全文获取类型
收费全文 | 4283篇 |
免费 | 155篇 |
国内免费 | 27篇 |
专业分类
化学 | 3145篇 |
晶体学 | 20篇 |
力学 | 116篇 |
数学 | 431篇 |
物理学 | 753篇 |
出版年
2023年 | 27篇 |
2022年 | 26篇 |
2021年 | 127篇 |
2020年 | 74篇 |
2019年 | 87篇 |
2018年 | 76篇 |
2017年 | 58篇 |
2016年 | 143篇 |
2015年 | 122篇 |
2014年 | 142篇 |
2013年 | 217篇 |
2012年 | 240篇 |
2011年 | 249篇 |
2010年 | 195篇 |
2009年 | 156篇 |
2008年 | 256篇 |
2007年 | 241篇 |
2006年 | 222篇 |
2005年 | 255篇 |
2004年 | 179篇 |
2003年 | 178篇 |
2002年 | 152篇 |
2001年 | 93篇 |
2000年 | 84篇 |
1999年 | 78篇 |
1998年 | 39篇 |
1997年 | 49篇 |
1996年 | 51篇 |
1995年 | 35篇 |
1994年 | 45篇 |
1993年 | 42篇 |
1992年 | 30篇 |
1991年 | 30篇 |
1990年 | 24篇 |
1989年 | 31篇 |
1988年 | 24篇 |
1987年 | 27篇 |
1986年 | 16篇 |
1985年 | 36篇 |
1984年 | 34篇 |
1983年 | 21篇 |
1982年 | 20篇 |
1981年 | 15篇 |
1980年 | 23篇 |
1979年 | 17篇 |
1978年 | 14篇 |
1976年 | 20篇 |
1975年 | 18篇 |
1974年 | 16篇 |
1972年 | 12篇 |
排序方式: 共有4465条查询结果,搜索用时 26 毫秒
71.
Victor Barba Julián Vázquez Rosa Santillan 《Journal of organometallic chemistry》2005,690(9):2351-2357
The syntheses of eight [4.3.0] heterobicyclic boronates containing a N → B coordinative bond are described. The monomeric compounds were prepared by reaction of arylboronic acids with a tridentate ligand having the ONO donor set of atoms. It was shown that substituents at the para-position of the B-phenyl moiety transmit electronic effects to the CN bond which in turn is polarized by formation of the N → B coordination bond. At the same time, related tridentate ligands were also reacted with 1,4-benzenediboronic acid in order to prepare benzene diboron complexes. The structure of this type of compounds was confirmed by X-ray analysis for one of the derivatives. 相似文献
72.
Mixtures of dioctadecyldimethylammonium chloride (DODAC) cationic vesicle dispersions with aqueous micelle solutions of the anionic sodium cholate (NaC) were investigated by differential scanning calorimetry, DSC, turbidity and light scattering. Within the concentration range investigated (constant 1.0 mM DODAC and varying NaC concentration up to 4 mM), vesicle → micelle → aggregate transitions were observed. The turbidity of DODAC/NaC/water depends on time and NaC/DODAB molar concentration ratio R. At equilibrium, turbidity initially decreases smoothly with R to a low value (owing to the vesicle–micelle transition) when R = 0.5–0.8 and then increases steeply to a high value (owing to the micelle–aggregate transition) when R = 0.9–1.0. DSC thermograms exhibit a single and sharp endothermic peak at Tm ≈ 49 °C, characteristic of the melting temperature of neat DODAC vesicles in water. Upon addition of NaC, Tm initially decreases to vanish around R = 0.5, and the main transition peak broadens as R increases. For R > 1.0 two new (endo- and exothermic) peaks appear at lower temperatures indicating the formation of large aggregates since the dispersion is turbid. All samples are non-birefringent. Dynamic light scattering (DLS) data indicate that both DODAC and DODAC/NaC dispersions are highly polydisperse, and that the mean size of the aggregates tends to decrease as R increases. 相似文献
73.
Silva Julio Cezar Soares de Lima Silva Diogo Ferreira Ferreira Luciano de Almeida-Filho Adiel Teixeira 《4OR: A Quarterly Journal of Operations Research》2022,20(1):139-164
4OR - Even though sovereign bonds represent low-risk alternatives that give investors a healthy income, the risk assessment process for these bonds is still considered subjective because of the... 相似文献
74.
Alessandro D'Aprano Camillo La Mesa Noemi Proietti Bianca Sesta Sonia Tatone 《Journal of solution chemistry》1994,23(12):1331-1346
The interactions between octyl--D-glucoside and glycine in water have been investigated by surface tension, viscosity, and density measurements. The results show that the -amino acid causes an unexpected lowering of the critical micellar concentration of octyl--D-glucoside. Such a finding has been interpreted in temss of dipole-dipole interactions between the hydrophilic site of the surfactant and the peptidic cosluttes. From three to seven amino acid molecules have been estimated to be coordinated with each glucoside unity in the micellar state. The research has been extended to glycine oligopeptides and L-lysine. The latter compound has effects similar to those observed with glycine whereas diglycine and triglycine show weaker effects on the micellization process. 相似文献
75.
Electroanalytical methods based on biosensor technology and differential pH measurement for the determination of l-lactic and l-malic acids in wine were developed. Lactic acid was determined according to two procedures consisting of the use of two lactate electrochemical biosensors, one based on a Clark O(2) probe and the other based on the H(2)O(2) probe. The two probes were assembled employing a polymeric membrane where the enzyme lactate oxidase was previously immobilized. Both sensors exhibited high storage and operational stabilities, and good reproducibility when used in wine matrix. Measurement of lactate was carried out using two different flow-through cells assembled with the lactate probes. The low detection limit of these probes and the relatively high concentration of lactate in wine samples required a serial dilution in the range 1:100 to 1:200, thus eliminating all potential electrochemical or enzyme interferences present in the sample. Malic acid was determined using a differential commercially available pH-meter and an enzymatic procedure. For this analysis, we employed the malic enzyme (EC 1.1.1.40) and the NADP(+) cofactor. The pH variation due to the action of this enzyme on malic acid was found to be proportional to the malic acid present in the sample. Experimental parameters such as pH, temperature, and co-factor concentration were optimized, resulting in malate determination in less than 1 min with good reproducibility. Various samples of wine and wine musts were assayed for lactate with the two biosensor procedures, and for malate with differential pH-metry. The results when compared with those obtained with the commonly used spectrophotometric procedure correlated well. 相似文献
76.
77.
Lazarus EA Navratil GA Greenfield CM Strait EJ Austin ME Burrell KH Casper TA Baker DR DeBoo JC Doyle EJ Durst R Ferron JR Forest CB Gohil P Groebner RJ Heidbrink WW Hong R Houlberg WA Howald AW Hsieh C Hyatt AW Jackson GL Kim J Lao LL Lasnier CJ Leonard AW Lohr J La Haye RJ Maingi R Miller RL Murakami M Osborne TH Perkins LJ Petty CC Rettig CL Rhodes TL Rice BW Sabbagh SA Schissel DP Scoville JT Snider RT Staebler GM Stallard BW Stambaugh RD St John HE Stockdale RE Taylor PL Thomas DM 《Physical review letters》1996,77(13):2714-2717
78.
Fustero S Navarro A Díaz D de La Torre MG Asensio A Sanz F González ML 《The Journal of organic chemistry》1996,61(25):8849-8859
Reaction of azaenolates of 2-alkyl-oxa(thia)zolines 6 with imidoyl chlorides 7 as electrophiles to furnish masked N-substituted beta-enamino acid derivatives 1-2 in 70-90% yield is described. Alternative routes are discussed. Compounds 1-2 generally appear in one tautomeric form, imino or enamino, depending on the nature of the imidoyl chloride. The configuration of the enamino moiety (Z) and the conformation (s-cis) of compounds 1-2 obtained were established by an NMR study and unequivocally set by nuclear Overhauser effect difference experiments. An X-ray structure of compound 1e is also reported, showing a strong intramolecular NH.N hydrogen bond. Ab initio calculations (HF/3-21G and HF/3-21+G) have been carried out on several representative examples (1e, 1p, and 1l) in an attempt to support and provide the correct geometry of these derivatives. Structural considerations among the possible isomers of compounds 1 are discussed. From these studies it was concluded that the theoretical calculations agree with the experimental results. In addition, a very simple one-pot procedure for the preparation of masked N-substituted alpha-alkylated beta-enamino acid derivatives 2 from 6, 7, and different alkyl halides (R(3)Y) is described. 相似文献
79.
Anhydrites(II)- CaSO4 were prepared from two waste gypsums (PRECHEZA Perov, FOSFA Potorná). The samples of anhydrites(II) with sulphate activators were tested on spillage, beginning and the end of setting time, bending and pressure strength. Both sodium and potassium sulphates accelerated setting of anhydrite, more impressively that prepared from Potorná gypsum. The addition of Na2SO4 influenced the strength of this anhydrite very favourably. On the contrary K2SO4 influenced favourably the strength of Perov anhydrite. Results confirm the necessity to evaluate properties of such materials with respect to their origin. 相似文献
80.