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500 个结果
  • 简介:采用密度泛函理论(DFT)对P450酶活性中心铁卟啉CpdI催化乙基亚硝胺(NDEA)代谢活化的反应机理进行了研究.结果表明,CpdI催化NDEA羟基化的过程包含氢抽提反应和回弹反应2个步骤.其中,氢抽提反应为控速步骤,氢自由基从NDEA转移到铁卟啉的FeO上,是典型的氢原子传递(HAT)过程;紧接着铁卟啉上的羟基经历无能垒的反应过程回弹到NDEA自由基上,形成羟基化代谢产物.NDEA羟基化过程中高自旋态(HS)和低自旋态(LS)均参与反应,整个羟基化过程呈现明显的双态反应性(TSR).研究比较了NDEA分子侧链上C^αH和C^βH羟基化反应的差异,得到C^αH和C^βH羟基化所需跨越的能垒分别为57.7/57.7kJ/mol(LS/HS)和76.4/74.3kJ/mol(LS/HS),表明C^αH比C^βH更易于在P450作用下发生羟基化;此外,C^βH羟基化所需克服的能垒并未过高,使得C^βH羟基化在生理条件下完全也有可能发生.本研究为深入揭示亚硝胺经代谢活化导致癌症的作用机制提供了可靠的理论依据.

  • 标签: 亚硝胺 细胞色素P450 羟基化反应 代谢活化 密度泛函理论.
  • 简介:Thecrystalandmolecularstructuresof[(C3H7O)2PS2]2(CCDCNo.217201)weredeterminedbymeansofX-raycrystallography.ItcrystallizedinatriclinicsystemwithspacegroupP1^-andlatticeparametersa=0.82794(3)nm,b=0.84764(2)nm,c=0.85034(3)nm,α=97.78(3)°β=110.77(3)°,γ=94.95(3)°,V=0.54701(9)nm^3,Z=1.Inthismolecule,thetwodiisopropyldithiophosphategroups,[(C3H7O)2PS2]2,whichareparalleltoeachother,arelinkedbyanS--Sbondandthereexistinversioncentersinthemolecule,Inthestructure,theP=Sbondsinthetwodithiophosphateunitsaretrans-orientedtoeachother.

  • 标签: X射线结晶学 二烃基二硫代磷酸盐 中心对称 2 晶体结构 O'-二异丙基二硫代磷酸盐
  • 简介:以4-[(8-羟基-5-喹啉)偶氮]-苯磺酸与氯化钴为原料,采用溶剂热法通过原位反应合成{[Co(5-氨基-8-羟基喹啉)_2]·H_2O}_n,并通过X-射线单晶衍射方法确定了该配合物的晶体结构.结构分析表明:标题配合物属于斜方晶系,Pbcn空间群,晶胞参数a=1.321(2)nm,b=0.811(2)nm,c=1.511(2)nm,α=β=γ=90.00°,V=1.619(3)nm~3,Z=4,R_1=0.0516,wR_2=0.1025.配合物中存在ππ堆积相互作用和氢键作用,将配合物连接形成三维超分子网络结构.

  • 标签: Co(Ⅱ)配合物 氢键 π…π堆积 超分子
  • 简介:研究了YBaCu3O6~超导催化剂上CO的加氢制醇反应。考察了温度、压力和空速等条件对催化剂反应性能的影响。反应的主要产物是甲醇、CO和少量甲醚。利用XPS、XRD和AFM等技术对催化剂的结构、铜的存在状态和反应活性位进行表征发现,在反应过程中,YBaCu3O6~由orthombic相转变为tetragonal相。反应活性位可能是Cu(I)物种。反应后催化剂颗粒的分散程度明显提高

  • 标签: CO2加氢 YBa2Cu3O6~7超导催化剂 结构 活性位
  • 简介:Lifetimemeasurementsoflow-lyingexcitedstatesin^87Zrhavebeenperformedviaβ-γcoincidences.The127MeV^32SbeamwasdeliveredfromtheSector-FocusingCyclotron(SFC)oftheHeavyIonResearchFacilityinLanzhou(HIRFL).Theparentnuclei^87Nbwereproducedbythereaction58Ni(32S,2p1n),atabeamenergy127MeVthrougha8umAldegrader.A200ug/cm^2layerof58Nievaporatedontoa200ug/cm^2thickcarbonfoilwasemployedasthetarget.Afterevaporationresidueswereseparatedfromtheprojectilebeamsbythegas-filledrecoilseparatorSHANS[1],thenucleiofinterest87Zrcanbeobtainedwithahigherpurityandthenwereimplantedintoa300umsilicondetector.

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  • 简介:TheapplicationofLanthanumBromide(LaBr3)detectorsprovidesauniqueopportunitytomeasurelifetimeofexcitedstatesinpicosecond-nanosecondregion.Reducingthebackgroundisofcriticalimportancetogetpreciseresults.Forsomeexcitedstatesfeedingfromisomerswithlifetimelongerthan1μs,itcanbeachievedbytheSpectrometerforHeavyAtomandNuclearStructure(SHANS)[1].143Eunucleiwerepopulatedviathe123Sb(24Mg,4n)fusion-evaporationreaction.Mostoftheevaporationresiduesatgroundstateorlong-livedisomersweretransferredtodetectionterminalafteraflightofabout1.4μsinSHANS.Inthecaseof143Eu,threetransitionshavebeenobserved(Fig.1).

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  • 简介:Atacertainhightemperature,thiscyclewillbedominantandendtherp-processtoheavierregion[2].Itprovidesanuppertemperaturelimitforrp-processalongtheprotondriplinetoproducenuclidesbeyondA=84,includingthelightpnuclidesof92;94Mo,96;94Ru.TheexistenceofZr-Nbcycleisanimportantquestioninrp-process[2].α-separationenergy(Sα)of84Moplaysanimportantroleintheformationofthiscycle.Astrongenhancementof83Nb(p,α)reactionrateisduetoaverylowSαof84Mo[1].

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  • 简介:标题化合物C26H26O5以2,3-萘甲醛和5-甲基-1,3-环己酮为原料,在醋酸溶剂中,室温下经搅拌多组分一锅法合成得到.其结构通过单晶X-射线衍射法确定,晶体属单斜晶系,空间群P21,相对分子质量Mr=418.47,晶胞参数a=0.99004(8)nm,b=1.09098(9)nm,c=1.04246(11)nm,V=1.08753(17)nm3,Z=2,晶胞密度Dc=1.278g/cm3,吸收系数μ=0.088mm-1,单胞中电子的数目F(000)=444.晶体结构用直接法解出,经全矩阵最小乘法对原子参数进行修正,最终的偏离因子为R1=0.0533,wR2=0.1293.在晶体结构中新形成的吡喃环为半椅式构象,而茚中五元环则为信封式构象.

  • 标签: 室温 双环化反应 多组分 晶体结构
  • 简介:Theneworganic-inorganiccompound,[C_6H_7N_2O_2]_3TeCl_5·2Clwassynthesizedanditsstructurewasdeterminedatroomtemperatureinthetriclinicsystem(P~-1)withthefollowingparameters:a=10.5330(11)?,b=10.6663(11)?,c=15.9751(16)?,α=82.090(2)°,β=71.193(2)°,γ=68.284(2)°andZ=2.ThefinalcycleofrefinementledtoR=0.057andRw=0.149.ThecrystalstructurewasstabilizedbyanextensivenetworkofN--H···Clandnon-classicalC--H···Clhydrogenbondsbetweenthecationandtheanionicgroup.Severalthermalanalysistechniquessuchasthermogravimetricanalysis,differentialscanningcalorimetricanalysisandevolvedgasanalysiswereused.Weusedisoconversionalkineticsmethodstodeterminethekineticsparameters.Weobservethatthedecompositionof[C_6H_7N_2O_2]_3TeCl_5·2Clentailstheformationhydrochloricacidofnitroanilineasvolatiles.Theinfraredspectrawererecordedinthe4000–400cm~(-1)frequencyregion.TheRamanspectrawererecordedintheexternalregionoftheanionicsublatticevibration50–1500cm~(-1).TheopticalbandgapwascalculatedfromtheUV-VisabsorbancespectrausingclassicalTaucrelationwhichwasfoundtobe3.12and3.67eV.

  • 标签: 结构分析 光学性质 合成 化合物 紫外-可见吸收光谱 差示扫描量热分析
  • 简介:Fourkeyreactions,12C(,)13O,13C(,n)16O,25Mg(p,)26Aland19F(p,)16O,willbestudiedforthefirsttimewithinorneartheastrophysicalrelevantenergyregions(Gamowwindow)atJinpingUndergroundlaboratoryforNuclearAstrophysics(JUNA)[1],whichwilltaketheadvantageoftheultra-lowbackgroundofChinaJinPingundergroundLaboratory(CJPL),highcurrentacceleratorbasedonECRsourceandahighlysensitivedetectionsystem.

  • 标签: Institute MODERN PHYSICS
  • 简介:Thispaperreportstwolanthanidecomplexesofformula(C9H7)Ln(C8H8)·(THF)2whereLnisProrNd,C9H7isindenyl,andC8H8iscyclooctatetraene(COT).ThecomplexeswerepreparedbythereactionofLnCl3withK(C9H7)andK2(C8H8)inTHF.(C9H7)Pr(C8H8)·(THF)2crystallizesinTHFat-15℃inthemonoclinicspacegroupP21:withunitcelldimensionsa=8.446(0),b=10.083(2),c=13.407(3),β=105.48(1)°,V=1100.43(35)3,Dc=1.52g/cm3andZ=2.ThefinalRvalueis0.033,Rwvalueis0.030,respectively.In(C9H7)Pr(C8H8)·(THF)2afive-memberedringcentroidofC9H7,theC8H8ringcentroidandthetwooxygenatomsfromthetwoTHFmoleculesformadistortedtetrahedralgeometryaroundthemetal.

  • 标签: complexes monoclinic membered C8H8)Ln C8H8)Pr C9H7
  • 简介:8,8′-Dibromo-6,6′,7,7′-tetramethoxy-5,5′-diisopropyl-3,3′-oxydimethylenedinaphtho[2,1-b:2′,1′-d]furan,C32H30Br2O;M.W.=670;triclinic;spacegroupP1;a=8.896(2),b=10.216(1),c=10.423(1)A,α=108.48(1),β=119.36(1),γ=99.26(1);V=723.5A3;Z=1,Dcal.=1.479g.cm-3.MoKα=28.11cm-1,F(000)=326,T=293K.Thestructurewassolvedbydirectmethodandfull-matrixleast-squaresrefinementconvergedatR=0.034for2377observedreflections.Theoxygenatominseven-memberedringexistsinadisorderedarrangement.Bothbisnaphthaleneandoxygen-containingfive-memberedringhaveplanarconformationswithdihedralangle6°,showingmarkedaromaticfeature.

  • 标签: FURAN derivative dibromo-6 6 TRICLINIC membered planar
  • 简介:用离子交换法将具有Keggin结构TBA4H3PW7Mo3Cu2O38(H2O)2(M=Fe2+,Co2+,Cu2+,Ni2+和Mn2+)嵌入到Zn2A1黏土中,得到层状化合物LDH-PW7Mo3Cu2O38(H2O)2(M=Fe2+,Co2+,Cu2+,Ni2+和Mn2+),并用XRD,IR,uV对其进行了表征.结果表明:杂多阴离子进入黏土后,仍保留了其Keggin结构.利用合成的层状化合物为催化剂,以顺丁烯酸与HzO。的环氧化反应为模型反应考察其催化活性,结果表明:层状化合物在环氧化反应中显示优良的催化性能.

  • 标签: 三元杂多阴离子 层状化合物 KEGGIN结构 环氧化反应
  • 简介:合成了通式为K10H5[Ln(PMo7W2VO39)2].nH2O(Ln-La^3+,Ce^3+,Pr^3+,Nd^3+,Sm^3+,Eu^3+,Gd^3+,Dy^3+,Yb^3)的9种五元新型杂多配合物,并用元素化学分析,TG,ICP,IR,UV,31^1P,51V-NMR,ESR,XPS,XRD进行了表征,结果表明新配合物仍保持Keggin结构,稀土元素处于配合物的内界。借助TG-DTA,不同温度下的IR,XRD的水溶性实验考察了新配合物的热解性质,得出了热稳定的温度范围为400℃-500℃,为催化研究提供了依据。

  • 标签: 稀土元素 钼钨钒磷杂多配合物 KEGGIN结构 合成 热稳定性
  • 简介:Kineticsofchloride/sulfate,chloride/nitrateandnitrate/sulfateforwardexchangesandreverseexchangesatsolutionconcentrationsof1N,0.2Nand0.02Non201×7strongbaseanionexchangeresin,respectively,havebeenexaminedat25℃.Itisfoundthattheforwardandthereverseexchangeratesofthetwogivenionsatlowsolutionconcentration,respectively,underidenticalconditionscanbecontrolledbydifferentmechanisms,whilethoseathighsolutionconcentrationareallcontrolledbyparticlediffusion.Theternaryexchangeratesofsulfate/(chloride+nitrate)andnitrate/(chloride+sulfate)havealsobeenexamined.

  • 标签: 二元离子交换 硫酸根-氯离子-硝酸根离子-201×7体系 三元离子交换 动力学
  • 简介:InsituhighpressureenergydispersiveX-raydiffractionmeasurementsonlayeredperovskite-likemanganateCa3Mn2O7underpressuresupto35GPahavebeenPerformedbyusingdiamondanvilcellwithsynchrotronradiation.Theresultsshowthatthestructureoflayeredperovskite-likemanganateCa3Mn2O7isunstableunderpressureduetotheeasycompressionofNaCl-typeblocks.ThestructureofCa3Mn2O7underwenttwophasetransitionsunderpressuresintherangeof0-35GPa.Onewasatabout1.3GPawiththecrystalstructurechangingfromtetragonaltgoorthorhombic.Theotherwasatabout9.5GPawiththecrystalstructurechangingformorthorhombicbacktoanothertetragonal.

  • 标签: 高压 X射线衍射 Ca3Mn2O7 钙钛矿结构 锰酸盐晶体 相变
  • 简介:Anewapproachtodeterminealltheelectro-elasticconstantsofthepiezoelectriccrystalsinclass4mmhasbeenputforward.Asanexample,alltheconstantsofLithiumTetraborate(Li2B4O7)crystalhavebeenmeasuredbymeansoftheapproach.Theoutstandingadvantageoftheapproachisthatiton-lyneedstoemployinmeasurementthreecrystalplatesdifferentlyoriented.

  • 标签: CONSTANTS lithium PIEZOELECTRIC outstanding INFINITE RESONANT
  • 简介:人们一直尝试合成可以替代现今高能炸药的新型炸药,期望新型炸药在相同的感度水平有更高的性能,或者在相同的性能水平下有更低的感度。1,1-氨基-2,2-硝基乙烯(简称FOX-7)就是在这种要求下研究较为活跃的一种新型低感炸药。文献报道FOX-7有3种或4种相态,在室温下存在α相,在113℃转变成β相,下一个相变开始于160℃或170℃。文中利用四圆衍射仪测定FOX-7的晶体结构,变温X射线衍射仪(XRD)研究FOX-7在加热时发生的相变。

  • 标签: 硝基乙烯 二氨基 相变 X射线衍射仪 FOX-7 高能炸药