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51.
The controlled decomposition of an Ru(0) organometallic precursor dispersed in 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI.PF(6)), tetrafluoroborate (BMI.BF(4)) or trifluoromethane sulfonate (BMI.CF(3)SO(3)) ionic liquids with H(2) represents a simple and efficient method for the generation of Ru(0) nanoparticles. TEM analysis of these nanoparticles shows the formation of superstructures with diameters of approximately 57 nm that contain dispersed Ru(0) nanoparticles with diameters of 2.6+/-0.4 nm. These nanoparticles dispersed in the ionic liquids are efficient multiphase catalysts for the hydrogenation of alkenes and benzene under mild reaction conditions (4 atm, 75 degrees C). The ternary diagram (benzene/cyclohexene/BMI.PF(6)) indicated a maximum of 1 % cyclohexene concentration in BMI.PF(6), which is attained with 4 % benzene in the ionic phase. This solubility difference in the ionic liquid can be used for the extraction of cyclohexene during benzene hydrogenation by Ru catalysts suspended in BMI.PF(6). Selectivities of up to 39 % in cyclohexene can be attained at very low benzene conversion. Although the maximum yield of 2 % in cyclohexene is too low for technical applications, it represents a rare example of partial hydrogenation of benzene by soluble transition-metal nanoparticles.  相似文献   
52.
Reaction of [(triphos)Re(CO)(2)(OTf)] (1) [triphos = MeC(CH(2)PPh(2))(3); OTf = OSO(2)CF(3)] with P(4)S(3) and P(4)Se(3) yields pairs of coordination isomers, namely, [(triphos)Re(CO)(2)[eta(1)-P(apical)-P(4)X(3)]](+) (X = S, 2; Se, 5) and [(triphos)Re(CO)(2)[eta(1)-P(basal)-P(4)X(3)]](+) (X = S, 3; Se, 6). The latter represent the first examples of the eta(1)-P(basal) coordination achieved by the P(4)X(3) molecular cage. Further reaction of 2/3 and 5/6 mixtures with 1 affords the dinuclear species [[(triphos)Re(CO)(2)](2)[mu,eta(1:1)-P(apical,)P(basal)-P(4)X(3)]](2+) (X = S, 4; Se, 7) in which the unprecedented M-eta(1)-P(basal)/eta(1)-P(apical)-M' bridging coordination of the P(4)X(3) molecule is accomplished. A theoretical analysis of the bonding properties of the two coordination isomers is also presented. The directionality of apical vs basal phosphorus lone pairs is also discussed in terms of MO arguments.  相似文献   
53.
Pure (7E,9Z-7, 9-dodecadien-1-yl acetate (1), the sex pheromone of Lobesiabotrana, has been prepared in 21.6% overall yield by a reaction scheme involving; (i) the cross-coupling of (E) - 8 - (2 - tetrahydropyranyloxy) -1 - octenyldisiamylborane with 1 - bromo - 1 - butyne, in the presence of a Pd (O) catalyst and base; (ii) the acetylation of the crude product of this reaction; (iii) the (Z)-stereoselective reduction of the obtained conjugated (E)-enyn-1-yl acetate. (E)-9,11-Dodecadien-1-yl acetate (2), a sex pheromone component of Diparopsiscastanea, has been analogously obtained (in 54.3% overall yield) by cross-coupling of (E) - 10 - (2 - tetrahydropyranyloxy) - 1 - decenyl borane with vinyl bromide, in the presence of a Pd (O) catalyst and base, followed by acetylation of the crude product. Compound 2, which was 87.7% chemically pure, was purified by column chromatography over SiO2-AgNO3. Chemically pure (9Z, 11E) - 9,11 - tetradecadien - 1 - yl acetate (3), a sex pheromone component of Spodopteralittoralis, has been prepared (in 30.2% overall yield) by reaction of 10 - (2 - tetrahydropyranyloxy) - 1 - decynylamagnesium bromide with (E)-1-iodo-1-butene, in the presence of a Pd (O) catalyst, followed by acetylation of the crude product and by (Z)-stereoselective reduction of the obtained (E)-enyn-1-yl acetate.The stereoisomeric purity of 1, 2 and 3 has been evaluated by glc analysis on glass capillary columns or by reverse phase hplc analysis.  相似文献   
54.
Conformational properties of polymers, such as average dihedral angles or molecular alpha-helicity, display a rather weak dependence on the detailed arrangement of the elementary constituents (atoms). We propose a computer simulation method to explore the polymer phase space using a variant of the standard multicanonical method, in which the density of states associated to suitably chosen configurational variables is considered in place of the standard energy density of states. This configurational density of states is used in the Metropolis acceptance/rejection test when configurations are generated with the help of a hybrid Monte Carlo algorithm. The resulting configurational probability distribution is then modulated by exponential factors derived from the general principle of the maximal constrained entropy by requiring that certain average configurational quantities take preassigned (possibly temperature dependent) values. Thermal averages of other configurational quantities can be computed by using the probability distributions obtained in this way. Moments of the energy distribution require an extra canonical sampling of the system phase space at the desired temperature, in order to locally thermalize the configurational degrees of freedom. As an application of these ideas we present the study of the structural properties of two simple models: a bead-and-spring model of polyethylene with independent hindered torsions and an all-atom model of alanine and glycine oligomers with 12 amino acids in vacuum.  相似文献   
55.
The Ser, Cys, and His side chains play decisive roles in the syntheses, structures, and functions of proteins and enzymes. For our structural and biomedical investigations of β‐peptides consisting of amino acids with proteinogenic side chains, we needed to have reliable preparative access to the title compounds. The two β3‐homoamino acid derivatives were obtained by Arndt–Eistert methodology from Boc‐His(Ts)‐OH and Fmoc‐Cys(PMB)‐OH (Schemes 2–4), with the side‐chain functional groups' reactivities requiring special precautions. The β2‐homoamino acids were prepared with the help of the chiral oxazolidinone auxiliary DIOZ by diastereoselective aldol additions of suitable Ti‐enolates to formaldehyde (generated in situ from trioxane) and subsequent functional‐group manipulations. These include OH→OtBu etherification (for β2hSer; Schemes 5 and 6), OH→STrt replacement (for β2hCys; Scheme 7), and CH2OH→CH2N3→CH2NH2 transformations (for β2hHis; Schemes 9–11). Including protection/deprotection/re‐protection reactions, it takes up to ten steps to obtain the enantiomerically pure target compounds from commercial precursors. Unsuccessful approaches, pitfalls, and optimization procedures are also discussed. The final products and the intermediate compounds are fully characterized by retention times (tR), melting points, optical rotations, HPLC on chiral columns, IR, 1H‐ and 13C‐NMR spectroscopy, mass spectrometry, elemental analyses, and (in some cases) by X‐ray crystal‐structure analysis.  相似文献   
56.
Summary The construction and set-up of a dual-flame photometric detector (DFPD) which, through three channel operation, allows the simulatneous selective determination of P-, S-, Cl-containing compounds eluted from a G. C. column is described. For P- and S-containing compounds the molecular emission bands HPO and S2 at 526 and 394 nm respectively are measured; for Cl-containing compounds, after reaction with In, the InCl band at 360 nm is recorded. Detectability, specificity, linearity as well as mutual interferences are discussed and compared with those of classical GC-detectors as thermionic (TID) and electron capture (ECD). Some practical applications concerning the pesticide residue analysis in animal and vegetable extracts are shown.
Zwei-Flammen-Photometer-Detektor (DFPD) für die gleichzeitige G. C. Bestimmung von P-, S-und Cl-enthaltenden organischen Verbindungen
Zusammenfassung Der Aufbau und die Justierung eines Zwei-Flammen-Photometer-Detektors, welcher durch 3-Kanal Arbeitsweise eine gleichzeitige selektive Bestimmung von P-, S- und Cl-enthaltenden Verbindungen erlaubt, wird beschrieben. Für P- und S-enthaltende Moleküle werden die Molekül-Linien HPO und S2 bei 526 bzw. 394 nm gemessen; bei Cl-enthaltenden Verbindungen wird, nach Reaktion mit In, die InCl-Linie bei 360 nm registriert. Nachweisgrenze, Spezifität, Linearität sowie Quereinflüsse wechselseitiger Interferenzen werden diskutiert und mit den entsprechenden Werten klassischer GC-Detektoren wie TID und ECD verglichen. Einige praktische Anwendungen bei der Pestizid-Rückstand-Analyse in Extrakten von Tieren und Pflanzen werden gezeigt.

Détecteur photométrique à double flamme (DPDF) pour la détermination simultantée des composés organiques contenant du P, S, Cl en CG
Résumé On décrit la construction et la mise au point d'undétecteur photométrique à double flamme («DFPD»=DPDF); celui-ci permet grâce à système à «3 canaux» de déterminersimultanément et sélectivement les substances organiques contenant du P, du S, du Cl, à la sortie des colonnes de chromatographie en phase gazeuse. Pour les substances contenant du P et du S, on mesure l'émission moléculaire correspondant aux bandes dûes à HPO et S2 (526 et 394 nm. respectivement); pour les composés chlorés, on mesure l'émission correspondant à la bande due à InCl (360 nm.) après réaction avec l'Indium des gaz brulés. Les problèmes relatifs à la limite de détection, à la specificité et à la linéarité de la réponse en fonction de la quantité de substance injectée, ainsi qu'aux interactions entre substances détectées, sont discutés et les rultats obtenus sont compar avec ceux fournis par les détecteurs classiques: thermo-ionique («TID»=DTI) ou à capture d'électrons («ECD»=DCE). Quelques applications pratiques dans le domaine de l'analyse des résidus de pesticides dans des extraits d'origine animale ou végétale sont données comme exemples.
  相似文献   
57.
The synthesis and characterization of two new macrocyclic ligands, the bis-macrocyclic compound 2,6-bis(1,4,13-triaza-7,10-dioxacyclopentadec-1-ylmethyl)phenol (L) and 38-methoxy-1,4,13,16,19,28-hexaaza-7,10,22,25-tetraoxatricyclo[14.14.7.1(32,36)]octatriconta-32,34,Delta(36,38)-triene (L1) are reported. Equilibrium studies of basicity and coordination properties toward metal ions such as Cu(II), Zn(II), Cd(II) and Pb(II) were performed for ligand by potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, I= 0.15 mol dm(-3)). L behaves as a hexaprotic base (logK(1)= 10.93, logK(2)= 9.70, logK(3)= 8.79, logK(4)= 8.05, logK(5)= 6.83, logK(6)= 2.55). All metal ions form stable mono- and dinuclear complexes: logK(MLH(-1))= 25.61 for Cu(II), 15.37 for Zn(II), 12.58 for Cd(II) and 13.79 for Pb(II); logK(M(2)LH(-1))= 31.61 for Cu(II), 23.38 for Zn(II), 24.49 for Cd(II) and 23.68 for Pb(II). All these dinuclear species show a great tendency to add the OH(-) group: the equilibrium constant for the addition reaction was found to be logK(M(2)LH(-1)OH)= 4.77 for Cu(II), 5.66 for Zn(II), 2.8 for Cd(II) and 3.18 for Pb(II). In the case of Ni(II), kinetic inertness prevents the possibility of solution studies. The dinuclear solid adducts [Ni(2)H(-1)L(N(3))(3)].EtOH and [Cu(2)H(-1)L(N(3))](ClO(4))(2) were characterized by X-ray analysis.  相似文献   
58.
Infections caused by multidrug resistant (MDR) bacteria are a major public health threat. Carbapenems are among the most potent antimicrobial agents that are commercially available to treat MDR bacteria. Bacterial production of carbapenem-hydrolysing metallo-β-lactamases (MBLs) challenges their safety and efficacy, with subclass B1 MBLs hydrolysing almost all β-lactam antibiotics. MBL inhibitors would fulfil an urgent clinical need by prolonging the lifetime of these life-saving drugs. Here we report the synthesis and activity of a series of 2-mercaptomethyl-thiazolidines (MMTZs), designed to replicate MBL interactions with reaction intermediates or hydrolysis products. MMTZs are potent competitive inhibitors of B1 MBLs in vitro (e.g., Ki = 0.44 μM vs. NDM-1). Crystal structures of MMTZ complexes reveal similar binding patterns to the most clinically important B1 MBLs (NDM-1, VIM-2 and IMP-1), contrasting with previously studied thiol-based MBL inhibitors, such as bisthiazolidines (BTZs) or captopril stereoisomers, which exhibit lower, more variable potencies and multiple binding modes. MMTZ binding involves thiol coordination to the Zn(ii) site and extensive hydrophobic interactions, burying the inhibitor more deeply within the active site than d/l-captopril. Unexpectedly, MMTZ binding features a thioether–π interaction with a conserved active-site aromatic residue, consistent with their equipotent inhibition and similar binding to multiple MBLs. MMTZs penetrate multiple Enterobacterales, inhibit NDM-1 in situ, and restore carbapenem potency against clinical isolates expressing B1 MBLs. Based on their inhibitory profile and lack of eukaryotic cell toxicity, MMTZs represent a promising scaffold for MBL inhibitor development. These results also suggest sulphur–π interactions can be exploited for general ligand design in medicinal chemistry.

Metallo-β-lactamases (MBLs) are major culprits of resistance to carbapenems in bacteria. A series of thiazolidines are potent MBL inhibitors, restoring the activity of carbapenems. Metal binding and sulphur–π interactions are key to inhibition.  相似文献   
59.
The reactions of 1-bromo-, 1-iodo-, 2-bromo-, 1,3-dibromo-, and 1,4-dibromoadamantane with Me(3)Sn(-) ions were studied in liquid ammonia. The photostimulated reaction of 1-haloadamantane (1-XAd, X = Br, I) or 2-BrAd with Me(3)Sn(-) ions gave in a few minutes excellent yields of the substitution products. The 1,3-dibromo- and 1,4-dibromoadamantane with Me(3)Sn(-) ions also reacted very fast under irradiation to give the disubstitution product in good yields. In competition experiments, 1-ClAd is 5.3 times more reactive than 5-chloro-2-adamantanone (9) toward Me(3)Sn(-) ions in liquid ammonia. When the nucleophile is the Ph(2)P(-) ion, 1-ClAd reacts 2.4 times faster than 9. This is the first time that no redox catalysis was observed when the bridgehead compound bears a carbonyl group as a pi acceptor. On the other hand, the nucleophile Me(3)Sn(-) ion was ca. >1000 times more reactive than Ph(3)Sn(-) ions toward 1-adamantyl radicals, in contrast to the behavior of aryl radicals, where both nucleophiles have the same reactivity.  相似文献   
60.
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