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51.
Borate complexes formed in the ternary system at pH 9.2 containing borate, (S)-3-amino-1,2-propanediol (SAP), and DL-pantothenic acid (DL-PTA) were identified by 13C and 11B NMR, and it is confirmed that the binary complexes, [B(OH)2(SAP)], [B(SAP)2]+ [B(OH)2(D- or L-PTA)]2-, and [B(D- or L-PTA)2]3- (including [B(D-PTA)(L-PTA)]3-), and the ternary complexes, [B(SAP)(D- or L-PTA)]-, coexist at equilibrium in the ternary system. Thermodynamic experiments by variable-temperature 11B NMR revealed that the ternary complex, [B(SAP)(D-PTA)]-, is entropically more stable than [B(SAP)(L-PTA)]-. Because two geometrical isomers are possible for the respective ternary complexes, semi-empirical molecular orbital calculations were performed by PM5, PM3, and AM1 methods in order to obtain the optimized structures. It is indicated from the calculated heats of formation and experimentally obtained thermodynamic parameters that the (S)-isomer is more probable for the respective ternary complexes with D- and L-PTA. In the optimized structure of (S)-[B(SAP)(D-PTA)]- in water, the SAP and D-PTA ligands were oppositely oriented to form a rather linear structure, while the diastereomer, (S)-[B(SAP)(L-PTA)]-, had a folded structure. Because such a difference in the solvated structure of the ternary complexes can give a different electrophoretic velocity in CE, the enantioseparation of DL-PTA in CE is reasonably attributed to a difference in the observed electrophoretic mobility for the equilibrated ternary systems containing the respective ternary complexes. 相似文献
52.
Six reducing monosaccharides (mannose, galactose, fucose, glucose, xylose, and arabinose) were derivatized with 1-phenyl-3-methyl-5-pyrazolone (PMP) and chiral resolution of these racemic PMP-monosaccharides was studied by ligand-exchange CE using borate anion as a central ion of the chiral selector and (S)-3-amino-1,2-propanediol (SAP) as a chiral selector ligand. PMP-mannose, PMP-galactose and PMP-fucose were successfully enantioseparated. Lowering the capillary temperature increased the resolution of PMP-mannose system, but decreased that of PMP-galactose and PMP-fucose systems. Whereas the maximum resolution was obtained at pH 8.9 in the PMP-mannose system, resolution increased gradually with pH in the PMP-galactose and PMP-fucose systems. Expecting the formation of the ternary borate complexes with SAP and PMP-monosaccharide in the CE experiments, the optimized structures of the borate diastereomers were obtained by semiempirical molecular orbital calculations to discuss the structural difference of the diastereomers in connection with the enantioseparation behaviors. 相似文献
53.
Sawada Y Furumi S Takai A Takeuchi M Noguchi K Tanaka K 《Journal of the American Chemical Society》2012,134(9):4080-4083
The highly enantioselective synthesis of helically chiral 1,1'-bitriphenylenes has been achieved via rhodium-catalyzed double [2 + 2 + 2] cycloaddition of biaryl-linked tetraynes with 1,4-diynes (up to 93% ee). Crystal structures and photophysical properties of these helically chiral 1,1'-bitriphenylenes have also been studied. 相似文献
54.
Naoko Asakuma Toshimi Fukui Mamoru Aizawa Motoyuki Toki Hiroaki Imai Hiroshi Hirashima 《Journal of Sol-Gel Science and Technology》2000,19(1-3):333-336
Structural changes stimulated by ultraviolet (UV) laser irradiations of sol-gel derived inorganic oxide films were investigated. Dried gel films of TiO2, Nb2O5, Ta2O5, SrTiO3 and Pb(Zr
x
Ti1–x
)O3 (PZT) were found to be crystallized by the laser irradiation. On the other hand, the photo-induced change in gel films of BaTiO3, LiNbO3 and LiTaO3 was not observed although the laser beams were absorbed in the films. These sol-gel films were thermally crystallized at almost the same temperature around 600–700°C except TiO2. Thus, the UV-laser-induced crystallization is not directly ascribed to a simple thermal effect with the irradiation. Photochemical properties of the cations are assumed to be important for the change in sol-gel films. 相似文献
55.
Hiroki Hotta Qiang Wang Mioko Fukuda Shoichi Aizawa Tomonari Umemura Kazutoshi Sekizawa Kin-ichi Tsunoda 《Analytical sciences》2008,24(6):795-798
The use of electrospray ionization mass spectrometry (ESI-MS) in negative ion mode was investigated as a direct probe for identifying Al species in Al-accumulating hydrangea (Hydrangea macrophylla) samples. Cell sap solutions of hydrangea leaves were purified using Sephadex G-10 liquid chromatography and each fraction was analyzed using ESI-MS and ESI-MS/MS to identify Al species. In hydrangea leaves, a 1:1 Al-citrate complex was found as [AlH(-1)cit](-) (m/z 215), where H(3)cit denotes citric acid. This result is consistent with that of Ma et al. who used (27)Al-NMR. 相似文献
56.
57.
Diffusion of linear aliphatic mono- and diesters (C
N
) havingN main chain atoms (N=13–68) in bulk medium-density polyethylene (MDPE) has been studied under hydrostatic pressures up to 2500 bar at temperatures between 60°C and 125°C. Three triglycerides, phenyl stearate, and p-aminoazobenzene (pAAB, 80°C) as the diffusants and low-density (LDPE) and high-density (HDPE) polyethylenes as polyethylene substrate were used for comparison. Diffusion coefficientD was determined from concentration distribution of the diffusants through stacked PE sheets as substrate. Regarding the linear esters at 90°C, the relationshipD N
holds at constant pressures. Under the atmospheric pressure, became –2.10 in accordance with de Gennes's proposal (1971)D N
–2 as well as with the experimental results reported by Klein and Briscoe (1979) forN larger than 30.D's for the glycerides deviate from the relationshipD N
–2 toward the smaller values by comparison at the sameN. The exponent is pressure-dependent. It decreases with increasing pressure according to =–2.10–0.000942P, whereP is measured by the unit of bar. Plots of lnD vsP for all the diffusants show linear relationships with negative slopes, from which activation volume for the diffusion V
was calculated. At 90°C, V
increases slowly with increasingN and increasingV
Ki, the intrinsic molecular volume of the diffusant, from 39.3 cm3/mol for ethyl caprate (C
13,V
Ki=136 cm3/mol) to 76.8 cm3/mol for behenyl behenate (C45,V
Ki=466 cm3/mol). Observed V
s are explainable on the basis of the reptation mode of the chain molecule diffusion. V
s for C25 and C45 are found to increase with increasing degree of crystallinity where MDPE, heat-treated MDPE, LDPE, and HDPE were used. The results obtained by varying temperature are as follows. V
for C45 was always found to be larger than C25. Both decreased linearly with increasing temperature, giving two linear lines with different slopes whose extensions intersected at 132°C, the melting point of the MDPE, where the difference in V
disappeared. The apparent activation energiesE
Ds for the diffusion of C25 and C45 increased linearly with increasing pressure, whose slopes are explainable according toE
D=E
0+PV
[1-(dln V
/dlnT)
P
]. 相似文献
58.
59.
A bio-electrochemical sensor specific for hydrogen peroxide is described. The sensor consists of two membranes—a catalase-collagen membrane and a teflon membrane—an alkaline solution, a platinum cathode and a lead anode. The catalase-collagen membrane is prepared electrochemically, the thickness being 1 μ; the enzyme activity is similar to that of native catalase. The sensor responds to hydrogen peroxide with a response time of only 1–2 min. The calibration curve is quite linear over a concentration range of 0–1.5 mmol l-1 for hydrogen peroxide. The utility of the sensor in continuous usage is discussed. 相似文献
60.
Yoshio Imai Mitsuru Ueda Tatsuo Aizawa 《Journal of polymer science. Part A, Polymer chemistry》1976,14(11):2797-2805
A novel class of polypyridazinophthalazinediones has been synthesized by the solution cyclopolycondensation in m-cresol of dibenzoylphthalic acids with aromatic dihydrazines such as bis(4-hydrazinophenyl)methane and bis(4-hydrazinophenyl) sulfone. The polyheterocycles derived from 4,6-dibenzoylisophthalic acid, which had inherent viscosities of up to 0.5, were soluble in m-cresol and hot dichloroacetic acid, whereas the polymers from 2,5-dibenzoylterephthalic acid were practically insoluble in organic solvents. Thermogravimetric analyses showed that all the polymers underwent weight losses of 10% at 490–520°C in both air and nitrogen. 相似文献