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71.
Pampa Mukherjee Michael G.B. Drew Vassilis Tangoulis Marta Estrader Carmen Diaz Ashutosh Ghosh 《Polyhedron》2009,28(14):2989-2996
Three new linear trinuclear nickel(II) complexes, [Ni3(salpen)2(OAc)2(H2O)2]·4H2O (1) (OAc = acetate, CH3COO−), [Ni3(salpen)2(OBz)2] (2) (OBz = benzoate, PhCOO−) and [Ni3(salpen)2(OCn)2(CH3CN)2] (4) (OCn = cinnamate, PhCHCHCOO−), H2salpen = tetradentate ligand, N,N′-bis(salicylidene)-1,3-pentanediamine have been synthesized and characterized structurally and magnetically. The choice of solvent for growing single crystal was made by inspecting the morphology of the initially obtained solids with the help of SEM study. The magnetic properties of a closely related complex, [Ni3(salpen)2(OPh)2(EtOH)] (3) (OPh = phenyl acetate, PhCH2COO−) whose structure and solution properties have been reported recently, has also been studied here. The structural analyses reveal that both phenoxo and carboxylate bridging are present in all the complexes and the three Ni(II) atoms remain in linear disposition. Although the Schiff base ligand and the syn–syn bridging bidentate mode of the carboxylate group remain the same in complexes 1–4, the change of alkyl/aryl group of the carboxylates brings about systematic variations between six- and five-coordination in the geometry of the terminal Ni(II) centres of the trinuclear units. The steric demand as well as hydrophobic nature of the alkyl/aryl group of the carboxylate is found to play a crucial role in the tuning of the geometry. Variable-temperature (2–300 K) magnetic susceptibility measurements show that complexes 1–4 are antiferromagnetically coupled (J = −3.2(1), −4.6(1), −3.2(1) and −2.8(1) cm−1 in 1–4, respectively). Calculations of the zero-field splitting parameter indicate that the values of D for complexes 1–4 are in the high range (D = +9.1(2), +14.2(2), +9.8(2) and +8.6(1) cm−1 for 1–4, respectively). The highest D value of +14.2(2) and +9.8(2) cm−1 for complexes 2 and 3, respectively, are consistent with the pentacoordinated geometry of the two terminal nickel(II) ions in 2 and one terminal nickel(II) ion in 3. 相似文献
72.
Boudalis AK Pissas M Raptopoulou CP Psycharis V Abarca B Ballesteros R 《Inorganic chemistry》2008,47(22):10674-10681
Complex [Ni 5{pyCOpyC(O)(OMe)py} 2(O 2CMe) 4(N 3) 4(MeOH) 2].2MeOH.2.6H 2O ( 1.2MeOH.2.6H 2O) was synthesized by the reaction of Ni(O 2CMe) 2.4H 2O with pyCOpyCOpy and NaN 3 in refluxing MeOH. It crystallizes in the monoclinic C2/ c space group and consists of five Ni (II) atoms in a helical arrangement. Direct current magnetic susceptibility studies reveal ferromagnetic interactions between the Ni (II) ( S = 1) ions, stabilizing an S = 5 ground state. Alternating current susceptibility experiments revealed the existence of out-of-phase signals indicative of slow magnetic relaxation. Analysis of the signals showed that they are composite, suggesting more than one relaxation process, while analysis of their magnitudes suggests not all molecules undergo slow magnetic relaxation. Magnetization field-sweep experiments revealed hysteresis at 1.8 K, and magnetization decay experiments clearly verified the appearance of slow magnetic relaxation at that temperature. 相似文献
73.
Boudalis AK Clemente-Juan JM Dahan F Psycharis V Raptopoulou CP Donnadieu B Sanakis Y Tuchagues JP 《Inorganic chemistry》2008,47(23):11314-11323
Complexes [Fe(Hhbi)(2)(NO(3))].2EtOH (1.2EtOH) and [Fe(2)(mu-OH)(2)(Hhbi)(4)].2H(2)O.8EtOH (2.2H(2)O.8EtOH) crystallize in the orthorhombic Fdd2 and P4(2)2(1)2 space groups, respectively (Hhbi(-) = the monoanion of 2-(2'-hydroxyphenyl benzimidazole). Complex 1 exhibits paramagnetic relaxation as evidenced by Mossbauer spectroscopy, and significant axial zero-field splitting (1.5 cm(1) 相似文献
74.
Catherine Gkioni Athanassios K. Boudalis Yiannis Sanakis Leondios Leondiadis Vassilis Psycharis Catherine P. Raptopoulou 《Polyhedron》2008
The systematic investigation of the parameter space of the CuCl2/H2mal/phen reaction system in MeOH resulted in the isolation of seven different complexes either as mixtures or in pure form, six of which have been structurally characterized. The molar ratios of the reactants and the crystallization methods have been systematically varied, leading to the isolation of compounds [Cu(H2O)(phen)(mal)] (1), [Cu(MeOH)(phen)(mal)] (2), [Cu2Li2Cl2(phen)2(mal)2(MeOH)4] (3), [Cu2(phen)4(mal)][CuCl(phen)(mal)](OH) (4), [CuCl(phen)2]Cl (5), and [CuCl(phen)(mal)][CuCl(phen)2][Cu(phen)2(Hmal)]Cl (6). The coordination versatility of the malonato ligand has been confirmed by the presence of three different coordination modes and its two deprotonation states in compounds 1–6. Solution studies on methanolic solutions of 2–4 and 6 by mass spectrometry revealed the absence of parent ion peak and the presence of fragment ions of low relative abundance not previously found in their crystal structure, thus indicating decomposition and rearrangement/reorganization of the complexes in solution and confirming the dynamic character of their solutions. Compounds 3 and 4 have been also studied in the solid state by EPR spectroscopy and magnetic measurements. 相似文献
75.
Curative radiation therapy of pelvic malignancies, frequently results in dose limiting toxicities such as serous, mucoid, or more rarely, bloody diarrhea. Several studies have evaluated the cytoprotective effects of amifostine in preventing rectal mucositis associated with radiation treatment. We searched Medline for published comparative studies that evaluated the use of amifostine to reduce radiation-induced toxicity associated with pelvic irradiation. In ten studies there was an evidence-based cytoprotection (P less than 0.05)by amifostine. Although results are variable, current evidence suggests that amifostine may have a radioprotective effect in the rectal mucosa, particularly when administered intrarectally. Significant improvements were seen in both symptomatic and objective(rectosigmoidoscopy) end points. There is a need to conduct well-designed clinical trials with sufficient numbers of participants to confirm these findings together with a cost benefit study. Objective measurements using rectosigmoidoscopy are superior to subjective measures such as WHO or RTOG/EORTC toxicity grading scales. 相似文献
76.
Fitilis I Fakis M Polyzos I Giannetas V Persephonis P Mikroyannidis J 《The journal of physical chemistry. A》2008,112(21):4742-4748
Two photon absorption (TPA) and photophysical properties of three new symmetrical chromophores with electron accepting phthalimide edge substituents have been studied. The three chromophores contain fluorene, alcoxy-substituted divinyl benzene, and carbazole moieties as central cores, respectively. The femtosecond time-resolved fluorescence upconversion spectroscopy and two photon excited fluorescence technique have been carried out. The effect of solvent polarity on TPA and on photophysics has also been determined. Ultrafast fluorescence dynamics, with decay times ranging from 1 to 13 ps, are revealed in polar solvents. This is attributed to the relaxation of the chromophores to the intramolecular charge transfer state. The chromophore bearing fluorene central core, being of the type A-pi-A, is the most efficient concerning TPA. Strong TPA, with a cross section value as high as 2100 GM at an excitation wavelength of 770 nm is found in acetophenone which is a solvent of intermediate polarity. The TPA spectra were also reproduced using a sum over states three-state model. A study of the TPA induced photobleaching of the fluorene molecule, doped in a solid poly(methyl-methacrylate) film, has shown that this material is very promising for efficient TPA optical data storage. 相似文献
77.
Georgopoulou AN Adam R Raptopoulou CP Psycharis V Ballesteros R Abarca B Boudalis AK 《Dalton transactions (Cambridge, England : 2003)》2011,40(32):8199-8205
Complex [Fe(II)Gd(III){pyCO(OEt)pyCOH(OEt)py}(3)](ClO(4))(2) (1) crystallizes in the Cc space group and contains one hexacoordinate ferrous ion and one enneacoordinate Gd(III) ion. Complex [Fe(2)(II)Gd(III){pyCO(OEt)py}(4)(NO(3))(H(2)O)][Gd(NO(3))(5)](0.5)(ClO(4)) (2) crystallizes in the C2/c space group and contains two hexacoordinate ferrous ions and one octacoordinate Gd(III) ion. Both complexes have been prepared by the metal-assisted ethanolysis of ligands di-2,6-(2-pyridylcarbonyl)pyridine (pyCOpyCOpy, dpcp) and di-2-pyridyl ketone ((py)(2)CO, dpk), which exhibit similar structures. M?ssbauer spectroscopic studies of 2 revealed the presence of two quadrupole-split doublets of equal intensities, each assigned to a ferrous site. These doublets exhibit similar isomer shifts (δ(1) = 1.14 mm s(-1), δ(2) = 1.11 mm s(-1)) but quite different quadrupole splittings (ΔE(Q1) = 3.55 mm s(-1), ΔE(Q2) = 2.74 mm s(-1)). Magnetic studies revealed weak ferromagnetic Fe(II)-Gd(III) interactions for both complexes (J(FeGd) = +0.68 cm(-1), D(Fe) = 12.0 cm(-1) for 1 and J(FeGd) = +0.03 cm(-1), J(FeFe) = -1.73 cm(-1) for 2, according to the -JS(i)S(j) spin-Hamiltonian formalism). 相似文献
78.
Christina D. Polyzou Helen Nikolaou Catherine P. Raptopoulou Konstantis F. Konidaris Vlasoula Bekiari Vassilis Psycharis Spyros P. Perlepes 《Molecules (Basel, Switzerland)》2021,26(6)
The first use of methyl 2-pyridyl ketoxime (mepaoH) in homometallic lanthanide(III) [Ln(III)] chemistry is described. The 1:2 reactions of Ln(NO3)3·nH2O (Ln = Nd, Eu, Gd, Tb, Dy; n = 5, 6) and mepaoH in MeCN have provided access to complexes [Ln2(O2CMe)4(NO3)2(mepaoH)2] (Ln = Nd, 1; Ln = Eu, 2; Ln = Gd, 3; Ln = Tb, 4; Ln = Dy, 5); the acetato ligands derive from the LnIII—mediated hydrolysis of MeCN. The 1:1 and 1:2 reactions between Dy(O2CMe)3·4H2O and mepaoH in MeOH/MeCN led to the all-acetato complex [Dy2(O2CMe)6(mepaoH)2] (6). Treatment of 6 with one equivalent of HNO3 gave 5. The structures of 1, 5, and 6 were solved by single-crystal X-ray crystallography. Elemental analyses and IR spectroscopy provide strong evidence that 2–4 display similar structural characteristics with 1 and 5. The structures of 1–5 consist of dinuclear molecules in which the two LnIII centers are bridged by two bidentate bridging (η1:η1:μ2) and two chelating-bridging (η1:η2:μ2) acetate groups. The LnIII atoms are each chelated by a N,N’-bidentate mepaoH ligand and a near-symmetrical bidentate nitrato group. The molecular structure of 6 is similar to that of 5, the main difference being the presence of two chelating acetato groups in the former instead of the two chelating nitrato groups in the latter. The geometry of the 9-coordinate LnIII centers in 1, 5 and 6 can be best described as a muffin-type (MFF-9). The 3D lattices of the isomorphous 1 and 5 are built through H-bonding, π⋯π stacking and C-H⋯π interactions, while the 3D architecture of 6 is stabilized by H bonds. The IR spectra of the complexes are discussed in terms of the coordination modes of the organic and inorganic ligands involved. The Eu(III) complex 2 displays a red, metal-ion centered emission in the solid state; the TbIII atom in solid 4 emits light in the same region with the ligand. Magnetic susceptibility studies in the 2.0–300 K range reveal weak antiferromagnetic intramolecular GdIII…GdIII exchange interactions in 3; the J value is −0.09(1) cm−1 based on the spin Hamiltonian Ĥ = −J(ŜGd1·ŜGd2). 相似文献
79.
Tarushi A Kastanias F Psycharis V Raptopoulou CP Psomas G Kessissoglou DP 《Inorganic chemistry》2012,51(14):7460-7462
The interaction of ZnCl(2) with 2-dipyridylketonoxime (=Hpko) and flufenamic acid (=Hfluf) in a basic methanolic solution leads to the formation of a hexanuclear 24-membered metallacoronate, [Zn(6)(OH)(2)(pko)(4)(fluf)(6)] (1), with a [Zn-O-C-O] repeat unit and a nonsteroidal antiinflammatory drug as the constructing ligand. Compound 1 retains its structure in a dimethyl sulfoxide solution, as shown by (1)H NMR spectroscopy and molar conductance. 相似文献
80.
Abstract The glycosylation reaction based upon anomeric free hydroxyl group activation by its transformation into an alkcxyiminium salt by the action of the N,N-dimethylformamide/phosgene complex has been extended to the pentofuranose series. The mechanism of this glycosylation is discussed. Nine glycosides have been prepared. 相似文献