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61.
K. W. Busch M. A. Busch S. Gopalakrishnan E. Chibowski 《Colloid and polymer science》1995,273(12):1186-1192
Potentiometric titrations of TiO2 (anatase) suspensions in solutions of 10–2, 10–3, and 10–4 M NaCl prior to treatment with a radiofrequency (RF) electric field gave values of pHpzc and pHiep of 5.75±0.1 and 5.85±0.1, respectively, within the range of literature values. Surface charge plots versus pH for untreated samples gave curves with a common intersection point, indicating that NaCl acts as an indifferent electrolyte. Identical suspensions of anatase were then exposed for 30 min to an RF electric field with a peak-to-peak, no-load amplitude of 34V and a frequency of 44 MHz. Portions of the treated suspension were titrated after different time periods following removal of the field (2, 15, 30, and 45 min). At 2 min, the pHpzc had shifted to 6.50±0.1, and at 15, 30 and 45 min, the curves for the three NaCl concentrations were found to lack a common intersection point, an effect which became more pronounced with time. It is proposed that RF treatment results in the formation of a porous gel layer of hydrous titanium dioxide on the surface of the anatase particles that subsequently undergoes a slow ion-exchange reaction involving ions of the supporting electrolyte. 相似文献
62.
M. Gopalakrishnan P. Sureshkumar V. Kanagarajan J. Thanusu 《Research on Chemical Intermediates》2007,33(6):541-548
Condensation of structurally diverse aldehydes including heterocyclic aldehydes, like furfural, with various amines in the
presence of calcium oxide affording the corresponding imines in solvent-free conditions in good to excellent yields under
microwave irradiation is described. A comparative study has been done under thermal conditions. The synergy between dry media
and microwave irradiation in this reaction is evaluated by condensing less electrophilic aldehydes with poorly nucleophilic
amines. The main advantages of this environmentally friendly protocol are the use of the non-toxic and inexpensive reagent
calcium oxide and the considerable rate enhancement in comparison with a thermal reaction. 相似文献
63.
J. Gopalakrishnan 《Journal of Chemical Sciences》1984,93(3):421-432
A survey of recent developments in preparative solid state chemistry shows that, with a knowledge of structural chemistry
and reactivity patterns of solids, it is possible to synthesize a variety of new solids possessing novel structures. A distinction
is made between synthesis ofnew solids and synthesis of solids bynew methods. Three new routes to solid state synthesis are recognized: the precursor method, and topochemical methods involving redox
and ion-exchange reactions. The low-temperature topochemical methods enable synthesis of metastable phases that are inaccessible
by the high temperature route. Several illustrative examples of solid state synthesis from the recent literature are presented. 相似文献
64.
Karthikeyan Gopalakrishnan Mohanraj Kuttappan Elango Kuppanagounder P. Girishkumar Krishnapillai 《Transition Metal Chemistry》2004,29(1):86-90
A series of LnIII–tetracycline complexes of the type [Ln(TC)Cl3]·2H2O [Ln = lanthanum, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium and yttrium; TC = tetracycline] have been synthesized and characterized by analytical, i.r., electronic, 1H-n.m.r. spectral studies, X-ray diffraction and thermogravimetric analysis. A pentagonal bipyramidal structure has been tentatively proposed for the new complexes. The ligand and the new complexes were tested in vitro to evaluate their activity against the bacteria Escherichia coli and Staphylococcus aureus. 相似文献
65.
Sivakumar T Ramesha K Lofland SE Ramanujachary KV Subbanna GN Gopalakrishnan J 《Inorganic chemistry》2004,43(6):1857-1864
We describe the synthesis of two new quadruple perovskites, Sr(2)La(2)CuTi(3)O(12) (I) and Ca(2)La(2)CuTi(3)O(12) (II), by solid-state metathesis reaction between K(2)La(2)Ti(3)O(10) and A(2)CuO(2)Cl(2) (A = Sr, Ca). I is formed at 920 degrees C/12 h, and II, at 750 degrees C/24 h. Both the oxides crystallize in a tetragonal (P4/mmm) quadruple perovskite structure (a = 3.9098(2) and c = 15.794(1) A for I; a = 3.8729(5) and c = 15.689(2) A for II). We have determined the structures of I and II by Rietveld refinement of powder XRD data. The structure consists of perovskite-like octahedral CuO(4/2)O(2/2) sheets alternating with triple octahedral Ti(3)O(18/2) sheets along the c-direction. The refinement shows La/A disorder but no Cu/Ti disorder in the structure. The new cuprates show low magnetization (0.0065 micro(B) for I and 0.0033 micro(B) for II) suggesting that the Cu(II) spins are in an antiferromagnetically ordered state. Both I and II transform at high temperatures to 3D perovskites where La/Sr and Cu/Ti are disordered, suggesting that I and II are metastable phases having been formed in the low-temperature metathesis reaction. Interestingly, the reaction between K(2)La(2)Ti(3)O(10) and Ca(2)CuO(2)Cl(2) follows a different route at 650 degrees C, K(2)La(2)Ti(3)O(10) + Ca(2)CuO(2)Cl(2) --> CaLa(2)Ti(3)O(10) + CaCuO(2) + 2KCl, revealing multiple reaction pathways for metathesis reactions. 相似文献
66.
Gopalakrishnan Vaidyanathan M. Todd Coolbaugh James F. Garvey 《Journal of Cluster Science》1991,2(3):183-201
The study of van der Waals clusters is an area of growing interest and is being widely studied for a number of reasons. The measurement of the ionization efficiency (IE) curves have yielded a wealth of information by enabling ionization and appearance energies of ions to be determined which are essential for the calculation of thermochemical data. In the case of van der Waals clusters, the measurement ofIE curves enables one to determine the qualitative trends in the ionization potentials as a function of cluster size. In additionIE curves have also offered valuable insight into ionization related processes occurring in clusters. This paper will cover some of the more recent studies of Penning ionization, exciton induced decay and Coulomb explosion in van der Waals clusters through the use of electron impactIE curves. 相似文献
67.
68.
69.
A Legendre spectral element model for sloshing and acoustic analysis in nearly incompressible fluids
D. Krishna Kishor S. Gopalakrishnan Ranjan Ganguli 《Journal of computational physics》2010,229(7):2605-2624
A new spectral finite element formulation is presented for modeling the sloshing and the acoustic waves in nearly incompressible fluids. The formulation makes use of the Legendre polynomials in deriving the finite element interpolation shape functions in the Lagrangian frame of reference. The formulated element uses Gauss–Lobatto–Legendre quadrature scheme for integrating the volumetric stiffness and the mass matrices while the conventional Gauss–Legendre quadrature scheme is used on the rotational stiffness matrix to completely eliminate the zero energy modes, which are normally associated with the Lagrangian FE formulation. The numerical performance of the spectral element formulated here is examined by doing the inf–sup test on a standard rectangular rigid tank partially filled with liquid. The eigenvalues obtained from the formulated spectral element are compared with the conventional equally spaced node locations of the h-type Lagrangian finite element and the predicted results show that these spectral elements are more accurate and give superior convergence. The efficiency and robustness of the formulated elements are demonstrated by solving few standard problems involving free vibration and dynamic response analysis with undistorted and distorted spectral elements, and the obtained results are compared with available results in the published literature. 相似文献
70.
Gönen ZS Paluchowski D Zavalij P Eichhorn BW Gopalakrishnan J 《Inorganic chemistry》2006,45(21):8736-8742
A new soft-chemical transformation of layered perovskite oxides is described wherein K2O is sequentially extracted from the Ruddlesden-Popper (R-P) phase, K2La2Ti3O10 (I), yielding novel anion-deficient KLa2Ti3O(9.5) (II) and La2Ti3O9 (III). The transformation occurs in topochemical reactions of the R-P phase I with PPh4Br and PBu4Br (Ph = phenyl; Bu = n-butyl). The mechanism involves the elimination of KBr accompanied by decomposition of PR4+ (R = phenyl or n-butyl) that extracts oxygen from the titanate. Analysis of the organic products of decomposition reveals formation of Ph3PO, Ph3P, and Ph-Ph for R = phenyl, and Bu3PO, Bu3P along with butane, butene, and octane for R = butyl. The inorganic oxides II and III crystallize in tetragonal structures (II: P4/mmm, a = 3.8335(1) A, c = 14.334(1) A; III: I4/mmm, a = 3.8565(2) A, c = 24.645(2) A) that are related to the parent R-P phase. II is isotypic with the Dion-Jacobson phase, RbSr2Nb3O10, while III is a unique layered oxide consisting of charge-neutral La2Ti3O9 anion-deficient perovskite sheets stacked one over the other without interlayer cations. Interestingly, both II and III convert back to the parent R-P phase in a reaction with KNO3. While transformations of the R-P phases to other related layered/three-dimensional perovskite oxides in ion-exchange/metathesis/dehydration/reduction reactions are known, the simultaneous and reversible extraction of both cations and anions in the conversions K2La2Ti3O10 right harpoon over left harpoon KLa2Ti3O9.5 right harpoon over left harpoon La2Ti3O9 is reported here for the first time. 相似文献