全文获取类型
收费全文 | 1380篇 |
免费 | 56篇 |
国内免费 | 3篇 |
专业分类
化学 | 827篇 |
晶体学 | 35篇 |
力学 | 56篇 |
数学 | 254篇 |
物理学 | 267篇 |
出版年
2024年 | 2篇 |
2023年 | 6篇 |
2022年 | 22篇 |
2021年 | 43篇 |
2020年 | 43篇 |
2019年 | 43篇 |
2018年 | 41篇 |
2017年 | 62篇 |
2016年 | 63篇 |
2015年 | 59篇 |
2014年 | 53篇 |
2013年 | 130篇 |
2012年 | 115篇 |
2011年 | 119篇 |
2010年 | 100篇 |
2009年 | 72篇 |
2008年 | 88篇 |
2007年 | 80篇 |
2006年 | 43篇 |
2005年 | 47篇 |
2004年 | 53篇 |
2003年 | 28篇 |
2002年 | 26篇 |
2001年 | 11篇 |
2000年 | 15篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 5篇 |
1996年 | 9篇 |
1995年 | 3篇 |
1994年 | 9篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1972年 | 2篇 |
1907年 | 1篇 |
排序方式: 共有1439条查询结果,搜索用时 78 毫秒
11.
Antimicrobial activity studies of the binuclear metal complexes derived from tridentate Schiff base ligands 总被引:1,自引:0,他引:1
Tümer Mehmet Köksal Hüseyin Sener M. Kasim Serin Selahattin 《Transition Metal Chemistry》1999,24(4):414-420
Three novel tridentate Schiff base ligands derived fromthe 3-hydroxysalicylaldehyde (H2L1), 4-hydroxysalicylaldehyde (H2L2) and 5-bromosalicylaldehyde (H2L3) with a new amine N-(pyridyl)-2-hydroxy-3-methoxy-5-aminobenzylamine (2) have been prepared. The ligands and their metal complexes have been characterized by elemental analyses, conductivity and magnetic susceptibility measurements, i.r., electronic absorption and 1H and 13C n.m.r. spectroscopy. All complexes are binuclear and, in some, the H2O molecules are coordinated to the metal ion. Antimicrobial activities of the ligands and their complexes have been tested against to the Bacillus subtilis IMG 22 (bacteria), Micrococcus luteus LA 2971 (bacteria) Saccharamyces cerevisiae WET 136 (yeast), and Candida albicans CCM 314 (yeast). Thermal properties of all complexes have been studied by t.g. and d.t.a techniques. 相似文献
12.
This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and
desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally
activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics,
thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better
adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter
case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed
in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated
the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption.
The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was
desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed
to higher energies of 2-CP adsorption. 相似文献
13.
Dai H Choe WS Thai CK Sarikaya M Traxler BA Baneyx F Schwartz DT 《Journal of the American Chemical Society》2005,127(44):15637-15643
We show that a protein with no intrinsic inorganic synthesis activity can be endowed with the ability to control the formation of inorganic nanostructures under thermodynamically unfavorable (nonequilibrium) conditions, reproducing a key feature of biological hard-tissue growth and assembly. The nonequilibrium synthesis of Cu(2)O nanoparticles is accomplished using an engineered derivative of the DNA-binding protein TraI in a room-temperature precursor electrolyte. The functional TraI derivative (TraIi1753::CN225) is engineered to possess a cysteine-constrained 12-residue Cu(2)O binding sequence, designated CN225, that is inserted into a permissive site in TraI. When TraIi1753::CN225 is included in the precursor electrolyte, stable Cu(2)O nanoparticles form, even though the concentrations of [Cu(+)] and [OH(-)] are at 5% of the solubility product (K(sp,Cu2O)). Negative control experiments verify that Cu(2)O formation is controlled by inclusion of the CN225 binding sequence. Transmission electron microscopy and electron diffraction reveal a core-shell structure for the nonequilibrium nanoparticles: a 2 nm Cu(2)O core is surrounded by an adsorbed protein shell. Quantitative protein adsorption studies show that the unexpected stability of Cu(2)O is imparted by the nanomolar surface binding affinity of TraIi1753::CN225 for Cu(2)O (K(d) = 1.2 x 10(-)(8) M), which provides favorable interfacial energetics (-45 kJ/mol) for the core-shell configuration. The protein shell retains the DNA-binding traits of TraI, as evidenced by the spontaneous organization of nanoparticles onto circular double-stranded DNA. 相似文献
14.
15.
Removal of methyl violet from aqueous solution by perlite 总被引:2,自引:0,他引:2
The use of perlite for the removal of methyl violet from aqueous solutions at different concentration, pH, and temperature has been investigated. Adsorption equilibrium is reached within 1 h. The capacity of perlite samples for the adsorption of methyl violet was found to increase with increasing pH and temperature and decrease with expansion and increasing acid-activation. The adsorption isotherms are described by means of the Langmuir and Freundlich isotherms. The adsorption isotherm was measured experimentally at different conditions and the experimental data were correlated reasonably well by the adsorption isotherm of Langmuir. The order of heat of adsorption corresponds to a physical reaction. It is concluded that the methyl violet is physically adsorbed onto the perlite. The removal efficiency (P) and dimensionless separation factor (R) have shown that perlite can be used for removal of methyl violet from aqueous solutions, but unexpanded perlite is more effective. 相似文献
16.
In this study, the Schiff base ligands H2L1–H2L3 and their CuII, CoII, NiII, FeIII RuIII and VOIV complexes have been prepared and characterized by spectroscopic and analytical techniques. All the complexes are mononuclear.
Keto-enol tautomeric forms of the ligands have been investigated in polar and apolar solvents. The ligands favor the keto-form
in the C7H8 and C6H14. The C–C coupling reaction of the 2,6-di-t-butylphenol has been investigated by the CoII and CuII complexes. Thermal properties of the complexes have been assessed using thermal techniques and similar properties were found.
In the FeIII and RuIII complexes, firstly, the coordinated water molecule is lost from the complex; in the second step, the chloride ion leaves
the molecule in the 300–350 °C temperature range. Finally, the complexes decompose to the appropriate metal oxide at the higher
temperature ranges. The electrochemical properties of the complexes have been studied in the two different solvents (DMF and
CH3CN). 相似文献
17.
Time series models, which are constructed from the projections of the molecular-dynamics (MD) runs on principal components (modes), are used to mimic the dynamics of two proteins: tendamistat and immunity protein of colicin E7 (ImmE7). Four independent MD runs of tendamistat and three independent runs of ImmE7 protein in vacuum are used to investigate the energy landscapes of these proteins. It is found that mean-square displacements of residues along the modes in different time scales can be mimicked by time series models, which are utilized in dividing protein dynamics into different regimes with respect to the dominating motion type. The first two regimes constitute the dominance of intraminimum motions during the first 5 ps and the random walk motion in a hierarchically higher-level energy minimum, which comprise the initial time period of the trajectories up to 20-40 ps for tendamistat and 80-120 ps for ImmE7. These are also the time ranges within which the linear nonstationary time series are completely satisfactory in explaining protein dynamics. Encountering energy barriers enclosing higher-level energy minima constrains the random walk motion of the proteins, and pseudorelaxation processes at different levels of minima are detected in tendamistat, depending on the sampling window size. Correlation (relaxation) times of 30-40 ps and 150-200 ps are detected for two energy envelopes of successive levels for tendamistat, which gives an overall idea about the hierarchical structure of the energy landscape. However, it should be stressed that correlation times of the modes are highly variable with respect to conformational subspaces and sampling window sizes, indicating the absence of an actual relaxation. The random-walk step sizes and the time length of the second regime are used to illuminate an important difference between the dynamics of the two proteins, which cannot be clarified by the investigation of relaxation times alone: ImmE7 has lower-energy barriers enclosing the higher-level energy minimum, preventing the protein to relax and letting it move in a random-walk fashion for a longer period of time. 相似文献
18.
Atom transfer radical polymerization conditions with copper(I) bromide/2,2′-bipyridine (Cu/2,2′-bpy) as the catalyst system were employed for the homopolymerization and random copolymerization of 1-phenoxycarbonyl ethyl methacrylate (PCMA) with methyl methacrylate (MMA). Temperature studies indicated that the polymerizations occurred smoothly in bulk at 110 °C. Poly(PCMA)(polydispersity index=1.27) homopolymer was characterized and then used as macroinitiator for increasing its molecular weight. The homopolymerization of PCMA was also carried out under free radical conditions using 2,2′-azobisisobutyronitrile as an initiator.The monomer and polymers were characterized by FT-IR and 1H and 13C-NMR techniques. The glass transition temperatures, the solubility parameters and average-molecular weights of the polymers were determined. Thermal stabilities of the polymers were given as compared with each other by using TGA curves. Thermal degradation products of poly(PCMA)s obtained by ATRP and free radical polymerization were compared with each other by using 1H-NMR technique. 相似文献
19.
For the determination of vanadium in biological materials by flame AAS an enrichment is described which comprises chelation with oxine and adsorption on activated carbon: The relative standard deviation for 10 g V/L was found to be 6% (n=15).Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday 相似文献
20.
An application of tissue-based electrodes aimed at eliminating interferences from co-existing electroactive constituents is described. The concept is illustrated using a zucchini-containing carbon paste electrode. The presence of the enzyme ascorbic acid oxidase (AAO) in the zucchini tissue effectively eliminates contributions from ascorbic acid, thus allowing selective measurement of dopamine or norepinephrine. In comparison with analogous enzyme-based AAO electrodes, the tissue “eliminator” electrode offers high biocatalytic stability and activity and extremely low cost. The effects of various experimental variables are studied using pulse voltammetry, chronoamperometry and flow-injection amperometry. The electrode has a useful lifetime of 4 weeks. Simultaneous elimination of uric acid interferences is obtained via the co-immobilization of uricase. Oxygen background currents are eliminated in the presence of ascorbic acid. 相似文献