全文获取类型
收费全文 | 1490篇 |
免费 | 66篇 |
国内免费 | 4篇 |
专业分类
化学 | 1299篇 |
晶体学 | 4篇 |
力学 | 9篇 |
数学 | 120篇 |
物理学 | 128篇 |
出版年
2023年 | 20篇 |
2022年 | 27篇 |
2021年 | 40篇 |
2020年 | 39篇 |
2019年 | 26篇 |
2018年 | 28篇 |
2017年 | 26篇 |
2016年 | 52篇 |
2015年 | 60篇 |
2014年 | 72篇 |
2013年 | 90篇 |
2012年 | 105篇 |
2011年 | 103篇 |
2010年 | 61篇 |
2009年 | 56篇 |
2008年 | 96篇 |
2007年 | 99篇 |
2006年 | 87篇 |
2005年 | 78篇 |
2004年 | 57篇 |
2003年 | 44篇 |
2002年 | 57篇 |
2001年 | 12篇 |
2000年 | 29篇 |
1999年 | 17篇 |
1998年 | 15篇 |
1997年 | 10篇 |
1996年 | 8篇 |
1995年 | 18篇 |
1994年 | 7篇 |
1993年 | 9篇 |
1992年 | 9篇 |
1991年 | 13篇 |
1990年 | 10篇 |
1989年 | 9篇 |
1988年 | 5篇 |
1987年 | 11篇 |
1986年 | 7篇 |
1985年 | 10篇 |
1984年 | 11篇 |
1983年 | 9篇 |
1982年 | 1篇 |
1981年 | 6篇 |
1980年 | 1篇 |
1979年 | 4篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1961年 | 1篇 |
排序方式: 共有1560条查询结果,搜索用时 31 毫秒
21.
Petra Spitzer Bruno Rossi Yves Gaignet Stéphane Mabic Uwe Sudmeier 《Accreditation and quality assurance》2005,10(3):78-81
There is currently a major issue with the calibration of conductivity meters used for high purity water: the lack of availability of a reference material or reference methods for low conductivity ranges (conductivity below 1 S cm–1 at 25.0 °C, resistivity >1 M cm at 25.0 °C). This paper describes the current status of conductivity measurements in high purity water. A new and improved approach, currently being investigated, should allow us to make the calibration of conductivity meters used for low conductivity ranges traceable to the SI.Milipore, Milli-Q and Elix are registered trademarks of Millipore Corporation. 相似文献
22.
Michael?Sch?ferlingEmail author Michael?Riepl Petra?Pavlickova Hubert?Paul Dev?Kambhampati Bo?Liedberg 《Mikrochimica acta》2003,142(4):193-203
Two different types of -substituted alkanethiol/disulfide compounds have been used to prepare monolayer architectures on gold serving as platforms for the immobilization of receptor probe molecules – antibodies. These are: (i) carboxylic acid alkanethiols post-reacted with amino biotin to generate streptavidin surfaces, and (ii) N-hydroxysuccinimide-terminated disulfide surfaces. The properties of the monolayers, with and without attached receptor probe molecules, were analysed using infrared spectroscopy, ellipsometry, fluorescence scanning and atomic force microscopy. Several experimental parameters, such as condensation reagents, additives, probe and target concentrations and immobilization time, were systematically varied to determine the dynamic range and to optimize the sensitivity and signal-to-noise ratio of the biochip platforms. Fluorescence screening using Cy5-labelled antigens finally demonstrated that both surfaces could be successfully employed to immobilize the antibodies. The pros and cons of the two approaches are also discussed.Received November 15, 2002; accepted March 25, 2003
Published online July 28, 2003 相似文献
23.
Crystalline title compound (1) prepared from aqueous solution of theophylline and 1,4-diaminobutane has been structurally and thermally characterized. Both the two-step TG decomposition curve and elemental analysis of the hexagonal crystals show that it consists of theophylline and 1,4-diaminobutane in 2:1 molar ratio. Actually, presence of one type of both theophyllinate anions and 1,4-diammoniumbutane dication have been indicated by FTIR spectroscopy. The molecular structure of lattice compound (1) has been determined by single crystal X-ray diffraction, where the hydrogen positions have been obtained from differential Fourier maps. It has confirmed that the crystal is really built up from these ionic constituents bound together with an extensive net of hydrogen bonds. The coupled TG-FTIR analysis of the evolved gases has revealed that the diamine is released as a whole molecule in the first decomposition step. Clathrate 1 and the proton migration in it might serve as a structural model of solid aminophylline whose crystal structure is still unknown. 相似文献
24.
Žaneta Mesíková Petra Šulcová M. Trojan 《Journal of Thermal Analysis and Calorimetry》2006,84(3):733-736
Synthesis of the green
spinel pigment Co0.46Zn0.55(Ti0.064Cr0.91)2O4 by a novel two-step method of preparation have
been investigated. Inorganic pigments are almost always prepared by a solid
state reaction. It is classical ceramic method which used oxides, hydroxides
or carbonates as precursors. The reaction is performed at temperature higher
than 1300°C and an agent of mineralization is usually present. The presented
novel method of preparation decreases the calcining temperature necessary
for reaching of bright and clear hue of the pigments prepared. Main attention
was focused on the influence of two types of titanium raw materials on the
temperature region of the spinel structure formation and on the colour properties
of the pigments. The mixture of precursors with TiO2
gives a one-phase system when calcining at 1100°C but the colour properties
are more interesting at 1150°C. Thermal stability of this pigment is limited
by temperature 1300°C. This temperature is connected with partial oxidation
of Cr(III) to Cr(VI). Thermal analysis provided the first information about
the temperature region of the pigment formation and determined the thermal
stability of pigment. 相似文献
25.
Petra Hoffman Siegfried Hünig Leonhard Walz Karl Peters Hans-Georg von Schnering 《Tetrahedron》1995,51(48):13197-13216
Azo compounds 1 and 3 containing a CC-double bond in a parallel but distant position are quatemized by Me3OBF4 to 1,MeBF4 and 3,MeBF4, whereas MeI produces the cage compounds 2,HX and 4,HX. These [3+2] cycloadducts also are quantitatively formed from 1,MeBF4 and 3,MeBF4 with catalytic amounts of azo compounds. Intermolecular [3+2] cycloadditions occur with a mixture of DBH (5) or DBO (8), MeI and a variety of alkenes (→ HI) salts of (6, 7, 9 — 12). The intermediate azomethineimines, if stabilized by a fluorenylidene group, can be isolated (20, 22,24), but not, however, in the presence of a close parallel CC-bond (25 → 26). 相似文献
26.
Helmut Viernstein Petra Weiss-Greiler Peter Wolschann 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):235-240
The solubility enhancement of triflumizole by complexation with -cyclodextrin and with dimethyl--cyclodextrin is compared with respect to the different physico-chemical properties of the host molecules. Although the inclusion reaction constants are rather similar for both complexation reactions, a completely different temperature dependence of the host-guest interaction is observed, which indicates a change of the reaction mechanisms. Moreover, the influence of ethanol as cosolvent is studied. 相似文献
27.
Petra J. W. Pouwels Robert Kaptein Rosemarie F. Hartman Seth D. Rose 《Photochemistry and photobiology》1995,61(6):575-583
A series of photo-CIDNP (chemically induced dynamic nuclear polarization) experiments were performed on pyrimidine monomers and dimers, using the electron-donor Nα-acetyltryptophan (AcTrp) as a photosensitizer. The CIDNP spectra give evidence for the existence of both the dimer radical anion, which is formed by electron transfer from the excited AcTrp* to the dimer, and its dissociation product, the monomer radical anion. The AcTrp spectra are completely different from those obtained with an oxidizing sensitizer like anthraquinone-2-sulfonate, because of different unpaired electron spin density distributions in pyrimidine radical anion and cation. In the spectra of the anti (1,3-dimethyluracil) dimers, polarization is detected that originates from a spin-sorting process in the dimer radical pair, pointing to a relatively long lifetime of the dimer radical anions involved. Although the dimer radical anions of the 1,1′-trimethylene-bridged pyrimidines may have a relatively long lifetime as well, their protons have only very weak hyperfine interaction, which explains why no polarization originating from the dimer radical pair is detected. In the spectra of the bridged pyrimidines, polarized dimer protons are observed as a result of spin sorting in the monomer radical pair, from which it follows that the dissociation of dimer radical anion into monomer radical anion is reversible. A study of CIDNP intensities as a function of pH shows that a pH between 3 and 4 is optimal for observing monomer polarization that originates from spin-sorting in the monomer radical pair. At higher pH the geminate recombination polarization is partly cancelled by escape polarization arising in the same product. 相似文献
28.
The present study is concerned with the application of nonaqueous capillary electrophoresis (NACE) with electrochemical detection (ED) to the separation and quantitative determination of hydrazine (Hy) and its methyl derivatives. The best performance of NACE-ED was found when using 4 mM sodium acetate/10 mM acetic acid/methanol: acetonitrile = 1:2 as the running buffer, with a bare platinum working electrode set at +1.0 V in an end-column amperometric detection cell. The choice and ratio of suitable solvents for the separation and injection media played an essential role for the performance characteristics of the method. The limits of detection for Hy, methylhydrazine, symmetrical dimethylhydrazine, and unsymmetrical dimethylhydrazine were 5, 2, 12, and 1 ng/mL, respectively. This is between one and two orders of magnitude lower than that achieved by previously reported CE-ED methods in aqueous buffer systems in conjunction with various types of chemically modified electrodes. The practical utility of the new NACE-ED methodology is demonstrated in terms of the determination of traces of Hys in spiked environmental samples containing a wide range of explosives and related compounds. 相似文献
29.
A major issue with the electrolytic conductivity measurement for pure water is the lack of standard or reference methods.
A primary method traceable to SI and suitable for pure-water conductivity measurement was developed at the Physikalisch-Technische
Bundesanstalt (PTB), Germany, as the base for the calibration method for the conductivity measuring devices at the low conductivity
level. This paper provides a novel method to calculate the bulk resistance of pure water using impedance measured at a single
frequency, which is one of the key procedures for the primary methods. 相似文献
30.
Römer W Lam YH Fischer D Watts A Fischer WB Göring P Wehrspohn RB Gösele U Steinem C 《Journal of the American Chemical Society》2004,126(49):16267-16274
We report for the first time on pore-suspending lipid bilayers, which we call micro-black lipid membranes (micro-BLMs), based on a highly ordered macroporous silicon array. Micro-BLMs were established by first functionalizing the backside porous silicon surface with gold and then chemisorbing 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol followed by spreading 1,2-diphytanoyl-sn-glycero-3-phosphocholine dissolved in n-decane. Impedance spectroscopy revealed the formation of single lipid bilayers confirmed by a mean specific capacitance of 0.6 +/- 0.2 microF/cm2. Membrane resistances were in the G omega-regime and beyond. The potential of the system for single channel recordings was demonstrated by inserting the transmembrane domain of the HIV-1 accessory peptide Vpu(1-32), which forms helix bundles with characteristic opening states. We elucidated different amilorides as potential drugs to inhibit channel activity of Vpu. 相似文献