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41.
Reaction of CuI with 1 or 2 equivalent(s) N,N′‐Bis(diphenylphosphino)‐2,6‐diaminopyridine (BDDP) gives two different complexes, [Cu(I)μ‐(BDDP‐κP,Npy)]2 ( 1 ) and [Cu(BDDP‐κP,Npy)2]I ( 2 ), in high yields. The determination of the molecular structure show that both CuI atoms are tetrahedrally coordinated, rather than a square‐planar geometry reported for Cr0, NiII‐BDDP complexes before, which contains a planar tridentate chelate ring system. The introduction of AuCl(tht) (tht = tetrahydrothiophene) into [Cu(BDDP‐κP,Npy)2]I leads unexpectedly to the formation of a digold complex 2,6‐[(ClAuPh2P)HN]2C5H3N and dimeric [Cu(I)μ‐(BDDP‐κP,Npy)]2. 相似文献
42.
To study the importance of charge–charge and cation-π interactions for the binding of positively charged amine ligands to
their receptors, the energies of interaction between [(CH3)4–N]+, [(CH3)3–NH]+, and [(CH3)4–NH3]+ and acetate, as a model of Asp and Glu, and with benzene, as a model of aromatic side chains, were obtained at the MP2/aug-cc-pVDZ
level of theory. The free energies of solvation in water were also calculated for the different amines. It was found that,
although primary amines form stronger charge–charge interactions with acetate than tertiary or quaternary amines, the difference
is not large enough to compensate their higher solvation energy. Quaternary amines show the weakest interaction with acetate.
However, their alkyl groups can interact with various aromatic groups, enhancing ligand binding to the receptor. The analysis
was completed with MD calculations on amine binding to the G protein-coupled receptors β2AR and CCR5. The calculations on the model systems were found to be in good agreement with the simulations of the ligand-receptor
complexes.
Contribution to the Serafin Fraga Memorial Issue. 相似文献
43.
Summary Improved energy-adjusted quasirelativistic pseudopotentials for lanthanoid atoms with fixed valency are presented and tested in molecular calculations for CeO, CeF, EuO, GdO, YbO, and YbF. The pseudopotential calculations treat the lanthanoid 4f shell as part of the core and yield accurate estimates for average bond lengths, vibrational frequencies and dissociation energies of all states belonging to a superconfiguration. Information for each individual state of the considered superconfiguration may be obtained from subsequent ligand field model calculations. The results of this combined pseudo-potential and ligand field approach (PPLFT) are compared to more accurate calculations with ab initio pseudopotentials that include the lanthanoid 4f orbitals explicitly in the valence shell and to available experimental data. 相似文献
44.
Summary Basic alumina-bonded diethylenetriaminepentaacetic acid (DTPA) has been utilized for the separation and preconcentration of
some transition metal ions on the basis of ligand exchange. Breakthrough capacity and rate of sorption have been studied.
The distribution coefficients of 16 transition metal ions have been determined in demineralized water, 0.01 M sodium citrate
and in four different pH systems. On the basis of differences in Kd values some quantitative separations of metal ions have
been achieved. The greater selectivity behaviour (higher Kd values) of the adsorbent for Pt(IV)and Cr(III) has been utilized
for their preconcentration in the presence of other metal ions. The method has been employed for the recovery of Pt(IV) and
Cr(III) from tapwater and sea-water samples. 相似文献
45.
Recognition of sheared and normal DNA by a novel metal complex [Co(phen)2hpip]3+ (phen=1,10-phenanthroline, HPIP=2-(2-hydroxyphenyl)imidazole[4,5-f][1,10]phenanethroline) is studied by molecular modeling. Calculating results indicate that, this complex can specifically recognize DNA segment of sequence –MMNNMM– (M means mismatch base pairs and N means normal base pairs). Intercalating from minor groove between the middle normal duplex into the sheared DNA with the depth of 1.2 nm is of preference and enantioselectivity is observed. Comparison on the two DNA structures of optimal conformation and analysis on the interaction between DNA and the two tail ligands of the complex show that, the effect of the two neighboring mismatch duplexes on the structure of the middle normal base pairs and the steric interaction between the mismatch duplexes and the two tail ligands of the complex are the essential reason to the segment specificity. Investigation on the detailed energy terms indicate that, in effecting enantioselectivity, the electrostatic distribution of the complex is in the majority and steric interaction is at the next place. But, steric interaction is surely the only factor determining the intercalating from minor groove. 相似文献
46.
Vaggelis Hondrellis Themistoclis Kabanos Spyros P. Perlepes John M. Tsangaris 《Monatshefte für Chemie / Chemical Monthly》1988,119(10):1091-1101
New complexes of the formulaeM(fur)2·2H2O (M = Mn, Cu, Zn),M(fur)2·3H2O (M = Co, Ni, Cd), Hg2(fur)3Cl2·2H2O, Pd(fur)Cl·H2O and Rh(fur)3·3H2O, wherefurH = 4-chloro-N-(2-furfuryl)-5-sulfamoylanthranilic acid, have been prepared and characterized by conductivity measurements, X-ray powder patterns, thermal methods, effective magnetic moments as well as by IR, ligand field,1H-NMR and ESR spectroscopic studies. The anionfur
– shows a chelated bidentate O(carboxylato), N(imino)-coordinating behaviour.
Metallkomplexe der diuretischen Droge Furosemid
Zusammenfassung Neue Komplexe der Verbindungen:M(fur)2·2H2O (M = Mn, Cu, Zn),M(fur)2·3H2O (M = Co, Ni, Cd), Hg2(fur)3Cl2·2H2O, Pd(fur)Cl·H2O und Rh(fur)3·3H2O, wobeifurH 4-chlor-N-(2-furfuryl)-5-sulfamoylanthanilsäure ist, wurden dargestellt. Die Komplexe wurden durch Leitfähigkeitsmessungen, Röntgen-Pulver-Aufnahmen, thermogravimetrische Analysen, Messungen des effektiven magnetischen Dipolemomentes sowie durch spektroskopische Untersuchungen (IR,1H-NMR und ESR) charakterisiert. Das Anionfur – zeigt das Verhalten einer Chelat-bidentat-O(carboxylato),N(imino)-Koordination.相似文献
47.
本文成功地运用了三跳动力学模型,通过相关函数和超精细分裂常数的关系, 推出了电子自旋共振波谱的线宽与基本线宽T_(2,0)~(-1)、溶液中各种异构体的超精细分裂常数、配体的交换寿命等之间的关系。求出了在290 K温度下(Ph_2C_2)Co(CO)[P(OEt)_3]_2的THF溶渡中P(OEt)_3配体的交换寿命是5.6×10~(-11)秒。 相似文献
48.
49.
利用二维离子速度成像(Ion-Velocity Imaging)方法对二溴甲烷分子在234和267 nm附近的光解动力学行为进行了研究. 实验中得到了二溴甲烷光解产生的Br*(2P1/2)和Br(2P3/2)在不同波长下的角度和平动能分布. 在平动能分布中发现两个高斯分布, 推测其中主要是C—Br的快速解离, 而高能宽分布则来自于CH2Br自由基的二次解离过程. 通过角度分布得到了Br*与Br中来自直接解离和非绝热交叉跃迁两种来源的比例. 结果表明Br*原子主要来自于B1态的直接解离, 而Br则绝大部分是从B1态向A1的非绝热交叉跃迁得到, 并导致了两种解离通道能量分布的差别. 相似文献
50.
The chiral separation of halogenated amino acids by ligand-exchange CE is described. Halogenated amino acids attracted increasing interest in recent years because of their physiological activities. Different chiral selectors, as there are L-4-hydroxyproline, L-histidine, and N-alkyl derivatives of L-4-hydroxyproline in form of their copper(II) complexes, are compared for their chiral recognition ability for halogenated amino acids. The influence of various parameters, such as selector concentration, pH, organic modifier, and field strength, on the resolution was investigated. All halogenated amino acids investigated were baseline-separated under optimized conditions. 相似文献