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71.
The enthalpy changes, entropy changes and equilibrium constants of coordination reactions of 18-crown-6 with the alkali ions Na+ and K+ at 298.15K were measured by using RD-496 microcalorimeter with methanol, ethanol, n-propanol and n-butanol as solvents respectively. The results indicated that the enthalpy changes △rHm, entropy changes △rSm, and the stability of the complexes are closely related with the polarity of the solvents, and the order of the stability is ethanol>methanol>n-propanol>n-butanol>H2O for the same complex in the solvents investigated. The stability order was reasonably explained by relating the stability constants of the complexes with the dielectric constants of these solvents, and by using the model of solvated-desolvated ions and ion pair in the coordination reactions. 相似文献
72.
Crystal Structure of the “Supramolecular” Complex [Cs2(18-crown-6)][HgI4] with Unusually Coordinated Cs Ions The reaction of 18-crown-6, 1,4,7,10,13,16-hexaoxacyclooctadecane, with HgI2/CsI in methanol yields crystals of [Cs2(C12H24O6)][HgI4]. The compound crystallizes monoclinically, space group P21/c, Z = 4, a = 1574.8(3), b = 1067.0(3), c = 1693.2(6) pm, and β = 98.29(3)º. The structure consists of a network made up of two different types of [Cs-(18-crown-6)-Cs]2+ cations, interconnected by [HgI4]2? anions. The cations form an “anti-sandwich” structure with relatively short Cs ? Cs distances of 382 pm in the first type of cations and a longer distance of 480 pm in the second type of cations. 相似文献
73.
Arelí Durón-Castellanos Vanesa Zazueta-Novoa Hortencia Silva-Jiménez Yolanda Alvarado-Caudillo Eduardo Peña Cabrera Roberto Zazueta-Sandoval 《Applied biochemistry and biotechnology》2005,121(1-3):279-288
Different soluble NAD+-dependent alcohol dehydrogenase (ADH) isozymes were detected in cell-free homogenates from aerobically grown mycelia of YR-1
strain of Mucor circinelloides isolated from petroleumcontaminated soil samples. Depending on the carbon source present in the growth media, multiple NAD+-dependent ADHs were detected when hexadecane or decane was used as the sole carbon source in the culture media. ADH activities
from aerobically or anaerobically grown mycelium or yeast cells, respectively, were detected when growth medium with glucose
added was the sole carbon source; the enzyme activity exhibited optimum pH for the oxidation of different alcohols (methanol,
ethanol, and hexadecanol) similar to that of the corresponding aldehyde (≈7.0). Zymogram analysis conducted with partially
purified fractions of extracts from aerobic mycelium or anaerobic yeast cells of the YR-1 strain grown in glucose as the sole
carbon source indicated the presence of a single NAD+-dependent ADH enzyme in each case, and the activity level was higher in the yeast cells. ADH enzyme from mycelium grown in
different carbon sources showed high activity using ethanol as substrate, although higher activity was displayed when the
cells were grown in hexadecane as the sole carbon source. Zymogram analysis with these extracts showed that this particular
strain of M. circinelloides has four different isozymes with ADH activity and, interestingly, one of them, ADH4, was identified also as phenanthrene-diol-dehydrogenase,
an enzyme that possibly participates in the aromatic hydrocarbon biodegradation pathway. 相似文献
74.
Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O], and (PPh4)2[SnCl6] · S8 · 2CH3CN . The reaction of PPh4[SnCl3] with Na2S4 in acetonitrile in the presence of small amounts of water yields (PPh4)2[Sn4Cl4S5(S3)O] and minor amounts of (PPh4)2[SnCl2(S6)2], PPh4Cl · 2S8 and (PPh4)2[SnCl6]. SnCl4 is partially reduced by (PPh4)2Sx, PPh4[SnCl3] and (PPh4)2[SnCl6] · S8 · 2CH3CN being produced. According to the X-ray crystal structure determination the [Sn4Cl4S5(S3)O]2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S3 group. In the [SnCl2(S6)2]2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S6 groups. Octahedral [SnCl6]2? ions and S8 molecules in the crown conformation are present in (PPh4)4[SnCl6] · S8 · 2CH3CN. 相似文献
75.
Pseudohalogeno Metal Compounds. LXXV. Pentacarbonylrhenium and Triphenylphosphinegold Complexes of Pseudohalide Anions: (OC)5ReX, Ph3PAuX (x = ONC(CN)2, o-MeC6H4SO2C(CN)2, o-MeC6H4SO2NCN, Ph2(S)PNCN) The pseudohalides (X?) nitrosodicyanmethanide, o-tosyldicyanmethanide, o-tosylcyanamide and diphenylthiophosphinylcyanamide react with the Organometallic Lewis Acids (OC)5Re+ (as (OC)5ReFBF3) and Ph3PAu+ (as Ph3PAuNO3) to give the neutral title complexes (OC)5Re—X and Ph3PAu? X, respectively. X-ray diffraction shows that nitroso-dicyanmethanide is coordinated through the nitroso N-atom to the Re(CO)5 fragment. Cyanide-N-coordination is observed for the complexes with o-tosyldicyanmethanide and o-tosylcyanamide whereas diphenylthiophosphinylcyanamide is S-coordinated to the gold atom. Spectroscopic data (IR, NMR) of 1–6 are described. 相似文献
76.
Hella Folkerts Kurt Dehnicke Jrg Magull Helmut Goesmann Dieter Fenske 《无机化学与普通化学杂志》1994,620(7):1301-1306
Phosphorane Iminato-Trichloroselenates(II): Syntheses and Crystal Structures of [SeCl(NPPh3)2]+SeCl3? and [Me3SiN(H)PMe3]2+[Se2Cl6]2? [SeCl(NPPh3)2]+SeCl3? has been synthesized by the reaction of Se2Cl2 with Me3SiNPPh3 in acetonitrile solution, forming orangered crystals, whereas red crystals of [Me3SiN(H)PMe3]2+[Se2Cl6]2? were obtained by the reaction of Me3SiNPMe3 with SeOCl2 in acetonitrile solution. Both complexes were characterized by X-ray structure determinations. [SeCl(NPPh3)2]+SeCl3?: Space group P21/n, Z = 4, structure solution with 7 489 observed unique reflections, R = 0.057. Lattice dimensions at ?60°C: a = 1 117.0; b = 2 241, c = 1 407.5 pm, β = 95.61°. In the cation [SeCl(NPPh3)2]+ the selenium atom is φ-tetrahedrally coordinated by the chlorine atom and by the nitrogen atoms of the phosphorane iminato ligands, whereas the anion SeCl3? has a T-shaped structure with φ-trigonal-bipyramidale surrounding of the selenium atom. [Me3SiN(H)PMe3]2+[Se2Cl6]2?: Space group P21/c, Z = 4, structure solution with 2 093 observed unique reflections, R = 0.080. Lattice dimensions at ?70°C: a = 956, b = 828, c = 1 973 pm, β = 93.80°. The structure consists of [Me3SiN(H)PMe3]+ ions and planar [Se2Cl6]2? anions, in which the selenium atoms are bridged nearly symmetrically by two chlorine atoms. 相似文献
77.
Felora Heshmatpour Dirk Nußhr Ralf Garbe Sigrid Wocadlo Werner Massa Kurt Dehnicke Helmut Goesmann Dieter Fenske 《无机化学与普通化学杂志》1995,621(3):443-450
Syntheses and Crystal Structures of the Phosphorane Iminato Complexes [MCl2(NPPh3)]2 with M = Al and Ga, [SbCl2(NPMe3)(DMF)]2, and of the Phosphorane Imine Complex [Ph3PNH · BF3] · THF The phosphorane iminato complexes [MCl2(NPPh3)]2 with M = Al and Ga and [SbCl2(NPMe3)(DMF)]2 are formed as colourless crystals by reactions of the anhydrous trichlorides MCl3 (M = Al, Ga, Sb) with the corresponding silylated phosphorane imines Me3SiNPR3 in acetonitrile and in dimethyl formamide, respectively. The phosphorane imine derivative [Ph3PNH · BF3] · THF is formed from Me3SiNPPh3 and boron trifluoride etherate in boiling tetrahydrofuran. The compounds are characterized by their i. r. spectra and by crystal structure analyses. [AlCl2(NPPh3)]2 : Space group P1 , Z = 1, structure solution with 1 585 observed unique reflections, R = 0.061. Lattice dimensions at ?70°C: a = 917.6, b = 1 053.5, c = 1 145.2 pm, α = 111.72°, β = 100.80°, γ = 109.95°. [GaCl2(NPPh3)]2 : Space group P1 , Z = 1, structure solution with 2 586 observed unique reflections, R = 0.066. Lattice dimensions at ?70°C: a = 917.5, b = 1 058.3, c = 1 153.7 pm, α = 105.52°, β = 107.75°, γ = 109.88°. In both compounds the metal atoms are linked to planar M2N2 four-membered rings via the N-atoms of the phosphorane iminato groups. [SbCl2(NPMe3)(DMF)]2 : Space group P21/n, Z = 4, structure solution with 3 805 observed unique reflections, R = 0.038. Lattice dimensions at ?70°C: a = 1 913.0, b = 726.8, c = 2 040.7 pm, β = 113.62°. The unit cell contains two symmetry independent dimeric molecules, in which the antimony atoms are centrosymmetricly μ2 linked via the N-atoms of the phosphorane iminato groups. Along with the oxygen atom of the dimethyl formamide molecule the Sb atoms achieve a ψ-octahedral environment. [Ph3PNH · BF3] · THF : Space group C2/c, Z = 8, structure solution with 2 048 observed unique reflections, R = 0.058. Lattice dimensions at ?70°C: a = 2 460.4, b = 869.2, c = 1 978.0 pm, β = 116.35°. 相似文献
78.
Reactions of MoNCl3 and WNCl3 with Elemental Fluorine. Crystal Structures of [MoO2F2(THF)2] and [WF4(NCl)(CH3CN)] The nitrido chlorides MoNCl3 and WNCl3 as well as WCl4(NCl) react with elemental fluorine forming the N-chloro imido complexes MoF4(NCl) and WF4(NCl), which were characterized by IR spectroscopy. With tetrahydrofurane MoF4(NCl) reacts to give [MoF4(NCl)(THF)], which in THF solution slowly converts into [MoO2F2(THF)2]. From WF4(NCl) with acetonitrile the complex [WF4(NCl)(CH3CN)] is obtained. Both donor acceptor complexes were characterized by crystal structure determinations. [MoO2F2(THF)2] : Space group P21/n, Z = 4, structure solution with 1823 unique reflections, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 636.2, b = 1119.5, c = 1625.2 pm; β = 93.92(1)º. The compound has a monomeric molecular structure with the fluorine atoms in trans-position to one another and with the oxygen atoms of the THF molecules in trans to the oxo ligands. [WF4(NCl)(CH3CN)] : Space group P21/m, Z = 2, structure solution with 1119 unique reflections, R = 0.038 for reflections with I > 2σ(I). Lattice dimensions at 20°C: a = 511.7, b = 714.9, c = 1002.5 pm; β = 102.59(10)º. The compound has a monomeric molecular structure in which the nitrogen atom of the acetonitrile molecule coordinates in trans-position to the N-chloro imido group W?N? Cl. The structural parameters of this group are WN = 172.2 pm, NCl = 161.1 pm, WNCl = 178.6º. 相似文献
79.
《Journal of Coordination Chemistry》2012,65(9):985-990
The crystal of pentaqua (catena-pyridine-3,5-dicarboxylato-O,O) calcium(II) contain zigzag molecular chains composed of Ca ions linked by two bridging oxygen atoms, each donated by one carboxylate group [Ca-O1 2.353(2) Å, Ca-O3III 2.334(1) Å]. The Ca ions, the ligand molecules and one water oxygen atom coordinated by each metal ion [Ca-O5 2.410(2) Å] are coplanar. The coordination of the Ca ion is completed by four other water oxygen atoms situated above and below the plane of the chain [Ca-O6 2.475(1) Å, Ca-O7 2.371(2) Å]. The coordination number of the calcium(II) ion is seven. The water molecules act as donors in a system of hydrogen bonds. 相似文献
80.
《Journal of Coordination Chemistry》2012,65(6):539-544
Silver(I) complexes of selenones, [LAgNO3] and [AgL2]NO3 (where L is imidazolidine-2-selenone or diazinane-2-selenone and their derivatives) have been prepared and characterized by elemental analysis, IR and NMR (1H, 13C and 107Ag) spectroscopy. An upfield shift in the C=Se resonance of selenones in 13C NMR and a downfield shift in N-H resonance in 1H NMR are consistent with selenium coordination to silver(I). In 107Ag NMR, the AgNO3signal is deshielded by 450-650 ppm on coordination to selenones. Greater upfield shifts in 13C NMR were observed for [LAgNO3] compared to [AgL2]NO3complexes, whereas the opposite trend was observed for 1H and107Ag NMR chemical shifts. 相似文献