土壤微生物ATP、脱氢酶和尿素酶活性的ED50值评价外源镧的生物毒性

０IntroductionRareearthsarenowappliedwidelyinChina，whichcanimprovecropsyieldsandthetheirqualit－ies犤１犦．Thebeneficialeffectsmaybeduetothestimu－latoryeffectsoftheseelementsonthenutrientuptakebyplantsorontheincreasingofchlorophyllsynthesisintheplants犤２犦．Whilealotofresearcheshavebeendoneontheimprovednutritionofcropsafterapplica－tionofrareearths，muchlessattentionhasbeenpaidtothedeteriorationofsoilqualityduetotheapplicationofrareearthsforyears犤３犦．Scientistshavediscoveredthataccumula…     

新型红色荧光粉Sr3Al2O6的合成和发光性能研究

稀土金属离子激活的多铝酸盐发光材料，在可见光区具有较高的量子效率犤１～４犦，充分显示出这类荧光发光材料，在高效节能、环保、电光源与新一代可见光显示器领域的应用前景犤４～９犦。特别是SrAl２O４∶Eu２＋的持续发光现象的发现犤２，３犦，激起了对以稀土金属离子为激活剂，碱土铝酸盐为基质的长余辉无机发光材料体系的兴趣。研究表明其发光强度和余辉时间是传统硫化物发光材料的十倍以上，利用其长余辉储光－发光特性，有望开发新型发光油漆、涂料、发光陶瓷、发光塑料、薄膜、发光纸、发光纤维犤４犦。早在七十年代，荷兰菲利…     

二(三苯基膦)水杨酸铜(Ⅰ)乙醇溶剂配合物的晶体结构

0IntroductionThestudyofcopper?complexesisinvestigatedinmanylaboratories.Amongthereasonsforcarryingouttheinvestigationofsuchspeciesaretheirstructuralfeatures犤1犦,theusefulnessofcopper?compoundsinorganicsyntheses犤2犦andthewell-documentedimpor-tanceofcopper?centersattheactivesitesofanumberofprotein犤3犦.Concerningcopper?carboxy-latesafurtherinterestexists,stemmingfromtheiruseinhomogeheouscatalysedhydrogenation犤4犦.Thecopper?bis(triphenylphosphine)cationisasoft,butflexi-bleacceptorionthatcanacc…     

二个新颖的一维聚合物{(PyH)_3[Cu_3Br_6]}_∞和{(γ-MePyH)_2[Cu_2Br_4]}_∞的合成和晶体结构(英文)

0IntroductionInthelastdecades,low-dimensionalcopper?-organichybridcomplexeshaveattractedmuchatten-tionduetotheirowncolorfulchemistry犤1～9犦andtheirpotentialapplicationsinfluorescentsensors犤10犦,olefinseparations犤11犦,andenantioseparation犤12犦.Intriguingly,thestructuresofsomepolycopper?anioniccomplexescouldbeinfluencedbythesize,shape,andchargedistributionoftheassociatedorganiccountercationssuchasquaternaryammoniumandphosphoniumcations犤13,14犦.Thebromocuprate?complexesdemon-stratelotsofexam…     

一个生物相关单一手性二维金属有机鲱骨形分子网格:双-3-氨基-(S)-酪氨酸钴(英文)

0IntroductionAlthoughtheself-assemblyofchiralsupramolec-ularentitiesiscommoninvivo,itremainsdifficulttorationalizedesignandpreparationofchiralartificialself-assemblingsystems犤1犦.Inrecentyears,chiralmet-al-organicsolidshaveattractedmuchattentionandhavebeenofintensecurrentinterestsduetothepo-tentialapplicationsinawidevarietyoffields犤2～4犦.Thechoiceofchiralaminoacidaseffectivemeanstoobtainhomochiralstructureshaveemergedmanyyears.Morerecently,Chinetal.reportedarationallydesignedaminoacidmetal…     

2-氨基-4, 6-二甲基嘧啶与锌盐配合物的制备及生成焓测定

Thepyrimidinesasaclassareknowntopossessextraordinarybiologicalpropertiesthataregenerallydistinguishedqualitativelybytheirapplicationsinpesticide,herbicide,bactericide,andmedicineinter-mediates犤1犦.Asurveyoftheseapplicationsandanum-beroftherelatedvariationsthataredevelopedrecent-ly,suchastheextraordinaryeffectiveherbicideofsulfonylsulfourea,revealsthebroadbiologicalimpor-tancejustbecauseofthewideoccurrenceofpyrimi-dinesringsystemsinthesemolecules犤2犦.Ithasbeenshownthatthemedicineintermediates…     

含乳清酸配体的两个单核配合物的合成与晶体结构

0IntroductionInthepastfewyears,themolecular-basedmag-neticpropertiesofheteronuclearcomplexessimultane-ouslycomprisinglanthanideandtransitionmetalionshaveattractedincreasinginterest犤1～6犦.Inourlaborato-ry,wehavesynthesizedsuchtypeofcomplexeswithdifferentcarboxylicbridgingligands犤7～10犦.Asanex-tensionofthisresearcharea,ourpresentworkaimstosynthesizenovelcomplexesofrareearthandtransi-tionmetalbyusingoroticacidasabridgingligand.Inthecourseofourinvestigationtwonewcomp-lexesof犤Cu(C5H2N2O4)(H…     

二氯四(苯丙酮-1, 2, 4-三唑)合钴六水配合物晶体结构

0IntroductionRecently,thecompoundscontaining1H-1,2,4-tr-iazolegrouphaveattractedmuchinterestbecauseoftheirexhibitingsomefungicidalactivityandplantgrowthregulatingactivity犤1犦,andshowingantibacterialactivityagainstPucciniareconditeandrootsgrowthregulationforcucumber犤2犦.Also,suchcompoundsareincreasinglybeingstudiedbecauseofthecoordinationchemistryofazolesactingasligandsintransitionmetalcompounds.Asamatteroffact,thetriazolederivativeshavebeenextensivelyusedasterminalandbridgingligands,andthey…     

二(三苯基膦)乙基黄原酸金属配合物的晶体结构和谱学表征

0IntroductionTheincreasingcommercialvalueoftransitionmetalcomplexesofxanthateshasarousedconsiderableinterestingintheirchemistry.Whiletheiranalyticalapplicationsarewellknown犤1犦,theyarenowfindingextensiveuseinvulcanizationofrubber,frothfloatationprocessforconcentrationofsulphideores,asantioxi-dants,lubricants犤2,3犦,andhavebeenfoundtopossessfungicidalandinsecticidalactivity犤4犦.Inrecentyears,therehasbeengrowinginterestinthestudyofd10metalcomplexes,whichexhibitrichphotophysicalandpho-tochemica…     

[C4N2H12]1.5[Zn2(PO4)(HPO4)2]·H2O晶体的合成与表征

由于在电学、磁学、光学、吸附、离子交换和催化等领域具有潜在的应用价值,具有开放骨架结构的金属磷酸盐的合成一直受到人们的广泛关注。在这些磷酸盐微孔化合物中,磷酸锌晶体是拓扑结构最为丰富的一种犤1犦。自从Stucky等犤2犦报道具有SOD、Li-ABW、FAU等已知结构磷酸锌的合成以来,已经有近百种具有0-D犤3,4犦,1-D犤5,6犦,2-D犤7～9犦,3-D犤10～13犦结构的磷酸锌被成功地合成出来。其中令人瞩目的是具有螺旋孔道的手性磷酸锌犤14犦以及具有二十四元环孔道的两种微孔磷酸锌化合物犤15,16犦的合成。这些化合物大多是采用水热技术以有…     

First Characterization of an Extended Ammonium‐Ammonia Complex [{NH4(NH3)4}+(μ‐NH3)2] in the Crystal Structure of [NH4(NH3)4][Co(C2B9H11)2] · 2 NH3

The compound [NH₄(NH₃)₄][Co(C₂B₉H₁₁)₂] · 2 NH₃ ( 1 ) was prepared by the reaction of Na[Co(C₂B₉H₁₁)₂] with a proton‐charged ion‐exchange resin in liquid ammonia. The ammoniate 1 was characterized by low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of [Co(C₂B₉H₁₁)₂]^‐ complexes, which are connected via C‐H···H‐B dihydrogen bonds. Furthermore, 1 contains an infinite equation/tex2gif-stack-2.gif[{NH₄(NH₃)₄}⁺(μ‐NH₃)₂] cationic chain, which is formed by [NH₄(NH₃)₄]⁺ ions linked by two ammonia molecules. The N‐H···N hydrogen bonds range from 1.92 to 2.71Å (DHA = Donor···Acceptor angles: 136‐176°). Additional N‐H···H‐B dihydrogen bonds are observed (H···H: 2.3‐2.4Å).     

Darstellung und Kristallstrukturen von [P(C6H5)4][1-(NH3)B10H9] und Cs[(NH3)B12H11] · 2CH3OH

Synthesis and Crystal Structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH The reduction of [1-(NO₂)B₁₀H₉]^2? with aluminum in alkaline solution yields [1-(NH₃)B₁₀H₉]^? and by treatment of [B₁₂H₁₂]^2? with hydroxylamine-O-sulfonic acid [(NH₃)B₁₂H₁₁]^? is formed. The crystal structures of [P(C₆H₅)₄][1-(NH₃)B₁₀H₉] (triclinic, space group P1 , a = 7.491(2), b = 13.341(2), c = 14.235(1) Å, α = 68.127(9), β = 81.85(2), γ = 86.860(3)°, Z = 2) and Cs[(NH₃)B₁₂H₁₁] · 2CH₃OH (monoclinic, space group P2₁/n, a = 14.570(2), b = 7.796(1), c = 15.076(2) Å, β = 111.801(8)°, Z = 4) reveal for both compounds the bonding of an ammine substituent to the cluster anion.     

溶胶凝胶法合成富锂正极材料Li[Li0.2Ni0.2Mn0.6]O2及性能表征

以LiOH.H2O、Mn(CH3COO)2.4H2O和Ni(CH3COO)2.4H2O为原料,分别用柠檬酸(CA)与乙二胺四乙酸(EDTA)为配位剂,采用溶胶凝胶法结合固相烧结法制备富锂固溶体正极材料Li[Li0.2Ni0.2Mn0.6]O2。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、激光粒度仪对所得样品的结构、形貌、粒径分布进行了表征,并测试了材料的电化学性能。采用CA配位制备的材料的电化学性能优于用EDTA配位制备的材料的电化学性能,室温下以18 mA.g-1的电流密度,在2.0~4.8 V电压范围内充放电,用CA制备的材料首次充电比容量高达324 mAh.g-1,首次库伦效率达82%;在180 mA.g-1的电流下,其可逆比容量保持在120 mAh.g-1。     

Water‐soluble and Halogen‐free Hexaammine Complexes of Metal Ions of Group 9 – Synthesis,Crystal Structures,and Vibrational Spectra

Reaction of [M(NH₃)₆]Cl₃ (M = Co, Rh, Ir) and [Ir(NH₃)₅(OH₂)]Cl₃ with (NH₄)₂C₂O₄ · H₂O in aqueous solution resulted in the isolation of [M(NH₃)₆]₂(C₂O₄)₃ · 4 H₂O and [Ir(NH₃)₅(OH₂)]₂(C₂O₄)₃ · 4 H₂O, respectively. The complexes have been characterized by X‐ray crystallography, IR and UV/VIS spectroscopy. The isomorphous compounds crystallize in the orthorhombic space group Pnnm (No. 58). Four molecules of crystal water are involved in an extended three‐dimensional hydrogen bonding network. The librational modes of the lattice water around 600 cm^–1 allow the characterization of [Ir(NH₃)₆]₂(C₂O₄)₃ · 4 H₂O and [Ir(NH₃)₅(OH₂)]₂(C₂O₄)₃ · 4 H₂O, respectively, by IR spectroscopy. The band around 600 cm^–1 shows a significant frequency shift in the IR spectra of the hexaammine and aquapentaammine complex of iridium(III) and, by that, a distinction is possible.     

Reaction of ammonia with accelerated benzoyl ions under multiple-collison conditions in a triple quadrupole instrument

The reaction of benzoyl ion with ammonia in multiple-collision conditions in the second quadrupole assembly of a triple quadrupole mass spectrometer at (laboratory) ion kinetic energies from 0 to 20 eV produced the even-electron ions [C₆H₅]⁺, [C₆H₅NH₃·(NH₃)_m]⁺ (m = 0, 1) and [C₆H₅CONH₃·(NH₃)_n]⁺ (n = 0, 1, 2, 3) and the odd-electron ions [C₆H₄NH₃·(NH₃)_p]⁺· (p = 0, 1). Thermochemical information could not be obtained under multiple-collision conditions: both exothermic and endothermic reactions were observed, with no translational-energy onset measurable for the endothermic processes, nor decrease in the yield of the exothermic processes at high energies. The behaviour of cluster-ion intensities as pressure varied was qualitatively as expected. There are pressure and energy regions where spectra change little; if this feature were to be general, it would point to some utility for these conditions in qualitative analysis.     

Two inclusion compounds of guanylthiourea and 1,3,5-thiadiazole-5-amido-2-carbamate

In the crystal structure of [(n-C₄H₉)₄N]⁺·[NH₂(C₂N₂S)NHCOO^?]·NH₂CSNC(NH₂)₂ (1), guanylthiourea molecules and 1,3,5-thiadiazole-5-amido-2-carbamate ions are joined together by intermolecular N–H…O, N–H…N, and weak N–H…S hydrogen bonds to generate stacked host layers corresponding to the (110) family of planes, between which the tetra-n-butylammonium guest cations are orderly arranged in a sandwich-like manner. In the crystal structure of [(n-C₃H₇)₄N]⁺·[NH₂(C₂N₂S)NHCOO^?]·NH₂CSNC(NH₂)₂·H₂O (2), the tetrapropyl ammonium cations are stacked within channels each composed of hydrogen bonded ribbons of guanylthiourea molecules, 1,3,5-thiadiazole-5-amido-2-carbamate ions and water molecules.     

Nieuwland's cuprocatalytic reaction in terms of crystal chemical analysis

Crystallochemical treatment of the Nieuwland reaction is carried out on the basis of structural data obtained for crystalline acetylene complexes of the formulas NH₄Cu₈Cl₉·4C₂H₂·1/2HCu₂Cl₃·H₂O (I), NH₄Cu₃Cl₄·C₂H₂ (II), KCu₈Cl₉·4C₂H₂·1/2HCu₂Cl₃·H₂O (III), KCu₃Cl₄·C₂H₂ (IV), (NH₄)₂Cu₃Cl₅·4/9H₂O·(xC₂H₂) with x=0 (Va), 1/9 (Vb), and 4/9 (Vc) and divinylacetylene (DVA) copper chloride compounds 2CuCl·DVA (VI) and 3CuCl·DVA (VII). Because of the π-coordination of a copper atom, the C≡C bond of the acetylene molecule is activated, as indicated by its significant (up to 1.32 Å) stretch (complexes I and II). The zeolite-like structure of complexes Va-Vc, which form in a catalytic solution, is realized as an infinite {[Cu₁₀₈Cl₁₆₈(H₂O)₁₆]^60?}_n anion with discrete [Cl(NH₄)₆]⁵⁺ cations inside. In this structure, only 16 Cu(1) atoms have a trigonal-pyramidal environment with the oxygen atom of the crystallization water located in the vertex (d_Cu?O=2.79 Å). Under the liquid-phase conditions of the Nieuwland reaction, these copper atoms are active centers stimulating the reaction to the subsequent acetylene oligomerization due to the π-interaction with the C₂H₂ molecule. The mutual arrangement of the catalytically active Cu(1) atoms in structure Va serves as a matrix for the synthesis of DVA, as shown by the structure of the 2CuCl·DVA adduct.     

Self‐Assembly,Spectroscopic and Electrochemical Studies of Nickel(II)‐4,8‐Diazaundecanediamide Complex

The self‐assembly of NiCl₂·6H₂O with a diaminodiamide ligand 4,8‐diazaundecanediamide (L‐2,3,2) gave a [Ni(C₉H₂₀N₄O₂)(Cl)(H₂O)] Cl·2H₂O ( 1 ). The structure of 1 was characterized by single‐crystal X‐ray diffraction analysis. Structural data for 1 indicate that the Ni(II) is coordinated to two tertiary N atoms, two O atoms, one water and one chloride in a distorted octahedral geometry. Crystal data for 1: orthorhombic, space group P 21nb, a = 9.5796(3) Å, b = 12.3463(4) Å, c = 14.6305(5) Å, Z = 4. Through NH···Cl–Ni (H···Cl 2.42 Å, N···Cl 3.24 Å, NH···Cl 158°) and OH···Cl–Ni contacts (H···Cl 2.36 Å, O···Cl 3.08 Å, OH···Cl 143°), each cationic moiety [Ni(C₉H₂₀N₄O₂) (Cl)(H₂O)]⁺ in 1 is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chainlike structure. Thermogrametric analysis of compound 1 is consistent with the crystallographic observations. The electronic absorption spectrum of Ni(L‐2,3,2)²⁺ in aqueous solution shows four absorption bands, which are assigned to the ³A_2g → ³T_2g, ³T_2g → ¹Eg, ³T_2g → ³T_1g, and ³A_2g → ³T_1g transitions of triplet‐ground state, distorted octahedral nickel(II) complex. The cyclic volammetric measurement shows that Ni²⁺ is more easily reduced than Ni(L‐2,3,2)²⁺ in aqueous solution.     

Uptake of pyridine and n-butylamine by crystalline zirconium phosphate

The titration curve of the hydrogen form of crystalline α-zirconium phosphate with pyridine shows only one end point and a phase Zr(C₅H₅NHPO₄)_0·45(HPO₄)_1·55 · H₂O with a basal spacing 10·9 Å is formed. The titration titration curve with a stronger base n-butylamine exhibits two plataux, showing the amine uptake to be a two-step process, and two phases formed through the process are Zr(C₄H₉NH₃PO₄)_1·34(HPO₄)_0·66 · H₂O and Zr(C₄H₉NH₃PO₄)_2·0 · H_2O with basal spacings 18·2 and 18·8 Å, respectively. Sodium ion-exchanged forms of crystalline α-zirconium phosphates also form complexes with pyridine and n-butylamine. The pH values of the amine solutions in this case differ from the case of the hydrogen form of the phosphates. On the basis of the uptake behaviors of pyridine and n-butylamine, two mechanisms of the complex formation of crystalline α-zirconium phosphates with these amines are proposed as follows: (1) Exchange reaction of interlayer cations of crystalline α-zirconium phosphate with pyridinium and n-butylammonium cations; (2) Intercalation reaction of these unionized organic bases into the interlayer spaces.     

The identification of an electronic Raman transition for the hexa-aquavanadium(III) ion. A direct spectroscopic determination of the trigonal field splitting of the 3T1g ground term

An electronic Raman transition (³E_g ← ³A_g) has been observed between the trigonally split components of the ³T_1g(F) ground term of the hexa-aquavanadium(III) ion in CsV(SO₄)₂·12H₂O and NH₄V(SO₄)₂·12H₂O. The magnitude of the splitting (1940 cm⁻¹) is in agreement with that estimated from earlier magnetic measurements (≈ 2000 cm⁻¹). The appearance of structure on the electronic Raman band can be interpreted in terms of transitions between spin-orbit coupled states.