全文获取类型
收费全文 | 2761篇 |
免费 | 127篇 |
国内免费 | 3篇 |
专业分类
化学 | 2183篇 |
晶体学 | 17篇 |
力学 | 34篇 |
数学 | 203篇 |
物理学 | 454篇 |
出版年
2023年 | 26篇 |
2022年 | 21篇 |
2021年 | 117篇 |
2020年 | 91篇 |
2019年 | 102篇 |
2018年 | 67篇 |
2017年 | 60篇 |
2016年 | 112篇 |
2015年 | 77篇 |
2014年 | 85篇 |
2013年 | 151篇 |
2012年 | 190篇 |
2011年 | 191篇 |
2010年 | 117篇 |
2009年 | 101篇 |
2008年 | 157篇 |
2007年 | 110篇 |
2006年 | 119篇 |
2005年 | 158篇 |
2004年 | 111篇 |
2003年 | 120篇 |
2002年 | 73篇 |
2001年 | 50篇 |
2000年 | 38篇 |
1999年 | 21篇 |
1998年 | 24篇 |
1997年 | 18篇 |
1996年 | 38篇 |
1995年 | 24篇 |
1994年 | 34篇 |
1993年 | 33篇 |
1992年 | 21篇 |
1991年 | 17篇 |
1990年 | 8篇 |
1989年 | 11篇 |
1988年 | 11篇 |
1987年 | 14篇 |
1986年 | 12篇 |
1985年 | 10篇 |
1984年 | 9篇 |
1982年 | 13篇 |
1981年 | 11篇 |
1980年 | 7篇 |
1979年 | 10篇 |
1978年 | 11篇 |
1977年 | 10篇 |
1976年 | 9篇 |
1975年 | 6篇 |
1973年 | 5篇 |
1898年 | 4篇 |
排序方式: 共有2891条查询结果,搜索用时 171 毫秒
71.
Marina DellaGreca Antonio FiorentinoMarina Isidori Lucio PreviteraFabio Temussi Armando Zarrelli 《Tetrahedron》2003,59(26):4821-4825
Investigation of the ethyl acetate extract of Juncus acutus rhizomes revealed seven benzocoumarins, probably derived from oxidation of phenanthrenes already isolated from the plant. The structures were determined by means of spectroscopic methods. The anti-algal activity of the isolated compounds tested on the green alga Pseudokirchneriella subcapitata are reported here. 相似文献
72.
73.
The Au-.CO2 ion-molecule complex has been studied by gas phase infrared photodissociation spectroscopy. Several sharp transitions can be identified as combination bands involving the asymmetric stretch vibrational mode of the CO2 ligand. Their frequencies are redshifted by several hundred cm(-1) from the frequencies of free CO2. We discuss our findings in the framework of ab initio and density-functional theory calculations, using anharmonic corrections to predict vibrational transition energies. The infrared spectrum is consistent with the formation of an aurylcarboxylate anion with a strongly bent CO2 subunit. 相似文献
74.
Alvarez-Lorenzo C Barreiro-Iglesias R Concheiro A Iourtchenko L Alakhov V Bromberg L Temchenko M Deshmukh S Hatton TA 《Langmuir : the ACS journal of surfaces and colloids》2005,21(11):5142-5148
The interactions of DNA (salmon testes) with two new cationic block copolymers made of poly(2-dimethylaminoethyl) methacrylate and poly(ethylene oxide), PEO-pDMAEMA, or poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), L92-pDMAEMA, were studied with the aim to understand their different in vitro transfection efficiencies when used as nonviral delivery vectors. PEO-pDMAEMA does not show surface activity while L92-pDMAEMA is as surface active as its parent Pluronic L92. Surface tension, titration microcalorimetry, ethidium bromide displacement, and zeta-potential measurements were carried out in phosphate buffers at pH 5 and 7. The association of L92-pDMAEMA with DNA was strongly exothermic at both pHs; the critical aggregation concentration (CAC) corresponded to a N/P ratio of 0.3, the maximum energy evolved was reached for N/P ratios of 0.82 and 1.27 at pH 5 and pH 7, respectively, and the saturation occurred for N/P ratios close to 2. The presence of L92 in the structure of this new block copolymer apparently did not modify the thermodynamic parameters of the interaction with DNA. In contrast, the interaction with PEO-pDMAEMA was significantly less exothermic, and CAC and saturation occurred for N/Ps equal to 0.43 and 1.37, respectively. The strong affinity of L92-pDMAEMA for DNA was reflected in its capacity to displace ethidium bromide and in the jump in the values of the zeta potential when N/P is near 1. Above the N/P ratio at which electroneutral polyplexes are formed, only at pH 5 an excess of L92-pDMAEMA is incorporated in the complexes, resulting in positively charged complexes. The profile of the zeta-potential values obtained for mixtures of L92-pDMAEMA with Pluronic P123 showed a shift to a lower N/P ratio, owing to an easier interaction of L92-pDMAEMA molecules with DNA in the presence of P123. Additionally, a visual inspection of the systems indicates that P123 contributes to stabilize/solubilize the DNA/cationic polymer aggregates, by avoiding the typical phase separation near the charge neutralization point. The information obtained can be particularly useful to optimize the conditions to form efficient polyplexes for gene delivery systems. 相似文献
75.
Alexandra P. Pleshkova Marina N. Uspenskaya Sergei V. Volkovitch 《Journal of mass spectrometry : JMS》1994,29(1):26-29
New examples of the ortho effect in bisphenol A derivatives including interaction of the hydrogen of the ortho-hydroxy group with the neighbouring aromatic ring have been observed. The characteristic ions [M ? PhOH]+middot; (m/z = 134) and [M ? CH3 ? PhOH]+ (m/z = 119) were shown to form through the hydrogen transfer from hydroxy and isopropyl groups, respectively. The spectra of cyclic derivatives having ortho-hydroxy functions show [M ? 43]+, [M ? C8H9O]+, m/z = 147, m/z = 135 and [M ? C9H10O]+ ions. The proposed mechanims of the corresponding transformations were supported by mass spectra of deuterated analogues, methyl and trimethyl silyl ethers. 相似文献
76.
Mikhail I. Kodess Marina A. Ezhikova Galina L. Levit Victor P. Krasnov Valery N. Charushin 《Journal of organometallic chemistry》2005,690(11):2766-2768
Experimental conditions for determination of enantiomeric composition of 1-substituted 3-aminocarboranes by 1H and 13C NMR spectroscopy using chiral shift reagent Eu(hfc)3 have been found. 相似文献
77.
Darío Gmez Marina Dos Santos Fabin Fujiwara Griselda Polla Julieta Marrero Laura Dawidowski Patricia Smichowski 《Microchemical Journal》2007,85(2):276-284
A study was undertaken to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in fly ashes collected in the electrostatic precipitator of a thermal power plant in San Nicolás (Argentina). Five samples were collected during one week of operation. For the fractionation, the scheme applied consisted in extracting the elements in four fractions namely (i) soluble and exchangeable elements; (ii) carbonates, oxides and reducible elements; (iii) bound to sulfidic metals; and (iv) residual elements. Metals and metalloids at μg g− 1 level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). For validation, a standard reference material (SRM 1633 coal fly ash) from NIST was subjected to the same chemical sequential extraction procedure that the samples. X-ray diffraction powder (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the major minerals present in the matrix. Total analyte concentration (in μg g− 1) varied from 10.6 for Pb to 17,622 for Al. Minimum and maximum concentrations (in μg g− 1) found in individual samples in the four fractions were: Al, 92.7–9668; As, < 0.3–143; Cr, 2.0–10.4; Cu, < 0.2–35.6; Fe, < 0.3–4992; Mn, < 0.1–128; Ni, < 0.3–139; Pb, < 0.5–9.1; Ti, < 0.3–2243; V, 17.0–112.9; and Zn, < 0.1–68.2. The leachability of the 11 elements under study proved to be different. Low percentages of Al (1%), V (7%) and Cr (8%) were detected in the most bioavailable fraction. Arsenic was found to be most abundant in the non-silicate phase, represented by the second and third fractions, while Cr, Fe, Ni, Pb and Zn were mostly associated to the residual fraction. 相似文献
78.
Cocchi M Faeti V Manfredini M Manzini D Marchetti A Sighinolfi S 《Journal of AOAC International》2005,88(2):393-398
The presence of some essential and toxic metals in fat supplements for swine diet was investigated. Collected samples represented a relevant production of the Italian industry. In particular, some samples were enriched with antioxidants or waste cooking oils. The method for the determination of Ca, Cu, Cd, Fe, Mg, Mn, Ni, Pb, and Zn in fat samples was developed by means of a certified reference material (CRM 186) and a representative fatty sample (RFS). All samples were digested in closed vessels in a microwave oven and then analyzed by flame atomic absorption or graphite furnace atomic absorption spectrometry. The entire analytical method provided a satisfactory repeatability and reproducibility confirmed by agreement between the experimental recovery data obtained for the CRM 186 sample and, with the method of standard additions, for the RFS material. The samples generally showed a small amount of metals compared with the recommended daily intake for the essential elements. On the other hand, some samples contained a significant concentration, from an analytical point of view, of Cd, Ni, and Pb. Principal component analysis (PCA) was applied to inspect the experimental data obtained from samples analysis. Basically no differences were detected in terms of metal concentration among the fat supplements analyzed. 相似文献
79.
Oleg V. Mikhailov Marina A. Kazymova Tatyana A. Shumilova Galina A. Chmutova Svetlana E. Solovieva 《Transition Metal Chemistry》2005,30(1):18-21
The complexing processes in the M
II
-dithiomalonamide-diacetyl triple system (M=Ni, Cu) occuring in the nickel(II)- and copper(II)hexacyanoferrate(II) gelatin-immobilized matrix in contact with aqueous alkaline solutions (pH~12) containing dithiomalonamide and diacetyl at room temperature, and between MCl2, dithiomalonamide
and
diacetyl
in
EtOH
solutions
upon
heating
to$80°C, have been studied. In the Ni
II
-dithiomalonamide-diacetyl system, template synthesis occurs in EtOH solution but does not occur in the gelatin-immobilized matrix, whereas in the Cu
II
-dithiomalonamide-diacetyl system, template synthesis occurs in the gelatin-immobilized matrix but not in EtOH solution. Dithiomalonamide and diacetyl are the ligand synthons in the processes indicated. 相似文献
80.
Gino Morisi Marina Patriarca Ferdinando Chiodo Anna Minoprio Antonio Menditto 《Mikrochimica acta》1996,123(1-4):281-290
Between 1992 and 1994, a new screening campaign for blood Pb monitoring in the Italian general population was carried out. Since the first campaign (started in 1978, in accomplishment of the European Community Directive 77/312/EEC) a working group of the Laboratory of Clinical Biochemistry at the Italian National Institute of Health (Istituto Superiore di Sanità), as the Reference Centre (RC), has coordinated the activity of various laboratories spread over the national territory. Appropriate quality assurance procedures, including an external quality assessment scheme (EQAS), were elaborated. Within the EQAS, three or four trials were carried out every year. Each laboratory participating in the trial analyzed eight control samples prepared from cow blood at different Pb concentrations. The results obtained by each peripheral laboratory and the RC between 1992 and 1994 have been compared by regression analysis. The same statistical method was adopted to compare the results obtained by each peripheral laboratory and the RC in the duplicate analysis of about 10 per cent of the human samples collected during the 1992–1994 monitoring campaign. There was no evidence of systematic differences between the regression lines obtained on control and human samples. In spite of the lower Pb concentration in the control samples analyzed during the 1992–1994 campaign, the analytical performance of the laboratories was better than that obtained in the previous screening campaign (1985–1986). Blood Pb levels observed in human samples collected between 1992 and 1994, confirm the downward time trend observed in the campaigns carried out in 1978–1979, 1980–1981 and 1985–1986. This study confirms that the results obtained in an EQAS are representative of the actual performance in the analysis of real (human) samples. 相似文献