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121.
Important aspects of the electrochemical reduction of a series of substituted benzyl thiocyanates were investigated. A striking change in the reductive cleavage mechanism as a function of the substituent on the aryl ring of the benzyl thiocyanate was observed, and more importantly, a regioselective bond cleavage was encountered. A reductive alpha-cleavage (CH(2)-S bond) was seen for cyano and nitro-substituted benzyl thiocyanates leading to the formation of the corresponding nitro-substituted dibenzyls. With other substituents (CH(3)O, CH(3), H, Cl, and F), both the alpha (CH(2)-S) and the beta (S-CN) bonds could be cleaved as a result of an electrochemical reduction leading to the formation of the corresponding substituted monosulfides, disulfides, and toluenes. These final products are generated through either a protonation or a nucleophilic reaction of the two-electron reduction-produced anion on the parent molecule. The dissociative electron transfer theory and its extension to the formation/dissociation of radical anions, as well as its extension to the case of strong in-cage interactions between the produced fragments ("sticky" dissociative electron transfer (ET)), along with the theoretical calculation results helped rationalize (i) the observed change in the ET mechanism, (ii) the dissociation of the radical anion intermediates formed during the electrochemical reduction of the nitro-substituted benzyl thiocyanates, and more importantly (iii) the regioselective reductive bond cleavage.  相似文献   
122.
We consider an agent-based model with exponentially distributed waiting times in which two types of agents interact locally over a graph, and based on this interaction and on the value of a common intolerance threshold \(\tau \), decide whether to change their types. This is equivalent to a zero-temperature ising model with Glauber dynamics, an asynchronous cellular automaton with extended Moore neighborhoods, or a Schelling model of self-organized segregation in an open system, and has applications in the analysis of social and biological networks, and spin glasses systems. Some rigorous results were recently obtained in the theoretical computer science literature, and this work provides several extensions. We enlarge the intolerance interval leading to the expected formation of large segregated regions of agents of a single type from the known size \(\epsilon >0\) to size \(\approx 0.134\). Namely, we show that for \(0.433< \tau < 1/2\) (and by symmetry \(1/2<\tau <0.567\)), the expected size of the largest segregated region containing an arbitrary agent is exponential in the size of the neighborhood. We further extend the interval leading to expected large segregated regions to size \(\approx 0.312\) considering “almost segregated” regions, namely regions where the ratio of the number of agents of one type and the number of agents of the other type vanishes quickly as the size of the neighborhood grows. In this case, we show that for \(0.344 < \tau \le 0.433\) (and by symmetry for \(0.567 \le \tau <0.656\)) the expected size of the largest almost segregated region containing an arbitrary agent is exponential in the size of the neighborhood. This behavior is reminiscent of supercritical percolation, where small clusters of empty sites can be observed within any sufficiently large region of the occupied percolation cluster. The exponential bounds that we provide also imply that complete segregation, where agents of a single type cover the whole grid, does not occur with high probability for \(p=1/2\) and the range of intolerance considered.  相似文献   
123.
In this paper, femtosecond optical pulses compression and supercontinuum generation in a triangular silicon photonic crystal fiber at 2500 nm are investigated. A region of large minimum anomalous group velocity dispersion, negligible higher order dispersions and unique nonlinearity of silicon are used to demonstrate compression of 100 fs initial input optical pulses to 2.5 fs and ultra-broadband supercontinuum generation with very low input pulse energy over short distances of the fiber.  相似文献   
124.
In this paper we proposed optical NOR and NAND gates. By combining nonlinear Kerr effect with photonic crystal ring resonators first we designed a structure, whose optical behavior can be controlled via input power intensity. The switching power threshold obtained for this structure equal to 2 kW/μm2. For designing the proposed optical logic gates we employed two resonant rings with the same structures, both rings at the logic gates were designed such that their resonant wavelength be at λ = 1550 nm. Every proposed logic gate has one bias and two logic input ports. We used plane wave expansion and finite difference time domain methods for analyzing the proposed structures.  相似文献   
125.
Photonic crystal ring resonators are promising candidates for realizing all optical filters with acceptable transmission efficiency and quality factor values. In this paper, by putting a12-fold quasi crystal at the middle of on 7 × 7 square cavity we created a ring resonator structure and designed a T-shaped channel drop filter. The drop wavelength of our filter is at 1551 nm, with transmission efficiency and quality factor equal to 90% and 387. Our structure is composed of dielectric rods immersed in air. Because in this kind of structures the dominant band gap is in TM mode, all of our simulations have been done in TM mode. The total footprint of our filter is 242.4 μm2, which makes it suitable for all optical integrated circuits.  相似文献   
126.
Molecular Diversity - A novel series of phenoxymethybenzoimidazole derivatives (9a-n) were rationally designed, synthesized, and evaluated for their α-glycosidase inhibitory activity. All...  相似文献   
127.
Dithiobisphthalimide is used as a new precursor for the spontaneous deposition of sulfur on gold surfaces in acetonitrile. Characterization of the modified surfaces is achieved using X‐ray photoelectron spectroscopy (XPS), electrochemistry and scanning tunneling microscopy (STM). The reported results indicate that the sulfur deposition is an efficient and fast process and that high coverages can be reached very quickly. Sequential high‐resolution STM in air allows the direct observation, for the first time, of the mobility of the usually observed rectangular structures as individual units. It also shows the reversible association/dissociation of these rectangles. The nature of these structures is highly debated in the literature and the present work provides new insights into their nature through the use of a new sulfur precursor under non‐traditional conditions. To explain our results we consider these structures as simple sulfur adlayers on the gold surface.  相似文献   
128.
Here, we report the fabrication of self-organized titania (TiO(2)) nanotube array supercapacitor electrodes through controlled phase transformation of TiO(2), with aerial capacitances as high as 2.6 mF cm(-2), which far exceeds the values so far reported in the literature. The role of phase transformation in the electrochemical charge-discharge behaviour of nanocrystalline TiO(2) nanotubes is investigated and discussed in detail. The ease of synthesis and the exceptional electrochemical properties make these nanotube arrays an alternative candidate for use in energy storage devices.  相似文献   
129.
The fruits of the edible and medicinal Egyptian palm, Medemia argun, were collected from Aswan in Egypt and the essential oil (EO) from fruits and headspace (HS) of the seeds and fleshy mesocarps were analyzed by GC and GC-MS. Results obtained by GC-MS analysis indicated a high variability in the oil and in the headspace from seeds and mesocarps. Sesquiterpene derivatives were the main group of volatiles in the EO from fruits and in the HS from seeds (45.0 and 64.0%, respectively), while oxygenated hydrocarbon derivatives were the main constituents in the HS obtained from fleshy mesocarps (96.5%). The different chemical composition of the headspace obtained from the seeds and mesocarps of M. argun can be correlated with the different roles that the different constituents play in the prevention of dehydration of the fruits in the desert region from where the plant was collected.  相似文献   
130.
A promiscuous UDP-sugar pyrophosphorylase (BLUSP) was cloned from Bifidobacterium longum strain ATCC55813 and used efficiently with a Pasteurella multocida inorganic pyrophosphatase (PmPpA) with or without a monosaccharide 1-kinase for one-pot multienzyme synthesis of UDP-galactose, UDP-glucose, UDP-mannose, and their derivatives. Further chemical diversification of a UDP-mannose derivative resulted in the formation of UDP-N-acetylmannosamine.  相似文献   
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