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991.
A simple aqueous solution route was introduced for the fabrication of CuO pricky microspheres (CPMs) using CuCl(2) x 2H(2)O, Na(2)(C(4)H(4)O(6)) x 3H(2)O and NaOH as starting materials. The CPMs were composed of compressed nanothorns exhibiting tapering feature with tip size of less than 10 nm, and the size of CPMs could be tuned from 100-200 nm to 4-6 microm. The effects of the molar ratios of tartrate anions and NaOH to Cu(2+) cations, reagent concentration, and reaction temperature on the products were investigated, showing that the morphology of CPMs was determined by the molar ratio of tartrate to Cu(2+) cations and the size was greatly affected by reagent concentration and the molar ratio of NaOH to Cu(2+) cations in the precursor solution. The fabrication of CPMs went through rapid nucleation of Cu(OH)(2), aggregation and in situ dehydration of Cu(OH)(2), oriented-aggregation-based growth, and normal crystal growth of CuO nanothorns. The nucleation and crystal growth were successfully separated by controlled releasing of Cu(2+) and OH(-) ions through the reversible reaction of Cu(2+) cations, OH(-), and C(4)H(4)O(6)(2-) anions. 相似文献
992.
Jiao H Costuas K Gladysz JA Halet JF Guillemot M Toupet L Paul F Lapinte C 《Journal of the American Chemical Society》2003,125(31):9511-9522
Density functional theory has been used to probe the bonding and electronic properties of the homo- and heterobimetallic sp carbon chain complexes (ML(m), = (eta(5)-C(5)R(5))(eta(2)-R(2)PCH(2)CH(2)PR(2))Fe, (eta(5)-C(5)R(5))(NO)(PR(3))Re; z = 0-4). All neutral complexes are best described by MCtbd1;CCtbd1;CM electronic structures, in accord with much experimental data. The singlet dications are best described by cumulenic (+)M=C=C=C=C=M(+) valence formulations. However, the diiron and rhenium/iron dications are found to possess triplet states of nearly identical energy, clarifying experimental magnetic data. Their electronic structures have dominant *(+)MCtbd1;CCtbd1;CM(+)* character, with some spin delocalization onto the carbon chain. The mixed valence monocation radicals exhibit delocalized unpaired electrons, in accord with class III (strongly coupled) and II (weakly coupled) assignments made from experimental data earlier, with some spin density on the carbon chain. An isolable diiron trication has a doublet ground state, but some computational data suggest a close-lying quartet. For the unknown diiron tetracation, a bis(carbyne) or (2+)Fetbd1;CCtbd1;CCtbd1;Fe(2+) electronic structure is predicted. Calculated adiabatic ionization potentials show the iron endgroup to be more electron-releasing than rhenium, in accord with electrochemical data. This polarizes the electronic structures of the rhenium/iron complexes. To help validate the computed model structures, crystal structures of ((eta(5)-C(5)Me(5))Fe(eta(2)-dppe))(2)(mu-C(4)) and [((eta(5)-C(5)Me(5))Fe(eta(2)-dippe))(2)(mu-C(4))](3+) 3PF(6)(-) are determined. Data are analyzed with respect to related diruthenium and dimanganese complexes. 相似文献
993.
The structures of [MCl2(C6H4B3CH2COPh)2] [M=Zn(II) (1), Co(II) (2)] have been determined by X‐ray crystallography. They were characterized by elemental analysis, IR spectrum, electronic spectrum and thermogravimetric‐differential thermal analysis. They all crystallize in the triclinic system, space pup Pi, with lattice parameters a=0.9449(2) nm, b=1.1291(2) nm, c=1.3637(3) nm, α=111.70(3)°, β= 94.33(3)°, y=90.97(3), Z=2 for compound 1; a=0.9437(2) nm, b= 1.1277(2) nm, c= 1.3650(3) nm, a=111.76(3)°, β=94.50(3)°, y=90.80(3)°, Z=2 for compound 2. The metal ions are all coordinated by two C1?‐ anions and two nitrogen atoms of 1‐benzoylmethyl‐bentriazole ligands. forming the distorted tetrahedral geometry. The Zn—Cl and Zn—N bond lengths are 0.2209(2), 0.2210(2) nm and 0.2059(4), 0.2067(4) nm. respectively. The CO‐Cl 3 and Co–N bond lengths are 0.2215(2). 0.2222(2) nm and 0.2028(5), 0.2045(5) nm. respectively. The thermogravimetric (TG) data indicate that they are nearly similar in TG curve, and there are not structural transitions in the two compounds. They all have a high thd stability. But, there is little difference in DTG (differential thermogravimetric) curves of those two compounds. Elemental analysis, electronic and IR spectra are in agreement with the structural data. 相似文献
994.
Determination of triptolide and triptonide in human plasma by high-performance liquid chromatography 总被引:3,自引:0,他引:3
An isocratic high-performance liquid chromatographic method for determination of triptolide and triptonide in human plasma is described. Plasma samples were extracted with OasisHLB solid-phase extraction (SPE) cartridges. After pretreatment, they were separated on a SymmetryShieldRP(18) column with a mobile phase of acetonitrile-water (40:60,v/v) at 40 degrees C. The effluent was monitored at UV 217 nm. Linearity (0.010-1.0 mg/L) was good, and the lower limit of detection was 3 ng/mL for triptolide and 4.5 ng/mL for triptonide (S/N = 3). The relative standard deviations of intra- and inter-day assay were less than 15% and the recoveries were better than 80%. The developed method was applied to the determination of triptolide and triptonide concentration in a patient's plasma after taking the medicament containing Tripterygium wilfordii Hook. F. 相似文献
995.
The hyperconjugation effect in the substituted methyl boranes, XCH(2)BH(2) (X = H, CH(3), NH(2), PH(2), OH, SH, F, Cl, Br), has been quantitatively evaluated by using the orbital deletion procedure (ODP), where the p(pi) orbital on boron is deactivated. Except for the case of X = NH(2), which forms a three-membered ring, the magnitude of the hyperconjugative stabilization in all other substituted methylborane ranges from 6.8 to 3.4 kcal/mol. Significant structural changes are observed, particularly the shortening of the central B-C bond distance and the reducing of the corresponding XCB and HCB bond angles. In general, the strength of the hyperconjugative interaction between the occupied sigma(C-X) bond and the vacant p(pi) orbital on boron is correlated to the electronegativity of X, and the competition between the donation ability of the sigma(C-X) and the sigma(C-H) bonds determines the preference of the staggered or eclipsed structure as the energy minimum state. When the donation abilities of the C-X and C-H bonds are comparable, other factors such as electron correlation and steric effect may play elaborate roles in the geometrical propensity of the most stable structures. 相似文献
996.
Xu J Zuo G Jiao P Wang H Jin S Chan AS 《Rapid communications in mass spectrometry : RCM》2000,14(8):633-636
The mass spectrometric behaviour of six 2a,4-disubstituted 5-benzoyl-2-chloro-2a,3,4,5-tetrahydroazeto[1,2-a][1,5]benzodia zepin-1(2H)-ones has been studied with the aid of mass-analysed ion kinetic energy spectrometry and accurate mass measurements under electron impact ionization. All compounds show a tendency to eliminate a chlorine atom, a chlorine atom plus benzaldehyde, benzoyl radical, chloroketene or chlorine atom plus CO and H2O molecules to yield, respectively, [M-Cl]+ ions, 2a,4-disubstituted 2a,3-dihydroazeto[1,2-a][1,5]benzodiazepin-1(2H)-one ions, [M-PhCO]+ ions, 2,4-disubstituted 1-benzoyl-2,3-dihydro-1H-1,5-benzodiazepine ions, or 1,2,4-trisubstituted 1H-1,7-benzodiazonine ions, which could also be formed from [M-Cl]+ ions by loss of CO and H2O molecules simultaneously. The [M-Cl]+ ions could further lose benzoyl radical to form [M-Cl-PhCO]+ ions, or lose benzoyl amide and undergo a rearrangement to form 4,6-disubstituted 1-benzoazocine-2(1H)-one ions. The [M-PhCO]+ ions could eliminate NH to produce 2a,4-disubstituted 2,2a,3,4-tetrahydroazeto[1,2,-a]quinolin-1-one ions, which could further eliminate chloroketene, CO and/or HCl to produce some important ions, respectively. 2,4-Disubstituted 1-benzoyl-2,3-dihydro-1H-1,5-benzodiazepine ions could lose benzoyl radical to yield 2,4-disubstituted 2,3-dihydro-1H-1,5-benzodiazepine ions, which could further yield other small fragment ions by loss of propene/styrene or small fragments. 相似文献
997.
Spin-polarized density functional theory calculations have been performed to characterize the hydrogen adsorption and diffusion on the Fe(111) surface at 2/3-, 1-, and 2-monolayer (ML) coverages. It is found that the most favored adsorption site for atomic hydrogen (H) is the top-shallow bridge site (tsb), followed by the quasi 4-fold site (qff) with the energy difference of about 0.1 eV, while the top site (t) is not competitive. Furthermore, the adsorbed atomic hydrogen (H) has a high mobility, as indicated by the small diffusion barriers. The local density of state (LDOS) analysis reveals that the Fe-H (tsb or qff) bond involves mainly the Fe 4s and 4p and H 1s orbitals with less contribution of the Fe 3d orbital, while the Fe 4s, 4p, and 3d orbitals all participate in the Fe-H (top) bond. In addition, the coverage effects on the adsorption configurations and adsorption energies are addressed. 相似文献
998.
Hongxia Xu Chengcheng Zhu Yuncong Chen Yang Bai Zhong Han Shankun Yao Yang Jiao Hao Yuan Weijiang He Zijian Guo 《Chemical science》2020,11(40):11037
Monitoring labile Zn2+ homeostasis is of great importance for the study of physiological functions of Zn2+ in biological systems. Here we report a novel ratiometric fluorescent Zn2+ sensor, CPBT, which was constructed based on chelation-induced alteration of FRET efficiency. CPBT was readily cell membrane permeable and showed a slight preferential localization in the endoplasmic reticulum. With this sensor, 3D ratiometric Zn2+ imaging was first realized in the head of zebra fish larvae via Z-stack mode. CPBT could track labile Zn2+ in a large number of cells through ratiometric flow cytometric assay. More interestingly, both ratiometric fluorescence imaging and flow cytometric assay demonstrated that the labile Zn2+ level in MCF-7 cells (cisplatin-sensitive) decreased while that in SKOV3 cells (cisplatin-insensitive) increased after cisplatin treatment, indicating that Zn2+ may play an important role in cisplatin induced signaling pathways in these cancer cells.A Zn2+ sensor exhibiting 3D ratiometric imaging and flow cytometric ability was constructed based on the FRET mechanism, and cisplatin-induced endogenous labile Zn2+ fluctuations were monitored in real time. 相似文献
999.
Assessment of the cyclic electron delocalization of the oxocarbon dianions, C(n)()O(n)()(2)(-) and their neutral counterparts C(n)()O(n)() (n = 3-6), by means of structural, energetic, and magnetic criteria, shows that C(3)O(3)(2)(-) is doubly aromatic (both sigma and pi cyclic electron delocalization), C(4)O(4)(2)(-) is moderately aromatic, but C(5)O(5)(2)(-), as well as C(6)O(6)(2)(-), are less so. Localized orbital contributions, computed by the individual gauge for localized orbitals method (IGLO), to the nucleus-independent chemical shifts (NICS) allow pi effects to be disected from the sigma single bonds and other influences. The C-C(pi) contribution to (NICS(0,pi) (i.e., at the center of the ring) in oxocarbon dianions decreases with ring size but shows little ring size effect at points 1.0 A above the ring. On the basis of the same criteria, C(4)O(4) exhibits cyclic electron delocalization due to partial occupancy of the sigma CC bonds. However, the dissociation energies of all the neutral oxocarbons, C(n)()O(n)(), are highly exothermic. 相似文献
1000.
Electrochemical studies of 1,5-dihydroxynaphthalene as substrate for voltammetric enzyme immunoassay
JIAO Kui YAO Hong XU Jin & ZHANG Shusheng College of Chemistry Molecular Engineering Qingdao University of Science Technology Qingdao China 《中国科学B辑(英文版)》2004,47(3):184-191
Immunoassay is one of the biochemical analytical techniques using the specific antigen antibody com-plexation for analytical purposes. It has extensive ap-plication in clinical diagnostics, prevention and cure of diseases, and virus diagnostics. The presentation and progress of immunoassay methodology are one of the greatest achievements of bioanalytical chemistry. It is estimated that several-hundred millions of immuno-analytical determinations are carried out every year all over the world. E… 相似文献