简介:采用HF/DFT的混合泛函PBE0和UPBE0优化了配合物[Os(PH3)2(CN)2(N^N)](其中N^N=2,2′-吡啶)的基态和激发态结构.在基态和激发态结构的基础上,利用含时密度泛函理论(TD-DFT)方法,结合极化连续介质(PCM)模型分别计算了它在二氯甲烷(1)、甲醇(2)、气态(3)和乙腈(4)溶液中的吸收和发射光谱.研究结果表明:优化得到的几何结构参数和相应的实验值符合得非常好.在极性较大的溶剂(2和4)中Os—P(1)和Os—C(1)键较长,Os—N(3)键较短,溶剂的极性会影响配合物的电子云分布.配合物在1-4溶剂中的最低能吸收和发射均来自分子轨道68→71的激发,该激发被指认为[d(Os)+π(CN)+π(N^N)→π*(N^N)]的跃迁具有混合的MLCT/LLCT特征.配合物在1-4溶剂中的最低能吸收和发射分别在471,410,488和445nm以及598,536,634和545nm,表明随着溶剂极性的逐渐增大(3〈1〈4〈2),最低能吸收和发射发生明显的蓝移.这显示出通过改变溶剂极性可以调节配合物的发光颜色.
简介:Objective: Toexploretheregulationofearlybraintissuemetabolicchangingafterbraininjuriesandtheclinicalsignificance. Methods: Therewere17patientswithbraininjuries.EarlydirectmonitoringofPtiO2,PtiCO2,pHandbraintemperature,dynamicobservationoftherelationbetweenvariousparametersandclinicsafterbraininjurieswereperformed. Results: EarlychangesofPtiO2,PtiCO2andpHwerecloselycorrelatedwithoutcome.ThedeathrateobviouslyincreasedwhenPtiO2wascontinuouslylowerthan9mm?Hgwithin24hoursafterinjuries.Secondarybraininjuryprolongedandaggravatedbraintissuemetabolicdisturbance.Whenintracerebralpressurewasover30mm?HgPtiO2begantodecrease.Thebraintemperatureinbraindeathpatientswasevidentlylowerthanaxillarytemperature. Conclusions: ThedirectmonitoringofPtiO2,PtiCO2,pHandbraintemperatureissafeandaccurateandcanfindearlyanoxiadamagetobraintissueandprovidereliablebasisforclinicaltherapy.Ithasaninstructivesignificanceinselectingandstudyinganewtreatmentmethodinbraininjuries.Anditcanbetakenasacriterioninclinicaljudgingbraindeaths.
简介:Thecopolymerizationofp-diethynylbenzene(PDEB)withphenylacetylene(PhA),4,4’-diethynylbiphenyl(DEBP)orm-diethynylbenzene(MDEB)arestudiedbyvaryingmoleratiosofmonomers.WhenthemoleratiosofPDEB/PhAarelessorequalto1/5,thecopolymersaresolubleandfusible,buttheothercopolymersareinsolubleandinfusible.Theresultsshowthatthegoodsolventofcross-linkedcopolymersisbenzeneandtheirsolubilityparameteris9.15cal0.5.cm(-1.5).Andtheirswellability(θp),Hugginsparameter(χ),density(d425)andtheaveragemolecularweightsbetweencrosslinks(c)aremeasured.Itisfoundthatθpandcofcopolymersaregreaterbutd425islessthanthatofrespectivehomopolymers.IRspectrashowthatthecopolymershavetransoidconfigurationandsmallnumberofunreactedethynylgroupsexistinthecopolymers.Themechanismaboutthepolymerizationoracetylenicderivativesinitiatedby(Ph3P)2PdCl2isdiscussed.
简介:一个全球海洋碳周期模型基于海洋将军发行量模型流行音乐和改进biogeochemical模型,OCMIP-2被采用在历史上观察的大气的CO2集中和不同未来情形(叫的代表性的集中小径,或RCP)下面模仿碳周期过程。在这份报纸的RCP为第五份评价报告(AR5)在气候变化(IPCC)上跟随Intergovernmental面板的设计。模型结果证明海洋从空气吸收CO2,被吸收将在四RCP下面在第21世纪继续。由空至海的CO2流动在历史的时间期间增加了并且到达的网1.87Pg/a(由碳计算了)在2005;然而,它将在第21世纪到达山峰然后减少。海洋主要专心于CO2中间的纬度,并且在赤道区域释放CO2。然而,在南极围绕天极的水流(ACC)区域,海洋将在升起的CO2集中下面从来源改变到水池,包括RCP4.5,RCP6.0,和RCP8.5。在2100,人为的碳将被搬运到40摥漠敶?桴?湥楴敲礠慥?獩爠畯桧祬?呼??湡?桴?潲敬漠???獩琠敨猠慭汬獥t
简介:WiththedecreaseofpHvaluefrom8.45to–1.0,theUV-Visabsorptionandfluorescentspectraof1,2-bis(4-pyridyl)ethylene(BPE)tookonthesamechangingtrendatfourdifferentsuccessivepHstages:8.45―7.20,7.20―5.62,5.62―2.60,and2.60―-1.0,namely,nochange,decrease,increase,anddecreaseagain.Amongthese,inarangeof7.20―5.62,thefluorescencewavelengthblueshiftedfrom418to359nm,buttheUV-Visabsorptionwavelength,incontrast,redshiftedfrom285to298nm.ThefluorescenceintensityofBPEhadadropeventoquenchuponadeclineinthepHvaluefrom2.60to–1.0probablyowingtoitscation-πinteractiontoreducetheπelectronclouddensityofBPE.Twodissociationconstants,pKa1(4.30±0.01)andpKa2(5.65±0.04),wereobtainedbasedonfluorescencedata.ThechangesoffluorescencespectraindicatethatBPEhas'off-on-off'switchbehavior.ThefluorescentspectraofBPEwerenearlyindependentonthepresenceofα-andβ-cyclodextrins.
简介:Monoammoniumphosphate(1molL^-1),monopotassiumphosphate(1molL^-1)andaluminumchloride(5×10^-3molL^-1)wereusedtoinvestigatetheinfluenceofpHontheformationofNH4-taranakiteandK-taranakiteinsystemswithahighNH4H2PO4orKH2PO4concentration.TheexperimentaldataindicatedthatthereactionproductsofaluminumwithNH4H2PO4orKH2PO4changedwiththepHinthesystems.InapHrangeof2.5to10.0,asthepHincreased,theproductsineitherammoniumorpotassiumsystemfollowedthesequence:taranakite,amorphous(NH4,K)2AIH(PO4)2.4H2O,andthencrystalline(NH4,K)AlPO4OH.2H2O.However,thepHrangesoftheformationoftheseproductsinammoniumsystemweredifferentfrompotassiumsystem.NH4-taranakiteformedfrompH2.75topH5.75,whereasK-taranakiteformedinthepHrangeof3.00to5.0,Fromthetheoreticalcalcuationbyacomputerprogram(GEOCHEMversion2.0),NH4-taranakteandK-taranakitecouldformatthepHfrom1.50to8.30andfrom1.25to8.45,respectively.ThesepHrangesweremuchwiderthantheexperimentalresults.Thedifferencebetweentheexperimentaldataandtheoreticaldatawasattributedtothelackofkineticdataand/ortheincompletenessandinaccuracyofthethermodynamicdatainthedatabaseoftheprogram.ThepHrangesoftheformationofthetaranakitesindicatedthatthetaranakitescouldexistintheimmediatevicinityofphosphateferilizerzoneasreactionproductsofphosphatefertilizerswithsoils,especiallyacideicsoils,resultinginthefixationofnotonlyphosphatebutalsonitrogenand/orpotassiuminsoils.
简介:为了探讨H7K(R2)2修饰的pH敏感脂质体对U87-MG细胞的靶向作用,本文选择香豆素-6(coumarin-6)为荧光探针构建了包载香豆素--6的H7K(R2)2修饰的pH敏感脂质体(coumarin--6--PSL--H7K(R2)2)。采用流式实验分别对H7K(R2)2在coumarin--6--PSL--H7K(R2)2中的比例以及coumarin-6--PSL--H7K(R2)2在U87--MG细胞的摄取途径进行研究。采用CD技术对H7K(R2)2在pH7.4和pH6.8条件下的二级结构进行考察。实验结果显示,H7K(R2)2在coumarin--6--PSL--H7K(R2)2中占2.5%时,其靶向作用优于1%和3.5%。细胞摄取途径实验表明,coumarin--6--PSL--H7K(R2)2进入U87--MG细胞不受菲律平、甲基--β--CD和氯丙嗪等抑制剂的影响。H7K(R2)2在pH6.8时的二级结构多为β--turn。本研究结果表明,在H7K(R2)2修饰的pH敏感脂质体中,H7K(R2)2的最佳比例可确定为2.5%。H7K(R2)2修饰的pH敏感脂质体进入肿瘤细胞的途径主要通过低pH条件下H7K(R2)2所产生的穿膜肽样作用。H7K(R2)2在pH6.8条件下所出现的发卡样二级结构是其产生靶向和穿透作用的可能机制。
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