全文获取类型
收费全文 | 78114篇 |
免费 | 352篇 |
国内免费 | 375篇 |
专业分类
化学 | 24316篇 |
晶体学 | 789篇 |
力学 | 6724篇 |
数学 | 31970篇 |
物理学 | 15042篇 |
出版年
2018年 | 10431篇 |
2017年 | 10260篇 |
2016年 | 6077篇 |
2015年 | 853篇 |
2014年 | 295篇 |
2013年 | 323篇 |
2012年 | 3786篇 |
2011年 | 10500篇 |
2010年 | 5646篇 |
2009年 | 6049篇 |
2008年 | 6592篇 |
2007年 | 8760篇 |
2006年 | 237篇 |
2005年 | 1305篇 |
2004年 | 1539篇 |
2003年 | 1970篇 |
2002年 | 1008篇 |
2001年 | 250篇 |
2000年 | 292篇 |
1999年 | 154篇 |
1998年 | 192篇 |
1997年 | 152篇 |
1996年 | 206篇 |
1995年 | 120篇 |
1994年 | 82篇 |
1993年 | 98篇 |
1992年 | 58篇 |
1991年 | 64篇 |
1990年 | 49篇 |
1989年 | 60篇 |
1988年 | 61篇 |
1987年 | 58篇 |
1986年 | 57篇 |
1985年 | 46篇 |
1984年 | 44篇 |
1983年 | 37篇 |
1982年 | 43篇 |
1981年 | 38篇 |
1980年 | 48篇 |
1979年 | 46篇 |
1978年 | 35篇 |
1973年 | 26篇 |
1914年 | 45篇 |
1913年 | 40篇 |
1912年 | 40篇 |
1910年 | 24篇 |
1909年 | 41篇 |
1908年 | 40篇 |
1907年 | 32篇 |
1904年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Ladislav Halás Andrej Oriňák Abubaker Sharif Monika Ádámová Juraj Ladomerský 《Central European Journal of Chemistry》2005,3(3):570-582
Acrylate monomers methylmethacrylate (MMA) and cyclohexylmethacrylate (CHMA) bioaccumulation has been determined in aquatic
organism, algae (Chlorella kessleri). Algae were collected in amount of 0.4 mg and directly injected to the pyrolytical cell. In algae bodies accumulated monomers
were analysed by pyrolysis gas chromatography (Py-GC) and pyrolysis gas chromatography coupled with mass spectrometry (Py-GC/MS).
Traces of the accumulated monomers in algae body can be determined after 1-, 2-, 3-weeks of incubation. Maximum content of
MMA was determined after 3-week of experiment, contrariwise in the case of CHMA after 2-week exposition. Relationship with
pyrolysis temperature has also been studied. 相似文献
992.
Microscale sample deposition onto hydrophobic target plates for trace level detection of neuropeptides in brain tissue by MALDI-MS 总被引:1,自引:0,他引:1
Wei H Dean SL Parkin MC Nolkrantz K O'Callaghan JP Kennedy RT 《Journal of mass spectrometry : JMS》2005,40(10):1338-1346
A sample preparation method that combines a modified target plate with a nanoscale reversed-phase column (nanocolumn) was developed for detection of neuropeptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). A gold-coated MALDI plate was modified with an octadecanethiol (ODT) self-assembled monolayer to create a hydrophobic surface that could concentrate peptide samples into a approximately 200-500-microm diameter spot. The spot sizes generated were comparable to those obtained for a substrate patterned with 200-microm hydrophilic spots on a hydrophobic substrate. The sample spots on the ODT-coated plate were 100-fold smaller than those formed on an unmodified gold plate with a 1-microl sample and generated 10 to 50 times higher mass sensitivity for peptide standards by MALDI-TOF MS. When the sample was deposited on an ODT-modified plate from a nanocolumn, the detection limit for peptides was as low as 20 pM for 5-microl samples corresponding to 80 amol deposited. This technique was used to analyze extracts of microwave-fixed tissue from rat brain striatum. Ninety-eight putative peptides were detected including several that had masses matching neuropeptides expected in this brain region such as substance P, rimorphin, and neurotensin. Twenty-three peptides had masses that matched peaks detected by capillary liquid chromatography with electrospray ionization MS. 相似文献
993.
V. L Gein E. N. Bezmaternykh L. F. Gein I. V. Krylova 《Chemistry of Heterocyclic Compounds》2004,40(10):1332-1334
It has been shown that 5-aryl-3-arylamino-4-benzoyl-1H-3-pyrrolin-2-ones cyclize in the presence of conc. H2SO4 to give pyrrolo[3,4-b]quinolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1543–1545, October, 2004. 相似文献
994.
Thanwarat Pipatchanchai Kawee Srikulkit 《Journal of Sol-Gel Science and Technology》2007,44(2):119-123
Water repellency of woven cotton fabric was achieved by coating with the aqueous dispersion containing organosilane agent
(HDTMS) and fumed silica. The coating agents were applied using padding method and then followed by batching the coated fabric
at the ambient temperature for 24 h to allow the condensation reaction between HDTMS silanol group and fumed silica silanol
group, rendering silica particles hydrophobic. An ultrasonicator was employed to prepare the homogenous coating dispersion.
The water repellency evaluated by water contact angle determination which showed the contact angle over 110° was obtained
with low amount of applied HDTMS of 1 wt%. The effect of fumed silica addition on an increase in fiber surface roughness geometry
showed the influential result in improving the water contact angle. From durability to washing test, the hydrophobic coatings
evidenced from SEM and ATR/FTIR remained adhering to fiber surface, indicating the durability. After washing, the coating
on the fabric with fumed silica addition appeared to be scatter particles which made a contribution to the higher contact
angle value when compared to sheet-like layer coating in case of HDTMS coating alone. 相似文献
995.
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
996.
Mixed micelles formed by zwitterionic surfactant dimethyldodecylammniopropane sulfonate and short-chain phospholipid 1,2-diheptanoyl-sn-glycero-3-phosphocholine in different proportions in an aqueous medium have been studied physicochemically at an air/water interface and in the bulk by using interfacial tension and pyrene fluorescence intensity measurements, respectively. The critical micellar concentration and free energies of micellization and of interfacial adsorption have been determined. The interfacial study reveals that a mixed monolayer is formed at the air/water interface by the adsorption of surfactant and phospholipid monomers. This has been confirmed by evaluating the interfacial parameters; the maximum surface excess, the minimum area per molecule of a surface-active compound, and the Gibbs surface excess related to surface pressure. The nonideality of mixing, expressed in the terms of the regular solution interaction parameter, #, has negative values over the whole mole fraction range. The negative # values indicate the mutual synergism between the surfactant and phospholipid monomers. The equilibrium distribution of components between micelle and monomer phases was evaluated using a theoretical treatment based on excess thermodynamics quantities evaluated by Motomura's formulation. 相似文献
997.
Ronald Callahan Orlando Ramirez Kerstin Rosmarion Robert Rothchild Kevin C. Bynum 《Journal of heterocyclic chemistry》2005,42(5):889-898
A series of hindered Diels‐Alder adducts have been prepared from phencyclone, 1 , with various unusual symmetrical cyclic dienophiles, including cyclohexene, 2a ; vinylene carbonate, 2b ; vinylene trithiocarbonate, 2c ; and the N‐aryl maleimides: N‐(4‐dimethylamino‐3,5‐dinitrophenyl)maleimide (“Tuppy's maleimide”), 2d ; and N‐[3,5‐bis(trifluoromethyl)phenyl]maleimide, 2e . The highly hindered adducts, 3a‐e , respectively, were extensively characterized by one‐ and two‐dimensional NMR methods, observing proton, carbon‐13 and fluorine‐19. High resolution COSY45 spectra permitted rigorous proton NMR assignments. The 2D heteronuclear C‐H chemical shift correlation spectra (HETCOR, XHCORR) were obtained for adducts 3a‐d , allowing specific assignments for protonated carbons. Corrections to earlier proton NMR assignments for the vinylene carbonate adduct are given; results of the gated decoupling 13C NMR experiment for this adduct supported endo adduct stereochemistry. Relative proton chemical shifts for bridgehead phenyls of adduct 3c appeared anomalous relative to other adducts, suggesting possible special anisotropic interactions (with endocyclic sulfur or other anisotropic groups in the product) due to the unusual calculated orientation of the phenyls. The unsubstituted bridgehead phenyls in all adducts were shown to exhibit slow exchange limit (SEL) 1H and 13C spectra on the NMR timescales at ambient temperatures (7 tesla) showing slow rotations about the C(sp3)‐C(aryl sp2) bonds. The rapid rotation of the N‐aryl rings of the maleimide adducts was indicated by fast exchange limit spectra, suggesting that ortho substitution of the N‐aryl ring may be necessary to slow this rotation to the SEL regime. Ab initio geometry optimizations at the Hartree‐Fock level were carried out for each adduct, with the 6‐31G* basis sets. Appreciable geometry differences were seen in calculated structures, and significant NMR chemical shift differences were experimentally observed, depending on the nature of the groups attached to the (Z)‐HC=CH moiety of the dienophiles. 相似文献
998.
With P(CH3)3 as the probe molecule adsorbed on titanium silicalite (TS-1) zeolite, the special and important role of T12 site in MFI-type zeolite was clearly elucidated. There are altogether three active sites present in TS-1 zeolite with Ti at the T12 site. Owing to the preferential adsorption of probe molecules on the first Brönsted acidic site, the Ti12 center will probably fail to show Lewis acidity. The ionic [HP(CH3)3]+ species can be stabilized by the first or second Brönsted acidic site, with the former energetically favored. The latter was formed through the transfer of the ionic [HP(CH3)3]+ species from the first to the second Brönsted acidic site. 相似文献
999.
Young Hyun Cho Wanno Lee Kun Ho Chung Geun Sik Choi Chang Woo Lee 《Journal of Radioanalytical and Nuclear Chemistry》2007,274(3):531-538
The seasonal variation of the 7Be activities in air and the size distribution of the 7Be aerosols were studied by using a continuous air sampler and a five stage cascade impactor. The mean monthly activity level
of 7Be at the Korea Atomic Energy Research Institute (KAERI) site varied from 0.5 to 4.8 Bq·m−3 and revealed a seasonal variation, in which the 7Be activity levels were high in winter and low in summer. The mass size distribution showed a bi-modal distribution with a
higher peak around 0.49 μm and a smaller peak between 3 μm and 7.2 μm. The activity median aerodynamic diameter (AMAD) decreased
with increasing ambient 7Be concentrations. The mean residence times by using a mean growth rate of 0.004 μm·h−1 were estimated to be 2.5–6.4 days. The AMAD has an increasing tendency with higher relative humidity. It seemed that the
high humidity condition facilitated the growth of the aerosol, resulting in increased deposition rates of the aerosols and
the low 7Be content in the surface air. The AMAD of the 7Be aerosols increased with an increasing temperature, but the temperature dependency of AMAD should be explained with geological
and meteorological conditions. 相似文献
1000.