全文获取类型
收费全文 | 27364篇 |
免费 | 602篇 |
国内免费 | 113篇 |
专业分类
化学 | 15520篇 |
晶体学 | 188篇 |
力学 | 818篇 |
综合类 | 9篇 |
数学 | 3789篇 |
物理学 | 7755篇 |
出版年
2023年 | 129篇 |
2022年 | 365篇 |
2021年 | 452篇 |
2020年 | 403篇 |
2019年 | 364篇 |
2018年 | 448篇 |
2017年 | 400篇 |
2016年 | 694篇 |
2015年 | 600篇 |
2014年 | 675篇 |
2013年 | 1108篇 |
2012年 | 1394篇 |
2011年 | 1584篇 |
2010年 | 905篇 |
2009年 | 860篇 |
2008年 | 1349篇 |
2007年 | 1295篇 |
2006年 | 1168篇 |
2005年 | 1594篇 |
2004年 | 1617篇 |
2003年 | 1144篇 |
2002年 | 795篇 |
2001年 | 656篇 |
2000年 | 598篇 |
1999年 | 393篇 |
1998年 | 326篇 |
1997年 | 325篇 |
1996年 | 383篇 |
1995年 | 347篇 |
1994年 | 344篇 |
1993年 | 355篇 |
1992年 | 352篇 |
1991年 | 284篇 |
1990年 | 230篇 |
1989年 | 216篇 |
1988年 | 204篇 |
1987年 | 183篇 |
1986年 | 184篇 |
1985年 | 245篇 |
1984年 | 229篇 |
1983年 | 199篇 |
1982年 | 216篇 |
1981年 | 201篇 |
1980年 | 187篇 |
1979年 | 160篇 |
1978年 | 183篇 |
1977年 | 150篇 |
1976年 | 145篇 |
1974年 | 141篇 |
1973年 | 128篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
The reaction of aluminium(III) with Hydroxynaphtol Blue (HNB) in aqueous media at apparent pH 5.5 results in a red complex that is stable for at least 4 hr. Beer's Law is obeyed up to 1.6 microg/ml of aluminium(III) with an apparent molar absorptivity of 1.66 x 10(4) l.mol(-1). cm(-1) at 569 nm. This paper proposes procedures for aluminium(III) determination by ordinary and first-derivative spectrophotometry. The results demonstrated that the linear dynamic range is 0.03-1.60 microg/ml for ordinary spectrophotometry and 11.8-320.0 ng/ml for first derivative spectrophotometry. The HNB is not selectivity for aluminium, but the addition of EDTA allows the aluminium determination in the presence of accepted amounts of Ca(II), Mg(II), Mn(II), Ba(II), Sr(II), Cd(II), Pb(II), La(III), In(III), Bi(III) and Zn(II). The interference of Cu(II) and Hg(II) can be masked by thiosulphate. Ions such as UO(2)(II), Mo(VI), Co(II), Ti(IV) and PO(4)(III) do interfere seriously. This method was applied for aluminium determination in copper-base alloy, zinc-base alloy, magnesium-base alloy, iron ore, manganese ore, cement, dolomite, feldspar and limestone. The results indicated high accuracy and precision. 相似文献
982.
Inductively coupled plasma optical emission spectrometry (ICP-OES) was applied to the analysis of major and minor elements of Ni-Nb alloys obtained by aluminothermic reduction process. Digestion of samples was made using a mixture of HF+HNO3. Minor and trace elements were determined without matrix separation. The precision for all constituents was <3%. Recoveries for the analyte-spiked samples were 95%. 相似文献
983.
Pinto FG Andrada D Magalhães CG Nunes BR de Amorim FR Franco MB Saint'pierre TD da Silva JB Curtius AJ 《Analytical and bioanalytical chemistry》2005,383(5):825-832
Different chemical modifiers for use with electrothermal atomic absorption spectrometry (ET AAS) were investigated in relation
to determining the selenium in human urine samples. The samples were diluted in a solution containing 1% v/v HNO3 and 0.02% m/v cetyltrimethylammonium chloride (CTAC). Studying the modifiers showed that the use of either Ru or Ir as the
permanent modifier gave low sensitivity to Se and the peak shape was very noisy, while Zr or Rh gave no peak at all. The same
occurred when Zr was used in solution. For mixtures of permanent modifiers, Ir plus Rh or Zr plus Rh gave very low sensitivity,
Zr plus Rh with co-injection of Ir in solution was also not efficient, Zr plus Rh in solution gave good sensitivity, but the
best results were obtained with a mixture of Zr and Rh as the permanent modifier and co-injection of Rh in solution. Using
this last modifier, the following dilutions with the HNO3 and CTAC were studied: 1:1, 1:2, 1:3 and 1:4. The best dilution was 1:1, which promoted good sensitivity and a more defined
peak shape and made it possible to correct for the background using a deuterium arc lamp. Under these conditions, a characteristic
mass of 26±0.2 pg was obtained for Se in aqueous solution. Six certified urine samples were analyzed using matrix matching
calibration and the measured concentrations were in agreement with the certified values, according to a t-test at the 95%
confidence level. Recovery tests were carried out and the recoveries were in the range 100–103%, with relative standard deviation
better than 9%. The limit of detection (LOD, 3 sd, n=10) was 3.0 μg L−1 in the sample. The treated graphite tube could be used for at least 600 atomization cycles without significant alteration
of the analytical signal. 相似文献
984.
985.
Albrecht M Mirtschin S de Groot M Janser I Runsink J Raabe G Kogej M Schalley CA Fröhlich R 《Journal of the American Chemical Society》2005,127(29):10371-10387
The ligands 4-7-H(2) were used in coordination studies with titanium(IV) and gallium(III) ions to obtain dimeric complexes Li(4)[(4-7)(6)Ti(2)] and Li(6)[(4/5a)(6)Ga(2)]. The X-ray crystal structures of Li(4)[(4)(6)Ti(2)], Li(4)[(5b)(6)Ti(2)], and Li(4)[(7a)(6)Ti(2)] could be obtained. While these complexes are triply lithium-bridged dimers in the solid state, a monomer/dimer equilibrium is observed in solution by NMR spectroscopy and ESI FT-ICR MS. The stability of the dimer is enhanced by high negative charges (Ti(IV) versus Ga(III)) of the monomers, when the carbonyl units are good donors (aldehydes versus ketones and esters), when the solvent does not efficiently solvate the bridging lithium ions (DMSO versus acetone), and when sterical hindrance is minimized (methyl versus primary and secondary carbon substituents). The dimer is thermodynamically favored by enthalpy as well as entropy. ESI FT-ICR mass spectrometry provides detailed insight into the mechanisms with which monomeric triscatecholate complexes as well as single catechol ligands exchange in the dimers. Tandem mass spectrometric experiments in the gas phase show the dimers to decompose either in a symmetric (Ti) or in an unsymmetric (Ga) fashion when collisionally activated. The differences between the Ti and Ga complexes can be attributed to different electronic properties and a charge-controlled reactivity of the ions in the gas phase. The complexes represent an excellent example for hierarchical self-assembly, in which two different noncovalent interactions of well balanced strengths bring together eleven individual components into one well-defined aggregate. 相似文献
986.
We develop nonorthogonal projectors, called L?wdin projectors, to construct an effective donor-acceptor system composed of localized donor (D) and acceptor (A) states of a long-distance electron transfer problem. When these states have a nonvanishing overlap with the bridge states these projectors are non-Hermitian and there are various possible effective two-level systems that can be built. We show how these can be constructed directly from the Schr?dinger or Dyson equation projected onto the D-A subspace of the Hilbert space and explore these equations to determine the connection between Hamiltonian and Green function partitioning. We illustrate the use of these effective two-level systems in estimating the electron transfer rate in the context of a simple electron transfer model. 相似文献
987.
A microwave assisted digestion procedure has been developed for dissolution of fly ash samples prior to the inductively coupled plasma-mass spectrometric determination of their elemental composition. The developed methodology was validated by carrying out the analysis of two high-silicate containing reference materials (CRM 134R sewage amended soil and NIES JR 1 rock) and by means of the comparison between results found by microwave-assisted digestion and ICP-MS of fly ash samples with those found by neutron activation analysis (NAA) for Sb, Cs, Cr, Co, Fe, U and Zn determination. The method developed can be recommended for routine multielement analysis of fly ash. 相似文献
988.
Analytically packed columns prepared with Versamid-930, Versamid-900, XE-60, and OV-225 as stationary phases were examined for quantitative gas-liquid chromatography of the potent monamine oxydase inhibitor (MAOI) drugs iproniazid and iproclozide. With the aid of chemically related substances as internal standards, response ratios were determined and linearities calculated by regression analysis. Using the 2-butyl analogs of compounds all four column systems permit quantitation of iproniazid and iproclozide with a percent standard deviation sigmaK of about 1% or less. 相似文献
989.
Heering HA Wiertz FG Dekker C de Vries S 《Journal of the American Chemical Society》2004,126(35):11103-11112
Cyclic voltammetry shows that yeast iso-1-cytochrome c (YCC), chemisorbed on a bare gold electrode via Cys102, exhibits fast, reversible interfacial electron transfer (k(0) = 1.8 x 10(3) s(-1)) and retains its native functionality. Vectorially immobilized YCC relays electrons to yeast cytochrome c peroxidase, and to both cytochrome cd(1) nitrite reductase (NIR) and nitric oxide reductase from Paracoccus denitrificans, thereby revealing the mechanistic properties of these enzymes. On a microelectrode, we measured nitrite turnover by approximately 80 zmol (49 000 molecules) of NIR, coadsorbed on 0.65 amol (390 000 molecules) of YCC. 相似文献
990.
Puertas AM Fernández-Barbero A Javier de Las Nieves F Rull LF 《Langmuir : the ACS journal of surfaces and colloids》2004,20(22):9861-9867
The structure of colloidal clusters formed by long-range attractive interactions under diluted conditions is studied by means of Monte Carlo simulations. For a not-too-long attraction range, clusters show self-similar internal structure with lower density than that typical for diffusive aggregation. For long-range interactions, low kappa, nonfractal clusters are formed (dense at short scales but open at long ones). The dependence on the volume fraction shows that more-compact clusters are grown the higher the colloidal density for diffusive aggregation and attraction-driven aggregation in the fractal regime. The whole trend is explained in terms of the interpenetration among aggregates. In attraction-driven aggregations, the interpenetration of clusters competes with aggregation in the tips of the clusters, causing low-density clusters. 相似文献