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41.
42.
Benjamin Schmidt Benjamin Schrder Karsten Sonnenberg Simon Steinhauer Sebastian Riedel 《Angewandte Chemie (International ed. in English)》2019,58(30):10340-10344
Pseudohalogens are defined as molecular entities that resemble the halogens in their chemistry. While our understanding of polyhalogen chemistry has increased over the last years, research on polypseudohalogen compounds is lacking. The pseudohalogen BrCN possesses a highly pronounced σ‐hole at the bromine side of the molecule, inducing strong halogen bonding. This allows the synthesis and characterization of new polypseudohalogen anions, as shown by the single‐crystal X‐ray diffraction of [PNP][Br(BrCN)] and [PNP][Br(BrCN)3]. Both the nearly linear anion [Br(BrCN)]? and the distorted pyramidal anion [Br(BrCN)3]? were characterized by Raman spectroscopy and quantum‐chemical calculations. The behavior of the polypseudohalogen compounds in solution and as room‐temperature ionic liquids (RT‐ILs) using the [NBu4]+ cation was studied by 13C and 15N NMR spectroscopy. These types of ILs are capable of dissolving elemental gold and offer themselves as promising compounds in metal recycling. 相似文献
43.
A method for semi-automatic background estimation in energy-dispersive x-ray fluorescence spectra is outlined. Two cubic splines were investigated and the spline called the Butland interpolant was chosen for further investigation. Prior to the calculation of the spline, peak regions are set up, and suitable knots are defined outside the peak regions. To set up the peak regions, an automatic peak-search routine and a calibration equation are used. For a given peak, the latter relates the full width at half maximum (FWHM) to the peak centre. In turn, the size of the peak regions are defined by the FWHM multiplied by a constant given by the user. The method was tested on several types of spectra. It was found that the optimal size of the peak region decreased with increasing peak density. Reproducibility tests showed that the standard deviation of the summation of counts within a peak region and after background subtraction was less than would be expected from the counting statistics. 相似文献
44.
More than a dozen stationary points on the potential energy surface for the 1:1 glycine zwitterion—water complex have been investigated at Hartree-Fock or MP2 levels of theory with basis sets ranging from split valence (4-31G) to split valence plus polarization and diffuse function (6–31 + + G**) quality. Only one true minimum (GLYZWM, C1 symmetry) could be located on the potential energy surface. GLYZWM features a bridged water molecule acting as both a hydrogen bond acceptor and donor with the NH3− and CO2− units of the glycine zwitterion. The total hydrogen bond energy in GLYZWM is computed as 16 kcal/mol (MP2/6–31 ++ G** // 6–31 ++ G**, including corrections for basis set superpositions errors). The computed vibrational frequencies and normal mode forms of the GLYZWM complex resemble in many cases experimental assignments made for the glycine zwitterion in bulk water on the basis of Raman spectroscopy. © 1996 by John Wiley & Sons, Inc. 相似文献
45.
Inside Cover: Synthesis of an All‐Ferric Cuboidal Iron–Sulfur Cluster [FeIII4S4(SAr)4] (Angew. Chem. Int. Ed. 36/2018) 下载免费PDF全文
46.
Karsten Haas J. Feldmann Rainer Wennrich Hans-Joachim Stärk 《Analytical and bioanalytical chemistry》2001,370(5):587-596
The analytical performance of an axial inductively-coupled-plasma time-of-flight mass spectrometer (ICP–TOFMS) as a detector
for fast transient chromatographic signals resulting from the coupling to capillary gas chromatography (CGC) was investigated.
A cryotrapping GC–ICP–TOFMS method for the determination of volatile metal(loid) compounds (VOMs) in gases was used and the
suitability of the TOF mass analyzer for multi-elemental speciation analysis and multi-isotope ratio determinations was studied
in terms of accuracy and precision. Isotope ratios 118Sn/120Sn and 121Sb/123Sb have been determined in in-house gas standard atmospheres in Tedlar bags at two different levels (100 pg and 1 ng) for
different elemental species (SnH4, MeSnH3, Me2SnH2, Me3SnH, BuSnH3, SbH3, and MeSbH2). A limitation arising from counting statistics in both detection modes could be shown. A solution containing rhodium (10
ng mL–1) and cadmium (40 ng mL–1) was introduced simultaneously to the GC outlet. Rhodium acts as a continuous internal standard and Cd is used for mass-bias
correction (by measuring the 111Cd/113Cd ratio). The detection system in both pulse counting and analog mode was examined. The best attainable precision was established
for Me2SnH2 (analog mode, 12 replicates, 1 ng, RSD 0.34%, accuracy 0.31%) whereas most other species ranged between 0.4 and 0.5% RSD
if higher concentrations were used. The limitations of the pulse counting system are clearly seen, with peak heights of more
than 2000 counts reaching saturation (for an integration time of 100 ms), which reduces the accuracy of isotope ratio determinations.
A dozen VOM could be detected in an aged landfill gas sample; several unidentified Sn compounds were present. Although their
isotope ratios are within the confidence value of the standards, it is not yet clear if the acquired precision is good enough
to identify isotopic fractionation of metal(loid)s through biovolatilization processes. With the precision achieved, the combination
of cryotrapping GC and ICP–TOFMS is a powerful tool for monitoring volatile multi-element species in multi-tracer experiments
and isotope dilution methodology.
Received: 23 November 2000 / Revised: 19 February 2001 / Accepted: 24 February 2001 相似文献
47.
The gpdA-promoter-controlled exocellular production of glucose oxidase (GOD) by recombinant Aspergillus niger NRRL-3 (GOD3-18) during growth on glucose and nonglucose carbon sources was investigated. Screening of various carbon substrates
in shake-flask cultures revealed that exocellular GOD activities were not only obtained on glucose but also during growth
on mannose, fructose, and xylose. The performance of A. niger NRRL-3 (GOD3-18) using glucose, fructose, or xylose as carbon substrate was compared in more detail in bioreactor cultures.
These studies revealed that gpdA-promoter-controlled GOD synthesis was strictly coupled to cell growth. The gpdA-promoter was most active during growth on glucose. However, the unfavorable rapid GOD-catalyzed transformation of glucose
into gluconic acid, a carbon source not supporting further cell growth and GOD production, resulted in low biomass yields
and, therefore, reduced the advantageous properties of glucose. The total (endo- and exocellular) specific GOD activities
were lowest when growth occurred on fructose (only a third of the activity that was obtained on glucose), whereas utilization
of xylose resulted in total specific GOD activities nearly as high as reached during growth on glucose. Also, the portion
of GOD excreted into the culture fluid reached similar high levels (≅ 90%) by using either glucose or xylose as substrate,
whereas growth on fructose resulted in a more pelleted morphology with more than half the total GOD activity retained in the
fungal biomass. Finally, growth on xylose resulted in the highest biomass yield and, consequently, the highest total volumetric
GOD activity. These results show that xylose is the most favorable carbon substrate for gpdA-promoter-controlled production of exocellular GOD. 相似文献
48.
49.
A group action is called polar if there exists an immersed submanifold (a section) which intersects all orbits orthogonally. We show how to construct a manifold admitting a polar group action by prescribing its isotropy groups along a fundamental domain in the section. This generalizes a classical construction for cohomogeneity-one manifolds.We give many examples showing the richness of this class of group actions and relate the topology of the section to the topology of the manifold. 相似文献
50.