloaddition of bis[1,2]dithiolo[1,4]thiazine ketothione 3 with 1 equiv of acyl or diacyl acetylenes gave [1,3]dithiolylidenyl[1,2]dithiolo[1,4]thiazines 4a-f in fair to high yields. Catalysis by scandium triflate was used in the reactions that implied the less reactive dipolarophiles. Treatment of 3 with 2 equiv of DBA gave the bis-aduct 5a, and reaction of 4c with DMAD gave the mixed bis-adduct 5b. Cyclic voltammetry of selected examples showed irreversible processes that were influenced by the electrochemical activity of peripheral groups bonded to the heterocyclic system. 相似文献
79.
Carlos Cativiela Maria D. Diaz De Villegas Jos A. Mayoral Alberto Avenoza Miguel A. Roy 《Journal of heterocyclic chemistry》1988,25(3):851-855
3(5)-Carbomethoxy-4-hetarylpyrazoles 3 can be obtained by the aromatization of the corresponding cis-3-benzamido-3-carbomethoxy-4-hetaryl-Δ1-pyrazolines 2 obtained by 1,3-dipolar cycloaddition of diazo-methane with methyl Z-2-benzamido-3-hetarylpropenoates 1. An explanation, based on FMO theory, for the different reactivity of the dipolarophiles with diazomethane is given. 相似文献
80.
Torre L. Kenny J. M. Recca A. Siracusa V. Tarzia A. Maffezzoli A. 《Journal of Thermal Analysis and Calorimetry》2000,61(2):565-578
An analysis of the crystallization behaviour of a new poly(aryl-ether-ether-ketone-ketone), PK99, by differential scanning
calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) is presented. Isothermal crystallization TG were obtained in the
whole range between the glass transition temperature (T
g) and the melting temperature (T
m) as a consequence of the slow crystallization kinetics stemming from the closeness of these transitions. The calorimetric
results, compared with WAXD data, were applied to determine the theoretical melting temperature and crystallization enthalpy.
The DSC and WAXD data were combined in order to calculate the total amount of the crystallizable fraction of the polymer,
and a model was proposed to explain the difference between the fractions of crystallinity observed with these techniques.
The thermal and X-ray data were also correlated with different lamellar morphologies arising from the crystallization conditions.
Finally, DSC experiments on the crystallized sample were used to detect the presence of a rigid amorphous phase which does
not relax at T
g.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献