全文获取类型
收费全文 | 452篇 |
免费 | 6篇 |
国内免费 | 2篇 |
专业分类
化学 | 254篇 |
晶体学 | 4篇 |
力学 | 12篇 |
数学 | 28篇 |
物理学 | 162篇 |
出版年
2023年 | 3篇 |
2022年 | 7篇 |
2021年 | 5篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2018年 | 4篇 |
2017年 | 6篇 |
2016年 | 13篇 |
2015年 | 8篇 |
2014年 | 9篇 |
2013年 | 25篇 |
2012年 | 25篇 |
2011年 | 27篇 |
2010年 | 19篇 |
2009年 | 14篇 |
2008年 | 28篇 |
2007年 | 31篇 |
2006年 | 22篇 |
2005年 | 24篇 |
2004年 | 10篇 |
2003年 | 13篇 |
2002年 | 13篇 |
2001年 | 7篇 |
2000年 | 5篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 9篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 10篇 |
1992年 | 6篇 |
1991年 | 6篇 |
1990年 | 5篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 13篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 7篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1970年 | 2篇 |
1961年 | 1篇 |
排序方式: 共有460条查询结果,搜索用时 0 毫秒
131.
In this paper we investigate to what extent the results of Z. Wang and D. Daigle on “nice derivations” of the polynomial ring over a field k of characteristic zero extend to the polynomial ring over a PID R, containing the field of rational numbers. One of our results shows that the kernel of a nice derivation on of rank at most three is a polynomial ring over k. 相似文献
132.
Chakraborty B Roy AS Dasgupta S Basu S 《The journal of physical chemistry. A》2010,114(51):13313-13325
Conventional spectroscopic tools such as absorption, fluorescence, and circular dichroism spectroscopy used in the study of photoinduced drug-protein interactions can yield useful information about ground-state and excited-state phenomena. However, photoinduced electron transfer (PET) may be a possible phenomenon in the drug-protein interaction, which may go unnoticed if only conventional spectroscopic observations are taken into account. Laser flash photolysis coupled with an external magnetic field can be utilized to confirm the occurrence of PET and authenticate the spin states of the radicals/radical ions formed. In the study of interaction of the model protein human serum albumin (HSA) with acridine derivatives, acridine yellow (AY) and proflavin (PF(+)), conventional spectroscopic tools along with docking study have been used to decipher the binding mechanism, and laser flash photolysis technique with an associated magnetic field (MF) has been used to explore PET. The results of fluorescence study indicate that fluorescence resonance energy transfer takes place from the protein to the acridine-based drugs. Docking study unveils the crucial role of Ser 232 residue of HSA in explaining the differential behavior of the two drugs towards the model protein. Laser flash photolysis experiments help to identify the radicals/radical ions formed in the due course of PET (PF(?), AY(?-), TrpH(?+), Trp(?)), and the application of an external MF has been used to characterize their initial spin-state. Owing to its distance dependence, MF effect gives an idea about the proximity of the radicals/radical ions during interaction in the system and also helps to elucidate the reaction mechanisms. A prominent MF effect is observed in homogeneous buffer medium owing to the pseudoconfinement of the radicals/radical ions provided by the complex structure of the protein. 相似文献
133.
Carbonate complexation of Mn2+ in the aqueous phase: redox behavior and ligand binding modes by electrochemistry and EPR spectroscopy 总被引:1,自引:0,他引:1
Dasgupta J Tyryshkin AM Kozlov YN Klimov VV Dismukes GC 《The journal of physical chemistry. B》2006,110(10):5099-5111
The chemical speciation of Mn2+ within cells is critical for its transport, availability, and redox properties. Herein we investigate the redox behavior and complexation equilibria of Mn2+ in aqueous solutions of bicarbonate by voltammetry and electron paramagnetic resonance (EPR) spectroscopy and discuss the implications for the uptake of Mn2+ by mangano-cluster enzymes such as photosystem II (PSII). Both the electrochemical reduction of Mn2+ to Mn0 at an Hg electrode and EPR (in the absence of a polarizing electrode) revealed the formation of 1:1 and 1:2 Mn-(bi)carbonate complexes as a function of Mn2+ and bicarbonate concentrations. Pulsed EPR spectroscopy, including ENDOR, ESEEM, and 2D-HYSCORE, were used to probe the hyperfine couplings to 1H and 13C nuclei of the ligand(s) bound to Mn2+. For the 1:2 complex, the complete 13C hyperfine tensor for one of the (bi)carbonate ligands was determined and it was established that this ligand coordinates to Mn2+ in bidentate mode with a 13C-Mn distance of 2.85 +/- 0.1 angstroms. The second (bi)carbonate ligand in the 1:2 complex coordinates possibly in monodentate mode, which is structurally less defined, and its 13C signal is broad and unobservable. 1H ENDOR reveals that 1-2 water ligands are lost upon binding of one bicarbonate ion in the 1:1 complex while 3-4 water ligands are lost upon forming the 1:2 complex. Thus, we deduce that the dominant species above 0.1 M bicarbonate concentration is the 1:2 complex, [Mn(CO3)(HCO3)(OH2)3]-. 相似文献
134.
Sardar PS Maity SS Ghosh S Chatterjee J Maiti TK Dasgupta S 《The journal of physical chemistry. B》2006,110(42):21349-21356
Human placental ribonuclease inhibitor (hRI) containing six tryptophan (Trp) residues located at positions 19, 261, 263, 318, 375, and 438 and its complex with RNase A have been studied using steady-state and time-resolved fluorescence (298 K) as well as low-temperature phosphorescence (77 K). Two Trp residues in wild-type hRI and also in the protein-protein complex with RNase A are resolved optically. The accessible surface area values of Trp residues in the wild-type hRI and its complex and consideration of inter-Trp energy transfer in the wild-type hRI reveal that one of the Trp residues is Trp19, which is located in a hydrophobic buried region. The other Trp residue is tentatively assigned as Trp375 based on experimental results on wild-type hRI and its complex. This residue in the wild-type hRI is more or less solvent exposed. Both the Trp residues are perturbed slightly on complex formation. Trp19 moves slightly toward a more hydrophobic region, and the environment of Trp375 becomes less solvent exposed. The complex formation also results in a more heterogeneous environment for both the optically resolved Trp residues. 相似文献
135.
We present a versatile, optical fiber coupled light emitting diode (LED) light source based flow-through optical absorbance detector. The LED source is readily changeable. Optical fibers are used to carry light from the electronics/display unit to a reflective flow-through cell and back. The cell can thus be located remotely from the electronics unit and the umbilical connection is not susceptible to electrical noise. The noise level of this detector with LEDs of different emission maxima were observed to be in the range of 3-20 muAU under actual use conditions, with a maximum short term drift of 4 muAU/min after the initial warm-up period. When the analyte absorbance is well matched with the source emission characteristics, the detector response is linear with concentration over at least two orders of magnitude. The liquid flow path through the cell is linear with a large exit aperture such that bubbles are not trapped in the optical path. The optical arrangement is such that the incident light crosses the liquid flow orthogonally and is reflected back by a rear mirror to the receiver fiber. This arrangement reduces the refractive index sensitivity by an order of magnitude relative to conventional Z-path flow cells. 相似文献
136.
Mitra RN Dasgupta A Das D Roy S Debnath S Das PK 《Langmuir : the ACS journal of surfaces and colloids》2005,21(26):12115-12123
The primary objective of the present article is to understand how the geometric constraints at the surfactant head affect the lipase activity in the reverse micellar interface. To resolve this issue, surfactants were designed and synthesized, and activity was measured in /water/isooctane/n-hexanol reverse micellar systems at z ([alcohol]/[surfactant])=5.6, pH 6.0 (20 mM phosphate), 25 degrees C across a varying range of W0 ([water]/[surfactant]) using p-nitrophenylalkanoates as the substrate. It was observed that lipase activity increases from surfactants to with the increment in surface area per molecule (Amin) because of the substitution by the bulky tert-butyl group at the polar head. However, the activity was found to be similar for despite an enhancement in the hydrophilic moieties at the interface. This unchanged lipase activity is presumably due to the comparable surface area of to originating from the rigidity at the surfactant head. Noticeably, the enzyme activity improved from with the simultaneous increment of both the hydroxyl group and the flexibility of the headgroup whereas that for increased exclusively with the flexibility of the headgroup. The common parameter in both groups of surfactants and is the flexibility of the headgroup, which possibly enhance Amin and consequently the lipase activity. Thus, the geometric constraints at the surfactant headgroup play a crucial role in modulating the lipase activity profile probably because of the variation in interfacial area. 相似文献
137.
A method has been described for the estimation of Cu, Co and Ni in polymetallic sea bed nodule samples by flame atomic absorption spectrometry using single component calibration standards. Interelemental interference plays a crucial role in the estimation of Cu, Co and Ni by flame AAS. Calibration by multicomponent matrix matching standards often fails because of wide variations in the compositions of actual samples. Cu, Co and Ni values are depressed in the presence of appreciable amounts of Fe and Mn present in the sea nodule matrix. Observed interferences have been eliminated computationally using a two parameter theoretical model. The method has been successfully applied for the estimation of Cu, Co and Ni in real life sea nodule samples by flame AAS using single component calibration standards. 相似文献
138.
139.
Kian-Tat Lim Sharon Brunett Mihail Iotov Richard B. McClurg Nagarajan Vaidehi Siddharth Dasgupta Stephen Taylor William A. Goddard 《Journal of computational chemistry》1997,18(4):501-521
We describe the implementation of the cell multipole method (CMM) in a complete molecular dynamics (MD) simulation program (MPSim) for massively parallel supercomputers. Tests are made of how the program scales with size (linearly) and with number of CPUs (nearly linearly) in applications involving up to 107 particles and up to 500 CPUs. Applications include estimating the surface tension of Ar and calculating the structure of rhinovirus 14 without requiring icosahedral symmetry. © 1997 by John Wiley & Sons, Inc. 相似文献
140.
We describe a multilayered open tubular anion exchange column fabricated by alternately pumping solutions of chitosan and glutaraldehyde. The column is terminated in an integrally bonded monolithic suppressor cast around a mandrel of a tungsten wire, composed of an acrylic acid (AA)-ethylene dimethacrylate (EDMA) monolith that is made with sufficient porogen for the monolith to function as a membrane. For a 4.5m long 75 μm bore column coated with 24 successive layers of the condensation polymer (estimated to contain ~72 molecular layers) and coupled to 1cm length of a suppressor fabricated with 55-60% AA, effective separation of several common anions (F(-), Cl(-), NO(2)(-), Br(-), NO(3)(-), average number of theoretical plates ~12,000) and adequate suppression of 1 mM KOH used as eluent was observed at a flow rate of 800 nL min(-1) to obtain sub-picomol detection limits at an operating pressure of ~1 bar. The separation is not time efficient but the system can be meritorious in unique niche applications where a small form factor is desired and liquid volume and power consumption are more important than separation speed. 相似文献