全文获取类型
收费全文 | 696篇 |
免费 | 12篇 |
国内免费 | 3篇 |
专业分类
化学 | 312篇 |
晶体学 | 3篇 |
力学 | 6篇 |
数学 | 89篇 |
物理学 | 236篇 |
无线电 | 65篇 |
出版年
2021年 | 8篇 |
2020年 | 5篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2017年 | 6篇 |
2016年 | 7篇 |
2015年 | 4篇 |
2014年 | 17篇 |
2013年 | 29篇 |
2012年 | 20篇 |
2011年 | 28篇 |
2010年 | 13篇 |
2009年 | 10篇 |
2008年 | 53篇 |
2007年 | 51篇 |
2006年 | 64篇 |
2005年 | 58篇 |
2004年 | 28篇 |
2003年 | 19篇 |
2002年 | 14篇 |
2001年 | 22篇 |
2000年 | 27篇 |
1999年 | 11篇 |
1998年 | 10篇 |
1997年 | 8篇 |
1996年 | 8篇 |
1995年 | 11篇 |
1994年 | 7篇 |
1993年 | 6篇 |
1992年 | 17篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 10篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1979年 | 5篇 |
1978年 | 5篇 |
1977年 | 8篇 |
1976年 | 8篇 |
1975年 | 8篇 |
1974年 | 5篇 |
1973年 | 9篇 |
1972年 | 4篇 |
1968年 | 4篇 |
1917年 | 2篇 |
排序方式: 共有711条查询结果,搜索用时 15 毫秒
681.
Aubert B Barate R Bona M Boutigny D Couderc F Karyotakis Y Lees JP Poireau V Tisserand V Zghiche A Grauges E Palano A Pappagallo M Chen JC Qi ND Rong G Wang P Zhu YS Eigen G Ofte I Stugu B Abrams GS Battaglia M Brown DN Button-Schafer J Cahn RN Charles E Day CT Gill MS Groysman Y Jacobsen RG Kadyk JA Kerth LT Kolomensky YG Kukartsev G Lynch G Mir LM Oddone PJ Orimoto TJ Pripstein M Roe NA Ronan MT Wenzel WA Barrett M Ford KE Harrison TJ Hart AJ Hawkes CM Morgan SE Watson AT Goetzen K Held T 《Physical review letters》2007,98(1):012001
A search for charmed baryons decaying to D(0)p reveals two states: the Lambdac(2880)+ baryon and a previously unobserved state at a mass of [2939.8+/-1.3(stat)+/-1.0(syst)] MeV/c2 and with an intrinsic width of [17.5+/-5.2(stat)+/-5.9(syst)] MeV. Consistent and significant signals are observed for the K(-)pi(+) and K(-)pi(+)pi(-)pi(+) decay modes of the D0 in 287 fb(-1) annihilation data recorded by the BABAR detector at a center-of-mass energy of 10.58 GeV. There is no evidence in the D+p spectrum of doubly charged partners. The mass and intrinsic width of the Lambdac(2880)+ baryon and relative yield of the two baryons are also measured. 相似文献
682.
683.
Ansell RJ Barrett SA Meegan JE Warriner SL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(16):4654-4664
The interactions of a range of monocarboxylic acids with tetramethoxysilane Si(OMe)(4) (TMOS), in methanol (MeOH), have been investigated by using (1)H, (13)C and (29)Si solution-phase NMR spectroscopy and electrospray mass spectrometry (ESMS). Si(OMe)(4) acts as a catalyst/reagent in the selective methylation of 2-hydroxycarboxylic acids (2HOAs) in MeOH at room temperature: glycolic acid, lactic acid and 2-hydroxybutyric acid are esterified more than a hundred times faster in MeOH and Si(OMe)(4) than in MeOH alone. No acceleration of methylation is observed for carboxylic acids lacking the 2-hydroxy group. Methylation of the 2HOAs is associated with the condensation of individual siloxane units to form oligomers. A mechanism is proposed in which 2HOAs attach to silicon via the alkoxy group, then subsequently via the carboxyl group in an intramolecular rearrangement to form an unstable and reactive cyclic intermediate. This intermediate may lead to accelerated methylation of the carboxylic acid via nucleophilic attack of MeOH at the carbonyl group, while a separate reaction pathway leads to condensation of silanols and/or alkoxysilanes leading to oligosiloxanes. The mechanism has implications for the use of 2HOAs as templates in sol-gel silica preparation. 相似文献
684.
Lazar HZ Forestier T Barrett SA Kilner CA Létard JF Halcrow MA 《Dalton transactions (Cambridge, England : 2003)》2007,(38):4276-4285
The syntheses of [FeL][BF(4)](2).H(2)O, [FeL][ClO(4)](2).H(2)O, [FeL][NO(3)](2).CH(3)NO(2) and [FeL][CF(3)SO(3)](2) (L = tris(4-{pyrazol-3-yl}-3-aza-3-butenyl)amine) are described. The isostructural BF(4)(-) and ClO(4)(-) salts are high-spin between 5-300 K, while the other two compounds are high-spin at room temperature but undergo gradual high-->low spin transitions upon cooling. For [FeL][NO(3)](2) this transition is centred at 139 K and proceeds to near-completeness, while for [FeL][CF(3)SO(3)](2) it is centred at 144 K and only proceeds to 50% conversion. The CF(3)SO(3)(-) salt also undergoes spin-crossover centred at 200 K in (CD(3))(2)CO solution, and exhibits dynamic inversion of its helical ligand conformation. All these compounds except the triflate salt have been crystallographically characterised, and show capped trigonal antiprismatic [6 + 1] coordination geometries. The NO(3)(-) and CF(3)SO(3)(-) salts undergo quantitative conversion to trapped, high-spin excited states upon irradiation with a green laser at 10 K (the LIESST effect; LIESST = Light-Induced Excited Spin State Trapping). The thermal stabilities of their LIESST excited states (T(LIESST) = 80-82 K) resemble those found for iron(ii) complexes of bidentate N-heterocyclic ligands. Hence, the LIESST properties of [FeL](2+) are those of a complex of three rigid bidentate domains linked by a flexible spacer, rather than of a single encapsulating podand. 相似文献
685.
686.
Rodriguez-Aristegui S Clapham KM Barrett L Cano C Desage-El Murr M Griffin RJ Hardcastle IR Payne SL Rennison T Richardson C Golding BT 《Organic & biomolecular chemistry》2011,9(17):6066-6074
Amino-substituted biphenyls were obtained by Suzuki cross-coupling of 2,6-dibromoaniline with a phenylboronic acid (substituted with Me, NO(2), OH, OMe or Cl) preferably assisted by microwave irradiation. Conversion of the amino group into a thiol preceded a base-induced intramolecular substitution, also facilitated by microwave heating, to generate the second C-S bond of the target dibenzothiophene. The 1-, 2-, 3- or 4-substituted 6-halodibenzothiophenes obtained were subjected to a palladium-mediated coupling with 2-morpholin-4-yl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4H-chromen-4-one to give the respective 6-, 7-, 8- or 9-substituted dibenzothiophen-4-ylchromenones. These compounds were evaluated as inhibitors of DNA-dependent protein kinase (DNA-PK) and compared to the parent 8-(dibenzo[b,d]thiophen-4-yl)-2-morpholin-4-yl-4H-chromen-4-one. Notably, derivatives bearing hydroxy or methoxy substituents at C-8 or C-9 retained activity, whereas substitution at C-7 lowered activity. Substitution with chloro at C-6 was not detrimental to activity, but a chloro group at C-7 or C-8 reduced potency. The data indicate permissive elaboration of hydroxyl at C-8 or C-9, enabling the possibility of improved pharmaceutical properties, whilst retaining potency against DNA-PK. 相似文献
687.
688.
Novel azobenzene polyelectrolytes have been used to fabricate biocompatible self-assembled multilayer (SAMU) thin films of variable absorbance, thickness, organization, and morphology. The prepared SAMU films are useful for directed cell growth, and this application relies directly on control of contact and surface energy, and requires the ability to tune the surface characteristics which are critical to their development. The azo polyelectrolytes employed here were similar in their degree of polymerization and repeat unit composition of acrylic acid monomer and azo monomers, and only differ from each other due to the presence of different substituted head R-groups present on the p-position of the aromatic ring of the azo chromophores. Possession of characteristics of both the self-assembly due to acrylic acid groups, and photoswitchability of the azo monomer enable the azobenzene functionalized polyelectrolytes to exhibit novel photo-reversible applications. The azo polyelectrolytes with the substituted R-group pairs of shorter-ionized hydrophilic COOH and SO3H, shorter-non-ionized hydrophobic H and OC2H5, and larger-nonionized hydrophobic octyl C8H17 and C8F17 were used as polyanions and counter charge PDAC used as polycation to fabricate the layer-by-layer SAMU films onto glass and silicon substrates. The fabricated SAMU films were also characterized by various techniques. The UV absorption maxima, λmax p of the SAMU films move to lower wavelength relative to solution to exhibit a blue shift for the hydrophobic R-groups, while this behaviour was not observed for the hydrophilic R-groups. Similarly, the thickness, organization, morphology and other properties of the thin films were found to be dependent on the type of substituted R-groups of the azo polyelectrolytes due to the inter-related factors of ionization, hydrophobicity/hydrophilicity, solubility, and aggregation of azo PEL in the dipping solutions used for fabrication of the SAMU films. Understanding and controlling the adsorption characteristics of azo multilayer thin–film of switchable functionalities are vital to explore their potential for the development and application of new devices in diverse areas of biosensor, drug delivery systems, on-chip microscale chemical process and microfluidics systems. 相似文献
689.
Wei Rao Adam D. Celiz David J. Scurr Morgan R. Alexander David A. Barrett 《Journal of the American Society for Mass Spectrometry》2013,24(12):1927-1936
The detection and identification of proteins adsorbed onto biomaterial surfaces under ambient conditions has significant experimental advantages but has proven to be difficult to achieve with conventional measuring technologies. In this study, we present an adaptation of desorption electrospray ionization (DESI) and liquid extraction surface analysis (LESA) mass spectrometry (MS) coupled with in-situ surface tryptic digestion to identify protein species from a biomaterial surface. Cytochrome c, myoglobin, and BSA in a combination of single and mixture spots were printed in an array format onto Permanox slides, followed by in-situ surface digestion and detection via MS. Automated tandem MS performed on surface peptides was able to identify the proteins via MASCOT. Limits of detection were determined for DESI-MS and a comparison of DESI and LESA-MS peptide spectra characteristics and sensitivity was made. DESI-MS images of the arrays were produced and analyzed with imaging multivariate analysis to automatically separate peptide peaks for each of the proteins within a mixture into distinct components. This is the first time that DESI and LESA-MS have been used for the in-situ detection of surface digested proteins on biomaterial surfaces and presents a promising proof of concept for the use of ambient MS in the rapid and automated analysis of surface proteins. Graphical abstract
? 相似文献
690.
Catalytic oxidation of alkanethiols and dialkyldisulfides to alkanesulfonic acids by H2O2/CH3ReO3 examined by electrospray ionization mass spectrometry 下载免费PDF全文