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11.
Electronic and structural factors controlling the competition between 5-exo-dig and 6-endo-dig cyclizations of sp2-radicals were analyzed using a combination of available experimental data and computation. Although the stereoelectronically favored 5-exo pathways usually has the lower activation energy, formation of a new aromatic ring not only makes the 6-endo process favorable thermodynamically in conjugated systems but also lowers its activation barrier to the extent where the 5-exo/6-endo selectivity is controlled by subtle factors such as the different sensitivity of the two pathways to strain effects in polycyclic systems. In particular, the stronger sensitivity of the 5-exo pathway to strain leads to a crossover in selectivity. The 6-endo cyclization is kinetically favored in smaller (and strained) cycles, whereas the 5-exo cyclization has lower barriers in the larger rings. 相似文献
12.
Manikandan P Muthukumaran R Thomas KR Varghese B Chandramouli GV Manoharan PT 《Inorganic chemistry》2001,40(10):2378-2389
Copper(II) azide complexes of three tridentate ligands namely 2,6-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L), 2,6-(pyrazol-1-ylmethyl)pyridine (L'), and dipropylenetriamine (dpt) yield three kinds of complexes with different azide-binding modes. The ligand L forms two end-on-end (mu-1,3) diazido-bridged binuclear complexes, [CuL(mu-N(3))](2)(ClO(4))(2) (1) and [CuL(mu-N(3))(ClO(4))](2).2CH(3)CN (2), and L' forms a perchlorato-bridged quasi-one-dimensional chain complex, [CuL'(N(3))(ClO(4))](n)() (3) with monodentate azide coordination. The ligation of dipropylenetriamine (dpt) gives a end-on (mu-1,1) diazido-bridged binuclear copper complex [Cu(dpt)(mu-N(3))](2)(ClO(4))(2) (4). The crystal and molecular structures of these complexes have been solved. Variable-temperature EPR results of 1 and 2 are identical and indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former dominating at low temperatures and the latter at high temperatures. The unusual temperature-dependent magnetic moment and EPR spectra of this dimer reveal the presence of temperature-dependent population of two triplet states, one being caused by antiferromagnetic and the other by ferromagnetic interaction, the former transforming to the latter on cooling. While the interaction of ground spin doublets of the two metal centers gives rise to a ferromagnetic coupling of J(g) = 90.73 cm(-1), the other coupling of J(e) = -185.64 cm(-1) is suggested to be caused by the interaction between an electron in one metal center and an electron from the azide of the other monomer by excitation of a d-electron to the empty ligand orbital. The ferromagnetic state is energetically favored by 104.39 cm(-1). Compound 3 exhibits axial spectra at room temperature and 77 K, and variable-temperature magnetic susceptibility data indicate that the copper centers form a weakly antiferromagnetic one-dimensional chain with J = -0.11 cm(-1). In the case of 4, the unique presence of two nonidentical dimeric units with different bond lengths and bond angles within the unit cell as inferred by crystal structure is proved by single-crystal EPR spectroscopy. 相似文献
13.
Ch. Syama Sundar N. Bakthavatchala Reddy S. Siva Prasad K. Uma Maheswara Rao S. H. Jaya Prakash C. Suresh Reddy 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):551-557
Abstract A new series of α-aminophosphonates have been synthesized by a one-pot three-component reaction of 2,3-dihydrobenzo[b][1,4]dioxine-6-carbaldehyde, various amines, and dimethyl phosphite by using nano-TiO2 as a catalyst under solvent-free conditions at 50°C. The major advantages of the present method are high yields, short reaction times, recyclable catalyst, and solvent-free reaction conditions. Among these new structurally diversified set of α-aminophosphonates, dimethyl (2,3-dihydrobenzo[b][1,4]dioxin-6-yl)(3-nitrophenylamino) methylphosphonate and dimethyl (2,3-dihydrobenzo[b][1,4]dioxin-6-yl)(4-fluoro-3-nitro-phenyl-amino) methylphosphonate have shown higher antioxidant activity in diphenyl picryl hydrazyl (DPPH) scavenging, reducing power assay, and lipid peroxidation methods. 相似文献
14.
15.
J. Siva Kumar U. V. Subba Rao K. V. Satyanarayana Rao K. Narasimha Reddy 《Crystal Research and Technology》1991,26(1):103-108
Thin films of various thicknesses in the MIM structure have been prepared from the the powders of SnO2, Sb2O3 and (SnO2 + Sb2O3) of high purity by the thermal evaporation technique in a vacuum of 10−5 Torr. Dielectric properties of SnO2, Sb2O3, and their mixed thin films have been studied with ac and dc electric fields and frequency. Capacitance and loss tangent are almost independent on dc voltage upto 1.0 V for SnO2, 10.0 V for Sb2O3 and 2.5 V for mixed films. These capacitors become unstable at 1.0 V for SnO2 films and 2.5 V for mixed films. For higher film thicknesses the decay in these films starts at higher voltages. Capacitance and loss tangent increases with applied ac voltage in SnO2, Sb2O3, and their mixed films. A comparison of the capacitance values of SnO2, Sb2O3, and their mixed films showed that the capacitance values are less in Sb2O3 as compared to SnO2 films. In mixed films the capacitance is greater than the constituent films. These studies have shown that Sb2O3 films are found to be more stable compared to SnO2 and their mixed films for ac and dc voltages. The results thus obtained on SnO2, Sb2O3, and their films are presented and discussed. 相似文献
16.
Dr. Siva Senthil Kumar Boominathan Kai-Hsin Chang Dr. Yu-Chiao Liu Chi-Shin Wang Cheng-Feng Wu Dr. Ming-Hsi Chiang Prof. Pi-Tai Chou Prof. Yao-Ting Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7280-7284
Diindeno-fused dibenzo[a,h]anthracene 6 and diindeno-fused dibenzo[c,l]chrysene 9 contain the key moieties 1,4-quinodipropene (1,4-QDP) and 2,6-naphthoquinodipropene (2,6-NQDP), respectively, and they both have an open-shell singlet ground state. The latter compound exhibits a strong biradical character and interesting properties, including a low ΔET−S (2.44 kcal mol−1), a small HOMO–LUMO gap (1.06 eV), a wide photoabsorption range (250–1172 nm), and a large two-photon absorption cross-section (σ=1342±56 GM). This work verifies that 6 has a slightly larger HOMO–LUMO gap and ΔET−S than its helical isomer diindeno[2,1-f:1′,2′-j]picene (DIP), but is a much stronger two-photon absorber, verifying the important effect of geometry on the photophysical properties. 相似文献
17.
Samir Kumar Sarkar Meenakshi Pegu Santosh Kumar Behera Siva Krishna Narra Pakkirisamy Thilagar 《化学:亚洲杂志》2019,14(24):4588-4593
Typically, molecules with a twisted donor–acceptor (D‐A) architecture have been exploited for constructing thermally activated delayed fluorescence (TADF) materials. Herein, we report the first example of a thiophene‐based thermally activated delayed fluorescent molecule without a D‐A architecture. Compound 1 (2,5‐bis(2,2‐di(thiophen‐2‐yl)vinyl)thiophene) is conformationally flexible and shows weak fluorescence in the solution state but displays bright TADFin both condensed and solid states. Compound 1 crystallized in two different polymorphs ( 1 a and 1 b ). Interestingly, both polymorphs show distinctly different TADF features. The broad spectral features and the TADF characteristics of 1 have been explored for the time‐dependent multicolor (green, yellow and red) imaging of living cells. 相似文献
18.
Samir Kumar Sarkar Meenakshi Pegu Santosh Kumar Behera Siva Krishna Narra Pakkirisamy Thilagar 《化学:亚洲杂志》2019,14(24):4431-4431
19.
B. Prasanna Lakshmi V. Rajagopal Reddy V. Janardhanam M. Siva Pratap Reddy Jung-Hee Lee 《Applied Physics A: Materials Science & Processing》2013,113(3):713-722
We report on the effect of an annealing temperature on the electrical properties of Au/Ta2O5/n-GaN metal–insulator–semiconductor (MIS) structure by current–voltage (I–V) and capacitance–voltage (C–V) measurements. The measured Schottky barrier height (Φ bo) and ideality factor n values of the as-deposited Au/Ta2O5/n-GaN MIS structure are 0.93 eV (I–V) and 1.19. The barrier height (BH) increases to 1.03 eV and ideality factor decreases to 1.13 upon annealing at 500 °C for 1 min under nitrogen ambient. When the contact is annealed at 600 °C, the barrier height decreases and the ideality factor increases to 0.99 eV and 1.15. The barrier heights obtained from the C–V measurements are higher than those obtained from I–V measurements, and this indicates the existence of spatial inhomogeneity at the interface. Cheung’s functions are also used to calculate the barrier height (Φ bo), ideality factor (n), and series resistance (R s ) of the Au/Ta2O5/n-GaN MIS structure. Investigations reveal that the Schottky emission is the dominant mechanism and the Poole–Frenkel emission occurs only in the high voltage region. The energy distribution of interface states is determined from the forward bias I–V characteristics by taking into account the bias dependence of the effective barrier height. It is observed that the density value of interface states for the annealed samples with interfacial layer is lower than that of the density value of interface states of the as-deposited sample. 相似文献
20.
Rama Moorhy Appa S. Siva Prasad Jangam Lakshmidevi Bandameeda Ramesh Naidu Manchala Narasimhulu Katta Venkateswarlu 《应用有机金属化学》2019,33(10)
An agro waste‐derived, ‘water extract of pomegranate ash’ (WEPA), has been utilized for the first time as a renewable medium for Pd(OAc)2‐catalysed Suzuki–Miyaura cross‐coupling at room temperature. This method offers a simple and sustainable synthesis of biaryls from aryl halides and arylboronic acids under ligand‐ and external base‐free aerobic and ambient conditions. This method has been found effective for both activated and unactivated aryl halides in the production of biaryls with moderate to nearly quantitative yields. The protocol shows high chemoselectivity over identical/similar reactive sites in aryl halides (i.e. selectivity over identical halogens or different halogens of aryl halides). This method exhibits high regioselectivity, i.e. the selective reactivity of a halogen over other identical halogens at different positions on the aromatic nucleus. Therefore, we disclose here a clean, benign, substantial chemo‐ and regioselective and highly economic alternative method for the palladium‐assisted synthesis of biaryls using an agro waste‐derived medium. 相似文献