全文获取类型
收费全文 | 4109篇 |
免费 | 125篇 |
国内免费 | 35篇 |
专业分类
化学 | 2886篇 |
晶体学 | 22篇 |
力学 | 110篇 |
数学 | 721篇 |
物理学 | 530篇 |
出版年
2024年 | 4篇 |
2023年 | 21篇 |
2022年 | 80篇 |
2021年 | 125篇 |
2020年 | 90篇 |
2019年 | 87篇 |
2018年 | 78篇 |
2017年 | 75篇 |
2016年 | 163篇 |
2015年 | 115篇 |
2014年 | 147篇 |
2013年 | 225篇 |
2012年 | 284篇 |
2011年 | 344篇 |
2010年 | 202篇 |
2009年 | 174篇 |
2008年 | 263篇 |
2007年 | 243篇 |
2006年 | 222篇 |
2005年 | 219篇 |
2004年 | 204篇 |
2003年 | 134篇 |
2002年 | 124篇 |
2001年 | 59篇 |
2000年 | 40篇 |
1999年 | 43篇 |
1998年 | 34篇 |
1997年 | 39篇 |
1996年 | 48篇 |
1995年 | 42篇 |
1994年 | 29篇 |
1993年 | 30篇 |
1992年 | 20篇 |
1991年 | 34篇 |
1990年 | 18篇 |
1989年 | 20篇 |
1988年 | 14篇 |
1987年 | 13篇 |
1986年 | 22篇 |
1985年 | 26篇 |
1984年 | 26篇 |
1983年 | 13篇 |
1982年 | 26篇 |
1981年 | 10篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 7篇 |
1977年 | 5篇 |
1976年 | 7篇 |
1973年 | 3篇 |
排序方式: 共有4269条查询结果,搜索用时 15 毫秒
91.
Ariana Posadaz Alicia Biasutti Csar Casale Jesús Sanz Francisco Amat‐Guerri Norman A. García 《Photochemistry and photobiology》2004,80(1):132-138
The Rose Bengal‐sensitized photooxidations of the dipeptides l ‐tryptophyl‐l ‐phenylalanine (Trp‐Phe), l ‐tryptophyl‐l ‐tyrosine (Trp‐Tyr) and l ‐tryptophyl‐l ‐tryptophan (Trp‐Trp) have been studied in pH 7 water solution using static photolysis and time‐resolved methods. Kinetic results indicate that the tryptophan (Trp) moiety interacts with singlet molecular oxygen (O2(1Δg)) both through chemical reaction and through physical quenching, and that the photooxidations can be compared with those of equimolecular mixtures of the corresponding free amino acids, with minimum, if any, influence of the peptide bond on the chemical reaction. This is not a common behavior in other di‐ and polypeptides of photooxidizable amino acids. The ratio between chemical (kr) and overall (kt) rate constants for the interaction O2(1Δg)‐dipeptide indicates that Trp‐Phe and Trp‐Trp are good candidates to suffer photodynamic action, with krlkt values of 0.72 and 0.60, respectively (0.65 for free Trp). In the case of Trp‐Tyr, a lower krlkt value (0.18) has been found, likely as a result of the high component of physical deactivation of O2(1Δg) by the tyrosine moiety. The analysis of the photooxidation products shows that the main target for O2(1Δg) attack is the Trp group and suggests a much lower accumulation of kynurenine‐type products, as compared with free Trp. This is possibly because of the occurrence of another accepted alternative pathway of oxidation that gives rise to 3a‐oxidized hydrogenated pyrrolo[2,3‐b]indoles. 相似文献
92.
Cárdenas F Caba JM Feliz M Lloyd-Williams P Giralt E 《The Journal of organic chemistry》2003,68(25):9554-9562
Aplidine (dehydrodidemnin B), a natural product with potent antitumor activity currently in multicenter phase II clinical trials, exists in DMSO as a mixture of four slowly interconverting conformations in a ratio of 47:33:13:7. NMR spectroscopy shows that these arise as a consequence of cis/trans isomerization about the NMe-Leu(7)-Pro(8) and Pro(8)-Pyr amide bonds of the molecule's side chain. Two major conformations account for 47% and 33% of the total population, a ratio of 60:40 between the two. They correspond to the cis- and trans-isomers, respectively, about the Pro(8)-Pyr amide bond. Two minor conformers arise as a consequence of similar isomerism about the Pro(8)-Pyr amide bond, but in structures in which the NMe-Leu(7)-Pro(8) amide bond is cis rather than trans. These account for approximately 13% and 7% of the total population, corresponding to a ratio of 65:35 cis/trans, respectively. Molecular dynamics simulations show that the three-dimensional structures of all four conformational isomers are similar in the macrocycle and that all are essentially unchanged with respect to the macrocycle of didemnin B. Significant differences in the conformation of the molecule's side chain are, however, observed between major and minor pairs. Analysis of hydrogen-bonding patterns shows that each major conformer exhibits a beta-turn like structure and is stabilized by hydrogen bonding between a different carbonyl group of the pyruvyl unit of the molecule's side chain and the NH of the Thr(6) residue. The minor isomers have a cis-amide bond between the NMe-Leu(7) and Pro(8) residues that obliges the side chain to adopt an extended disposition where hydrogen bonding to the macrocycle is absent. These results suggest that the ability of the molecule's side chain to adopt a beta-turn-like conformation may not be a prerequisite for biological activity in the didemnins and that conformations having an extended side-chain may play a role in the biological activity of aplidine. 相似文献
93.
Farida Larit Khaled M. Elokely Manal A. Nael Samira Benyahia Francisco Len Stephen J. Cutler Mohammed M. Ghoneim 《Molecules (Basel, Switzerland)》2021,26(4)
The in vitro activity of L. donovani (promastigotes, axenic amastigotes and intracellular amastigotes in THP1 cells) and T. brucei, from the fractions obtained from the hydroalcoholic extract of the aerial part of Hypericum afrum and the isolated compounds, has been evaluated. The chloroform, ethyl acetate and n-butanol extracts showed significant antitrypanosomal activity towards T. brucei, with IC50 values of 12.35, 13.53 and 12.93 µg/mL and with IC90 values of 14.94, 19.31 and 18.67 µg/mL, respectively. The phytochemical investigation of the fractions led to the isolation and identification of quercetin (1), myricitrin (2), biapigenin (3), myricetin (4), hyperoside (5), myricetin-3-O-β-d-galactopyranoside (6) and myricetin-3’-O-β-d-glucopyranoside (7). Myricetin-3’-O-β-d-glucopyranoside (7) has been isolated for the first time from this genus. The chemical structures were elucidated by using comprehensive one- and two-dimensional nuclear magnetic resonance (1D and 2D NMR) spectroscopic data, as well as high-resolution electrospray ionization mass spectrometry (HR-ESI–MS). These compounds have also been evaluated for their antiprotozoal activity. Quercetin (1) and myricetin (4) showed noteworthy activity against T. brucei, with IC50 and IC90 values of 7.52 and 5.71 µM, and 9.76 and 7.97 µM, respectively. The T. brucei hexokinase (TbHK1) enzyme was further explored as a potential target of quercetin and myricetin, using molecular modeling studies. This proposed mechanism assists in the exploration of new candidates for novel antitrypanosomal drugs. 相似文献
94.
Pilar Campíns-Falcó Adela Sevillano-Cabeza Luisa Gallo-Martínez Francisco Bosch-Reig Isidro Monzó-Mansanet 《Mikrochimica acta》1997,126(3-4):207-215
This paper discusses the spectrophotometric determination of cephalexin as the intact cephalexin or as its acid-induced degradation product. Cephalexin can be determined in the range 1 × 10–5–18 × 10–5
M with relative standard deviations of 5-1%. The limits of quantitation and detection were 10–5 and 0.3 × 10–5
M, respectively. These procedures were compared with reversed-phase HPLC determination. No interference was observed in the presence of common pharmaceutical adjuvants. The H-point standard additions method was applied in order to correct for the possible presence of the cephalexin precursor, 7-aminocephalosporanic acid; this improves the selectivity of the UV-vis spectrophotometric method. 相似文献
95.
Coronado E Gómez-García CJ Nuez A Romero FM Rusanov E Stoeckli-Evans H 《Inorganic chemistry》2002,41(18):4615-4617
The combination of hexacyanoferrate(III) anions, [Fe(CN)(6)](3)(-), with nickel(II) complexes derived from the chiral ligand trans-cyclohexane-1,2-diamine (trans-chxn) affords the enantiopure layered compounds [Ni(trans-(1S,2S)-chxn)(2)](3)[Fe(CN)(6)](2).2H(2)O (1) and [Ni(trans-(1R,2R)-chxn)(2)](3)[Fe(CN)(6)](2).2H(2)O (2). These chiral systems behave as ferromagnets (T(c) = 13.8 K) with a relatively high coercive field (H(c) = 0.17 T) at 2 K. They also exhibit an unusual magnetic behavior at low temperatures that has been attributed to the dynamics of the magnetic domains in the ordered phase. 相似文献
96.
Fontana José D. Almeida Eduardo R. A. Baron Madalena Guimaraes Manoel F. Deschamps Francisco C. Schwartsmann Gllberto Cervi Armando C. Zanette Flávio Vilegas Janete LanÇas Fernando M. 《Applied biochemistry and biotechnology》1994,(1):295-313
The acetogenins are strongly bioactive natural compounds present in the bark, roots, leaves, and seeds of manyAnnonaceae plants. They are modified fatty acids and their cytotoxicities have been determined for different biological models including
the in vitro growth inhibition of several human cancer cell lines.
Very low acetogenin yield (< 0.1 g%) has been found previously in native phytobiomass, and we have now investigated the nonpredatory
exploitation of the seeds as acetogenin sources characterizing the seed triacylglycerols (dominant fraction; > 90% of the
whole lipid extracts) as potential valuable by-products. 相似文献
97.
Francisco Ros Pilar Jiménez María Victoria Roux 《Monatshefte für Chemie / Chemical Monthly》2007,28(4):941-949
The cohesion potential energy of the crystal of one enantiomer of ethyl 3-cyano-3-(3,4-dimethyloxyphenyl)-2,2,4-trimethylpentanoate,
−47.7 ± 0.1 kJ mol−1 (0–90°C), was found out from the heat of sublimation (123.2 ± 5.1 kJ mol−1, 78.6°C) and the kinetic energies for the gas phase and the crystal. It was found that the entropy function of Debye’s theory of solids mathematically agreed with the vibrational entropy of the gas (variationally obtained), allowing to disclose
the vibrational energy using the Debye energy function (E
vib 835.0 kJ mol−1 (78.6°C), E
0 included). E
kin for the crystal (771.1 kJ mol−1 (78.6°C)) was obtained by Debye’s theory with the experimental heat capacity. The cohesion energy represented a moderate part of the sublimation energy.
The cohesion energy of the racemic crystal, −44.2 kJ mol−1, was obtained by the heat of formation of the crystal in the solid state (3.0 kJ mol−1, 83.3°C) and E
kin for the crystal (by Debye’s theory). The decrease in cohesion on formation of the crystal accounted for the energy of formation. The change in potential
energy on liquefaction of the racemate from the gas state was disclosed obtaining added-up E
vib + rot for the liquid in the way as to E
vib for the gas, the Debye entropy function being increasedly suited for the liquid (E
vib + rot 763.4 kJ mol−1 (115.4°C)). Positive ΔE
pot, 13.0 kJ mol−1, arised from the increase in electronic energy (Δ
l
νmean − 154.3 cm−1, by the dielectric nature of the liquid), added to the cohesion energy. 相似文献
98.
Francisco Batista-Viera Mariela Barbieri Karen Ovsejevi Carmen Manta Jan Carlsson 《Applied biochemistry and biotechnology》1991,31(2):175-195
A new method for the reversible immobilization of thiol bimolecules, e.g., thiolpeptides and thiolproteins, to beaded agarose
and other solid phases is reported. The method consists of an activation and a coupling step. The activation is based on oxidation
of disulfides (or thiol groups via disulfides) present in a solid phase by hydrogen peroxide at moderately acidic pH. This
oxidation leads to disulfide oxides (thiolsulfinate groups of which the majority are further oxidized to thiolsulfonate).
The thiolsulfonate groups react easily with thiol compounds, which become immobilized via disulfide bonds. The pH range for
thiol coupling is wide (pH 5-8), but for most thiols the reaction seems to proceed faster at pH>7. The stability of the reactive
group to hydrolysis, especially at neutral and weakly acidic pH, is very high. The activated gel, therefore, can be stored
as a suspension at pH 5 for extended periods. The method has been used to reversibly immobilize glutathione, β-galactosidase,
alcohol dehydrogenase, urease, and papain, all with exposed thiol groups as well as thiolated bovine serum albumin and sweet-potato
β-amylase.
Depending on the thiol content of starting thiol-agarose, thiol-sulfonate-agarose derivatives with different binding capacities
can be obtained. Thus, up to 5.0 mg (16 μmol) glutathione and 15 mg thiol-protein/mL gel derivative have been immobilized. 相似文献
99.
Pericàs MA Puigjaner C Riera A Vidal-Ferran A Gómez M Jiménez F Muller G Rocamora M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(18):4164-4178
New families of enantiopure bis(oxazolines) with 4,5-trans (5 a-g) or 4,5-cis (6 c) stereochemistry at the individual rings have been prepared in high yield. Their eta(3)-allyl palladium complexes (8 a-g, 9 c and 10) have been used as catalytic precursors in allylic alkylation reactions with excellent enantioselectivities (up to 96 %) for the trans oxazoline derivatives, while Pd/6 c system was inactive. NMR studies on palladium eta(3)-1,3-diphenylallyl intermediates (11 a, c and e) showed the presence of syn/syn- and syn/anti-allyl isomers in solution; this resembles the first example of eta(3)-eta(1)-eta(3) isomerism in Pd allylic complexes containing bis(oxazolines) derived from malonic acid. 相似文献
100.
Ana Valria de Oliveira Braz Mariana Carvalho Rodrigues Philippe Alencar Araújo Maia Ana Paula Dantas Pereira Jussara de Lima Silva Francisco Antonio Vieira dos Santos Luiz Everson da Silva Wanderley do Amaral Maura Lins dos Santos Henrique Douglas Melo Coutinho Tomasz Baj Grayna Kowalska Radosaw Kowalski Edinardo Fagner Ferreira Matias 《Molecules (Basel, Switzerland)》2022,27(18)
Commercialized mouthwashes are generally expensive for the most financially vulnerable populations. Thus, several studies evaluate the antimicrobial potential of herbal products, such as essential oils, to reduce the activity of microorganisms in the mouth. The objective of this research was to carry out the chemical characterization and antibacterial activity of the essential oil of Piper mosenii (EOPm), providing data that enable the development of a low-cost mouthwash formulation aimed at vulnerable communities. The analysis of the antibacterial potential and modulator of bacterial resistance was verified by the microdilution method to determine the minimum inhibitory concentration-MIC. The chemical components were characterized by gas chromatography coupled to mass spectrometry, where 23 chemical constituents were detected, with α-pinene, being the major compound. The EOPm showed a MIC ≥ 1024 µg/mL for all bacterial strains used in the tests. When the EOPm modulating activity was evaluated together with chlorhexidine, mouthwash and antibiotics against bacterial resistance, the oil showed a significant synergistic effect, reducing the MIC of the products tested in combination, in percentages between 20.6% to 96.3%. Therefore, it is recommended to expand the tests with greater variation of EOPm concentration and the products used in this research, in addition to the evaluation of toxicity and in vivo tests, seeking the development of a possible formulation of mouthwash accessible to the vulnerable population. 相似文献