全文获取类型
收费全文 | 420篇 |
免费 | 19篇 |
专业分类
化学 | 269篇 |
晶体学 | 9篇 |
力学 | 7篇 |
数学 | 56篇 |
物理学 | 98篇 |
出版年
2024年 | 1篇 |
2021年 | 5篇 |
2020年 | 5篇 |
2019年 | 2篇 |
2018年 | 10篇 |
2017年 | 7篇 |
2016年 | 19篇 |
2015年 | 22篇 |
2014年 | 18篇 |
2013年 | 27篇 |
2012年 | 25篇 |
2011年 | 31篇 |
2010年 | 20篇 |
2009年 | 10篇 |
2008年 | 31篇 |
2007年 | 27篇 |
2006年 | 20篇 |
2005年 | 23篇 |
2004年 | 22篇 |
2003年 | 13篇 |
2002年 | 8篇 |
2001年 | 5篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 5篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 1篇 |
1977年 | 2篇 |
1973年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1938年 | 1篇 |
1928年 | 2篇 |
排序方式: 共有439条查询结果,搜索用时 31 毫秒
11.
Brian A. Naughton Benson Sibanda Jory P. Weintraub Julia San Román Vafa Kamali 《Applied biochemistry and biotechnology》1995,54(1-3):65-91
A method of coculturing adult rat hepatic parenchymal cells (PC) and stromal cells in a three-dimensional framework of nylon
filtration screens or biodegradable polymer meshes was developed in our laboratory. Rat liver stroma, which includes vascular
and bile duct endothelial cells, fat-storing cells, fibroblasts, and Kupffer cells, were isolated by gradient centrifugation
afterin situ liver perfusion and expanded in monolayer culture prior to seeding onto nylon screens or bioresorbable polyglycolic acid
(PGA) polymers oriented into a felt-like construct. A second inoculum of freshly isolated PC was applied after the stromal
cells became established. Histological analyses revealed that PC proliferation occurred until all available space for expansion
within the template was exhausted. These cells retained their rounded morphology, and after 4–5 wk 7–9 “layers” of PC filled
the 140-μm deep template. Dioxin-inducible cytochrome P450 activity was detected for up to 58 d in culture, and albumin, fibrinogen,
transferrin, and soluble fibronectin were detected in the medium by enzyme-linked immunosorbent assay (ELISA) for 48 d in
vitro. Immunohistochemical analysis of sections through the cultures confirmed the presence of these proteins as well as cytokeratin
at the cellular level; the extracellular matrix stained for both collagen type III and laminin. Long-term PC proliferation
and function were enhanced by the presence of stromal cells as well as by a meshwork template whose geometry allows the interaction
of PC with stroma and matrix on several different planes. To permit transplantation, co-cultures of hepatic PC and stromal
cells were established on PGA felt constructs instead of nylon screens. After 24 d in vitro, these constructs were grafted
into sites in the mesentery, omentum, and sub-cutaneous tissues of adult Long-Evans rats. The growth of hepatocytes after
30 din situ was evident by histological analysis; grafts of co-cultures regenerated a liver-like architecture consisting of sinusoids
and putative biliary structures. In addition, PC at these extrahepatic graft sites were positive for albumin, transferrin,
and fibrinogen synthesis by immunohistochemistry. Graft survival was enhanced when recipients were subjected to 40% hepatectomy.
Hepatic PC:stromal cell cocultures may prove useful in the restoration of liver function either by direct transplantation
using PGA or similar templates, or as extracorporeal devices, using nylon screens. 相似文献
12.
When thermodynamic properties of a pure substance are transformed to reduced form by using both critical- and triple-point values, the corresponding experimental data along the whole liquid-vapor coexistence curve can be correlated with a very simple analytical expression that interpolates between the behavior near the triple and the critical points. The leading terms of this expression contain only two parameters: the critical exponent and the slope at the triple point. For a given thermodynamic property, the critical exponent has a universal character but the slope at the triple point can vary significantly from one substance to another. However, for certain thermodynamic properties including the difference of coexisting densities, the enthalpy of vaporization, and the surface tension of the saturated liquid, one finds that the slope at the triple point also has a nearly universal value for a wide class of fluids. These thermodynamic properties thus show a corresponding apparently universal behavior along the whole coexistence curve. 相似文献
13.
Román LU Guerra-Ramírez D Morán G Martínez I Hernández JD Cerda-García-Rojas CM Torres-Valencia JM Joseph-Nathan P 《Organic letters》2004,6(2):173-176
[structure: see text] The triterpenes 8,14-seco-oleana-8(26),13-dien-3beta-ol (1) and its acetyl derivative 2 were isolated from Stevia viscida and Stevia eupatoria, respectively. Their structures were elucidated by 2D NMR, including carbon-carbon connectivity experiments, and confirmed by X-ray diffraction analysis of ketone 3. The absolute configuration was determined by NMR analysis of the Mosher esters of 1. The biogenetic implications of the new substances are discussed. 相似文献
14.
Carabias Martínez R Rodríguez Gonzalo E Fernández Laespada M Sánchez San Román F 《Journal of chromatography. A》2000,869(1-2):471-480
The pollution of agricultural land due to herbicides was assessed in the Guare?a and Almar river basins, situated in the provinces of Zamora and Salamanca (Spain). A set of fifteen herbicides, including triazines, ureas, amides and others, was selected owing to their frequency of use, the amounts used, their toxicity and their persistence in the environment. Solid-phase extraction with polymeric cartridges, followed by HPLC with diode-array detection, were used to monitor the herbicides. This technique was chosen owing to the wide range of functionality and polarity of the analytes under study. The detection limits obtained were in the 0.004-0.025 microg/l range (lambda=220 nm). Surface and ground waters, taken from different locations in the basins, were analyzed over a 6-month period. The presence of six out of the fifteen herbicides monitored--chlortoluron, atrazine, terbutryn, alachlor, diflufenican and fluazifop-butyl--was detected in several samples at levels ranging from the detection limit to 1.2 microg/l. The relationship of these herbicides to the agricultural activities of the zone is discussed. 相似文献
15.
New physically adsorbed polymer coating for reproducible separations of basic and acidic proteins by capillary electrophoresis 总被引:1,自引:0,他引:1
In this work, a new physically adsorbed coating for capillary electrophoresis (CE) is presented. The coating is based on a N,N-dimethylacrylamide-ethylpyrrolidine methacrylate (DMA-EPyM) copolymer synthesized in our laboratory. The capillary coating is simple and easy to obtain as only requires flushing the capillary with a polymer aqueous solution for 2 min. It is shown that by using these coated capillaries the electrostatic adsorption of a group of basic proteins onto the capillary wall is significantly reduced allowing their analysis by CE. Moreover, the DMA-EPyM coating provides reproducible separations of the basic proteins with RSD values for migration times lower than 0.75% for the same day (n = 5) and lower than 3.90% for three different days (n = 15). Interestingly, the electrical charge of the coated capillary wall can be modulated by varying the pH of the running buffer which makes possible the analysis of basic and acidic proteins in the same capillary. The usefulness of this coating is further demonstrated via the reproducible separation of whey (i.e. acidic) proteins from raw milk. The coating protocol should be compatible with both CE in microchips and CE-MS of different types of proteins. 相似文献
16.
Andrés R Galakhov MV Gómez-Sal MP Martín A Mena M del Carmen Morales-Varela M Santamaría C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):805-811
The photochemical treatment of mu(3)-alkylidyne complexes [[TiCp*(mu-O)](3)(mu(3)-CR)] (R=H (1), Me (2), Cp*=eta(5)-C(5)Me(5)) with the amines (2,6-Me(2)C(6)H(3))NH(2), Et(2)NH, and Ph(2)NH and the imine Ph(2)C=NH leads to the partial hydrogenation of the alkylidyne moiety that is supported on the organometallic oxide, [Ti(3)Cp*O(3)], and the formation of new oxoderivatives [[TiCp*(3)(mu-CHR)(R'NR")] (R"=2,6-Me(2)C(6)H(3), R'=H, R=H (3), Me (4); R'=R"=Et, R=H (5), Me (6); R'=R"=Ph, R=H (7), Me (8)) and [[TiCp*(mu-O)](3)(mu-CHR)(N=CPh(2))] (R=H (9), R=Me (10)), respectively. A sequential transfer hydrogenation process occurs when complex 1 is treated with tBuNH(2), which initially gives the mu-methylene [[TiCp*(mu-O)](3)(mu-CH(2))(HNtBu)] (11) complex and finally, the alkyl derivative [[TiCp*(mu-O)](3)(mu-NtBu)Me] (12). Furthermore, irradiation of solutions of the mu(3)-alkylidyne complexes 1 or 2 in the presence of diamines o-C(6)H(4)(NH(2))(2) and H(2)NCH(2)CH(2)NH(2) (en) affords [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(6)H(4)NH)] (13) and [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(2)H(4)NH)] (14) by either methane or ethane elimination, respectively. In the reaction of 1 with en, an intermediate complex [[TiCp*(mu-O)](3)(mu-CH(2))(NHCH(2)CH(2)NH(2))] (15) is detected by (1)H NMR spectroscopy. Thermal treatment of the complexes 4-10 quantitatively regenerates the starting mu(3)-alkylidyne compounds and the amine R'(2)NH or the imine Ph(2)C=NH; however, heating of solutions of 3 or 4 in [D(6)]benzene or a equimolecular mixture of both at 170 degrees C produces methane, ethane, or both, and the complex [[TiCp*(mu-O)](3)[mu(3)-eta(2)-NC(6)H(3)(Me)CH(2)]] (16). The molecular structure of 8 has been established by single-crystal X-ray analysis. 相似文献
17.
Romá F Riccardo JL Ramirez-Pastor AJ 《Langmuir : the ACS journal of surfaces and colloids》2005,21(6):2454-2459
Experimental adsorption isotherms of five n-paraffins (ethane, propane, butane, pentane, and hexane) in 5A zeolite were described by means of a statistical thermodynamics model for linear adsorbates (MLA) developed by Ramirez-Pastor et al. (1999) and compared with the well-known multisite Langmuir model (MSL) of Nitta et al. (1984). The experimental data, obtained by different authors in a wide range of temperatures and pressures, were correlated by using an algorithm of multiple fitting. Two main conclusions were drawn from the analysis of experimental data: (i) for small molecules (ethane, propane), MLA is the more accurate model, validating the hypothesis of the linear rigid character of the adsorbate and reinforcing previous results obtained from the analysis of computational experiments developed for dimers and linear trimers; (ii) for large molecules (n-butane, n-pentane, n-hexane), the better performance of the MSL model suggests that the admolecules adsorb in a nonlinear structure. The isosteric heat of adsorption dependence on the number of carbons obtained from our study, ranging between 23.84 kJ/mol for ethane and 59.26 kJ/mol for hexane, showed a very good agreement with previous results reported in the literature, confirming the consistency of our analysis. 相似文献
18.
Comparison
of the fragility index of different eudragit polymers determined by activation
enthalpies
Gabriella Csóka A. Gelencsér Dorottya Kiss Eszter Pásztor I. Klebovich Romána Zelkó 《Journal of Thermal Analysis and Calorimetry》2007,87(2):469-473
The present study aimed to apply fragility
index (m) of polymers in the determination
of the optimal amount of plasticizer in polymer films. The fragility index
of different Eudragit polymers (RS, RL, EPO) was assessed by differential
scanning calorimerty (DSC), applying the Arrhenius connection (logq–1/T
g).
The fragility of Eudragit EPO films proved to be the highest, while in the
case of RS and RL, the increase of the alkyl-chain length caused the increase
of fragility. Studying the effect of plasticizer (triethyl citrate, TEC) on
the m value of Eudragit RL and RS films,
a near linear reduction of the fragility index could be observed between 5–30%
TEC concentration, but above 30%, this value leveled out to constant. 相似文献
19.
Román-Bravo P López-Cardoso M y García PG Höpfl H Cea-Olivares R 《Chemical communications (Cambridge, England)》2004,(17):1940-1941
The molecular structures of two lipophilic polyion aggregates derived from tetraphenyl imidodiphosphinate are described: [Na(crown ether)][MNa(2)[Ph(2)P(O)NP(O)Ph(2)](4)] with crown ether = 15-crown-5 for 1and benzo-15-crown-5 for (M = Na(+) for 1 and Na(H(2)O)(+) for 2). 相似文献
20.
A. Villamarín I. J. Sola M. V. Collados J. Atencia O. Varela B. Alonso C. Méndez J. San Román I. Arias L. Roso M. Quintanilla 《Applied physics. B, Lasers and optics》2012,106(1):135-141
We have designed and developed a pulse compressor with volume transmission holographic gratings to be implemented in post-compression experiments based on filamentation in gases. Pulse compression down to 13?fs has been demonstrated. The gratings have been recorded in commercial PFG-04 dichromated gelatin emulsions with a recording wavelength of 532?nm, attaining sufficient index modulation to achieve high efficiency when they are illuminated by an 800-nm laser. 相似文献