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991.
Jack M. Miller Kesgapillai Balasanmugam Adrian Fulcher 《Journal of mass spectrometry : JMS》1989,24(7):497-503
Some ion-formation processes during fast atom bombardment (FAB) are discussed, especially the possibility of reactions in the gas phase. Divided (two halves) FAB probe tips were used for introducing two different samples into the source at the same time. Our results showed [M + A]+ ions (where M = crown ethers and A = alkali metal ions), can be produced, at least in part, in the gas phase when crown ethers and sources of alkali metal ion are placed on two halves of the FAB probe tip. The extent of this ion formation depends on the volatility of the crown ether and on steric factors. Cluster ions such as (M + LiCl)Li+, (2M + LiCl)Li+, [2M + K]+ and [2M + Na]+ are also observed to form in the gas phase. Unimolecular decompositions contribute to some ions detected in FAB. When the alkali ion salt and the crown ether are mixed together the probability of [M + A]+ ion formation increases significantly, regardless of the volatility of the crown ether. 相似文献
992.
Fred L. Tobiason Greg H. Cain Jack W. Anderson 《Journal of polymer science. Part A, Polymer chemistry》1978,16(1):275-282
Dipole moments and their temperature dependence have been measured in p-dioxane for fractionated novolac phenol–, o-cresol–, and p-cresol–formaldehyde polymers. The phenol–formaldehyde fractions covered a molecular weight range of 200 to 6100, and the limiting dipole moment ratio 〈μ2〉/xm2 is 1.48. The p-cresol–formaldehyde dipole-moment ratio at a DP of 4 is 2.47, whereas the phenol–formaldehyde dipole-moment ratio is 1.40. That for o-cresol–formaldehyde is intermediate in value. The dipole-moment temperature coefficients are positive for p-cresol chains and negative for the phenol–formaldehyde chains. These results indicate that the hydroxyl groups along the p-cresol–formaldehyde polymer are highly ordered, with the aromatic rings closer to the sterically hindered planar position than in the phenol–formaldehyde polymers. 相似文献
993.
Araújo CS Drew MG Félix V Jack L Madureira J Newell M Roche S Santos TM Thomas JA Yellowlees L 《Inorganic chemistry》2002,41(8):2250-2259
The synthesis and properties of 3 new ligand-bridged bimetallic complexes, 1(2+), 2(2+), and 3(2+), containing [RuCl([9]aneS(3))](+) metal centers are reported. Each complex was bridged by a different ditopic ligand. 1(2+) is bridged by 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz), while 2(2+) and 3(2+) are bridged by 2,3-bis(2-pyridyl)pyrazine (dpp) and 2,2'-bipyrimidine (bpym), respectively. The Ru([II]) isovalent states of these complexes have been investigated using a variety of techniques. In the case of 3(2+), X-ray crystallography studies show preferential crystallization of an anti form with respect to coordinated chloride ligands (crystal data for [3][Cl(2)].4H(2)O: C(20)H(38)Cl(4)N(4)O(4)Ru(2)S(6), monoclinic, space group P2(1)/a, a = 10.929(14), b = 13.514(17), c = 11.299(16) A, beta = 90.52(1), V = 1669 A(3), Z = 2). UV/vis spectroscopy shows that spectra of these complexes are dominated by intraligand (pi-->pi) and metal-to-ligand Ru(d)-->L(pi) charge transfer transitions. Electrochemical studies reveal that metal-metal interactions are sufficiently intense to generate the Ru(III)/Ru(II) mixed valence [[RuCl([9]aneS(3))(2)](L-L)](3+) state, where L-L = individual bridging ligands. Although the 1(3+), 2(3+), and 3(3+) mixed valence states were EPR silent at room temperature and 77 K, isotropic solution spectra were observed for the electrochemically generated radical cations 1(+), 2(+), and 3(+), with 1(+) displaying well-resolved hyperfine coupling to bridging ligand nitrogens. Using UV/vis/NIR spectroelectrochemistry, we investigated optical properties of the mixed valence complexes. All three showed intervalence charge transfer (IVCT) bands that are much more intense than electrochemical data indicate. Indeed, a comparison of IVCT data for 1(3+) with an analogous structure containing [(NH3)(3)Ru](2+) metal centers shows that the IVCT in the new complex is an order of magnitude more intense. It is concluded that although the new complexes show relatively weak electrostatic interactions, they possess large resonance energies. 相似文献
994.
W.A. Shantha Nandana Jack Passmore D.C. Neil Swindells Peter S. White Chi-Ming Wong 《Journal of fluorine chemistry》1982,21(1):14
Antimony pentafluoride acts as a useful oxidising agent towards many non-metals, giving interesting cations, and in the process is itself reduced. It would be helpful to know what the reduced products are, and under what conditions they are formed. Therefore, SbF5 and the known SbF5·SbF3(1) in AsF3 solution were reduced by iodine and/or PF3 giving crystals of the new adduct, (SbF3)6(SbF5)5 [Monoclinic, a = 11.638(1), b = 8.995(1), c = 16.723(3) ā, β = 106.81(1)°, P21/c]; (SbF3)5(SbF5)3 [Orthorhombic, a = 19.187(9), b = 15.890(2), c = 15.713(3) ā, Pnma] and (SbF3)3SbF5 [Monoclinic, a = 10.895(3), b = 10.941(3), c = 4.772(1) ā, β = 96.66(3)°, P21/m]. (SbF3)3SbF5 seemed to be the most reduced adduct, no evidence was obtained for (SbF3)n(SbF5) n > 3, under these conditions. The (SbF3)6(SbF5)5 adduct has a Raman spectrum identical to that reported by Gillespie(2) and coworkers for an adduct of approximate composition SbF3·SbF5 and has a very different structure to that of (SbF3)6(SbF6)5 reported by Edwards.(3) The crystal structures of the new adducts will be discussed and the cations they contain compared with those found in SbF3·SbF5(1) and (SbF5)6(SbF5)5(3) (Edward's form). 相似文献
995.
Jack D. Anderson N. Kent Dalley Ganapathi R. Revankar Roland K. Robins 《Journal of heterocyclic chemistry》1986,23(6):1869-1878
Several 3-alkoxysubstituted pyrazolo[3,4-d]pyrimidine ribonucleosides structurally related to adenosine, inosine and guanosine have been prepared by the direct glycosylation of preformed aglycon precursor containing a 3-alkoxy substituent. Ring closure of 5(3)-amino-3(5)-ethoxypyrazole-4-carboxamide ( 6b ) with either formamide or potassium ethyl xanthate gave 3-ethoxyallopurinol ( 7b ) and 3-ethoxy-6-thioxopyrazolo[3,4-d]-pyrimidin-4(5H,7H)-one ( 10 ), respectively. Methylation of 10 gave the corresponding 6-methylthio derivative 15 . Similar ring annulation of 5(3)-methoxypyrazole-4-carboxamide ( 6a ) with formamide afforded 3-methoxyallopurinol ( 7a ). Treatment of 5(3)-amino-3(5)-methoxypyrazole-4-carbonitrile ( 5a ) with formamidine acetate furnished 4-amino-3-methoxypyrazolo[3,4-d]pyrimidine ( 4 ). High-temperature glycosylation of 7b with 1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose in the presence of boron trifluoride etherate gave a 2:1 mixture of N-1 and N-2 glycosyl blocked nucleosides 11b and 13b . Deprotection of 11b and 13b with sodium methoxide gave 3-ethoxy-1-β-D-ribofuranosylpyrazolo[3,4-d]pyrimidin-4(5H)-one ( 12b ) and the corresponding N-2 glycosyl isomer 14b , respectively. Similar glycosylation of either 4 or 7a , and subsequent debenzoylation gave exclusively 4-amino-3-methoxy-1-β-D-ribofuranosylpyrazolo[3,4-d]pyrimidine ( 9 ) and 3-methoxy-1-β-D-ribofuranosylpyrazolo[3,4-d]pyrimidin-4-(5H)-one ( 12a ), respectively. The structural assignment of 12a was made on the basis of single-crystal X-ray analysis. Application of this general glycosylation procedure to 15 gave the corresponding N-1 glycosyl derivative 16 as the sole product, which on debenzoylation afforded 3-ethoxy-6-(methylthio)-1-(3-D-ribofuranosylpyrazolo[3,4-d]pyrimidin-4(5H)-one ( 17 ). Oxidation of 16 and subsequent ammonolysis furnished the guanosine analog 6-arnino-3-ethoxy-1-β-D-ribofuranosylpyrazolo[3,4-d]-pyrimidin-4(5H)-one ( 19 ). Similarly, starting from 3-methoxy-4,6-bis(methylthio)pyrazolo[3,4-d]pyrimidine ( 20 ), 6-amino-3-methoxy-1-β-D-ribofuranosylpyrazolo[3,4-d]pyrimidin-4(5H)-one ( 23 ) was prepared. 相似文献
996.
Forrest T. Smith Jack Deruiter Deborah Ann Carter 《Journal of heterocyclic chemistry》1989,26(6):1815-1817
Synthetic routes to 1,2,3,5,10,10a-hexahydropyrrolo[1,2,-b]isoquinolin-5-ones functionalized at C-10 were investigated. Attempts to prepare the ketone 2 , and subsequently introduce the desired C-10 hydroxymethylene group were unsuccessful due to the failure of 6 to cyclize and the unreactivity of 9 to relevant nucleophiles. Compound 1 was prepared by the condensation of 1-pyrroline with 7-methoxyisobenzopyran-1,3,-(4H)-dione to give 12 in quantitative yield. Acyl halide formation and subsequent reduction gave the desired compound 1. 相似文献
997.
Eric C. Huang Jack D. Henion 《Journal of the American Society for Mass Spectrometry》1990,1(2):158-165
Tryptic digests were analyzed by means of online microbore liquid chromatography combined with mass spectrometry (LC/MS) for some common proteins. Following conventional enzymatic digestion with trypsin, the freeze-dried residues were dissolved in high-performance liquid chromatography (HPLC) eluent and subjected to gradient reversed-phase microbore HPLC separation with mass spectrometric detection. The latter was done in the full-scan single or tandem (MS/MS) mass spectrometry mode. The formation of gas-phase ions from dissolved analytes was accomplished at atmospheric pressure by pneumatically assisted electrospray (ion spray) ionization. This produced field-assisted ion evaporation of dissolved ions, which could then be mass-analyzed for molecular mass or structure. In the full-scan LC/MS mode, the masses for the peptide fragments in the tryptic digests can be determined as either their singly or multiply charged ions. When the molecular weights of the peptides lie outside the mass range of the mass spectrometer, the multiply charged feature of these experimental conditions still provides reliable molecular weight determinations. In addition, collision-activated dissociation (CAD) on selected peptide precursor ions provides online LC/MS/MS sequence information for the tryptic fragments. Results are shown for the tryptic digests of horse heart cytochrome c, bovine β-lactoglobulin A, and bovine β-lactoglobulin B. 相似文献
998.
Jack Huet 《Tetrahedron》1981,37(4):731-741
13C NMR chemical shifts of ethylenic carbon atom Cβ of α alkoxy-indenes and α-alkoxy-styrenes are affected by the conformation of the OR group with respect to the double bond and hence the efficiency of p- Π conjugation but, contrary to previous results, δCα is not affected. The phenyl group exerts a diamagnetic Π- effect on Cα and Cβ which is a function of its dihedral angle with the double bond. Although δCβ is especially sensitive to the Π-electron density, the chemical shifts of the ethylenic carbons are best understood by considering the total charge density. The σ and Π contributions to the total charge density are discussed using the preferred conformation of the molecules. This approach strongly suggests that the correlation between the gradual shift of δCα to low frequency and the gradual shift of δCβ to high frequency (relative to TMS) as R changes from RCH3 to RtC4H9 in certain series of enol-ethers is not due to pΠ conjugation variations. This method of interpreting 13C NMR shifts, as opposed to previous methods, is compatible with explanations of other physico-chemical properties of alkyl vinyl ethers. Although it is sometimes possible to correlate the gradual shifts of δCβ with (σ + Π) electron density variations in a homogeneous series, it seems impossible to predict the relation. In all cases, there is no evident correlation between gradual shifts of δCβ(orδCα) and the reactivity of enol ethers because one cannot consider the role of the out-of-plane conformation of the alkoxy group (which increases from RCH3 to RtC4H9); however, the out of plane conformation does not have an identical effect on δCβ and the reactivity. 相似文献
999.
A finite groupG isQ-admissible if there exists a division algebra finite dimensional and central overQ which is a crossed product forG. AQ-admissible group is necessarily Sylow-metacyclic (all its Sylow subgroups are metacyclic). By means of an investigation into the structure of Sylow-metacyclic groups, the inverse problem (is every Sylow-metacyclic groupQ-admissible?) is essentially reduced to groups of order 2 a 3 b and to a list of known “almost simple” groups. 相似文献
1000.
V—V energy transfer from a large molecule excited to vibrational energies of chemical interest has been demonstrated by detection of ≈ 1.5% yield of CO2(001) due to energy transfer from azulene (Evib ≈ 30600 cm?1. Also, the average enery lost per collision by azulene was measured as a function of Evib, and the rate constant for CO2(001) deactivation by azulene was determined. 相似文献