氯代烃光解活泼自由基的ESR研究

本文用2,4-二硝基苯亚甲基特丁基氮氧化物(DNPBN)作自由基捕捉剂研究了氯代烃光解过程产生的自由基中间体。实验结果表明在汞灯照射下键能较低的多氯代烷烃分子中的碳-氯键极易发生均裂而产生碳中心自由基与活泼的氯原子,并且后者可被DNPBN捕获,形成颇为稳定的氮氧自由基加合物[Cl-DNPBN]~·。对多氯代苯,随着取代氯原子数目增多,加合物[Cl-DNPBN]~·的ESR信号强度也明显增加。此外,DNPBN对氯原子的大量捕捉实验还证明它对氯原子是一种高效的特征捕捉剂。     

有机锡化合物光解活泼自由基的ESR研究

本文用自旋捕捉技术与ESR相结合的方法,研究了六种有机锡化合物的光解反应历程。结果表明:有机锡化合物紫外光照时,碳-锡键发生均裂,产生碳中心和锡中心自由基。其中碳中心自由基易被捕捉剂α-苯基-N-特丁基氮氧化物(PBN)或2,3,5,6-四甲基亚硝基苯(ND)所捕获;而锡中心自由基可与菲醌形成稳定的环状加合物。由于环状加合物中配体的不同,产生的空间效应也不同,从而导致加合物中的未偶电子云密度发生变化,给出相异的ESR信号。     

2-溴代环己酮引发的苯乙烯原子转移自由基聚合

在铜体系催化的卤原子转移自由基聚合反应中 ,已有多种卤化物被作为引发剂使用 ,如α-卤代酯、α-卤代腈、多卤代烃、卤代苄基化合物及芳磺酰氯等 [1] ,最近又有报道称 N-氯代磺酰胺也可以作为引发剂使用 [2 ] .但以 α-卤代酮作引发剂只在钌系 [3～ 7]、铁系 [8]及镍系 [9]催化的原子转移自由基聚合中进行了研究 ,尤其是 Swawamoto等 [3～ 6] 对 Ru Cl2 (PPh3 ) 3 作催化剂 ,α,α-二氯苯甲酮和 1 ,1 ,1 -三氯丙酮作引发剂进行的甲基丙烯酸甲酯的原子转移自由基聚合进行了非常系统的研究 .由于羰基的吸电子能力较强 ,α-卤代酮的卤原子…     

新型含磷酰基的脂溶性自由基捕捉剂的合成及其ESR研究

超氧阴离子自由基的研究最近得到了广泛的关注 ,这主要是因为超氧阴离子自由基及由其诱导产生的各种活性氧 ( HOO· ,HO· 和 H2 O2 )与许多病理过程有关 ,如发炎 [1] 、缺血再灌综合症 [2 ] 、 DNA损伤[3] 和神经死亡疾病 [4 ] 等 .自旋捕捉技术是检测自由基最有效的方法 [5～ 9] ,近年来在生物体系活性氧自由基检测中得到广泛应用 [10 ,11] ,大力推动了生物自由基领域的研究 .合成新型自由基捕捉剂及改善其对超氧阴离子自由基的捕捉性能一直是人们追逐的热点 ,我们正致力于这方面的研究 [12 ] .其中提高自由基捕捉剂的脂溶性 ,扩大自…     

气相光解自由基的捕捉与检测

用自由基捕捉剂S将反应过程中形成的瞬态活泼自由基R·转变为较为稳定的自由基加合物RS·,由ESR测定其结构。为研究自由基反应机理提供了一种新方法,引起人们极大的重视。但大量工作主要是针对液相反应,对气相反应探讨甚少。显然,检测     

在光动力光疗中类卟啉稀土配合物光敏作用原初反应的特征: 产生自由基I型机制的ESR研究

本文用ESR方法研究了类卟啉稀土配合物[(CO_2H-APPC)Gd]Cl_2的光敏反应.用4-hydro-tetramethylpiperidine-N-oxide radical(4-hydro-TEMPO)作探针,通过对其消自旋的作用,证实[(CO_2H-APPC)Gd]Cl_2光敏反应中有阳离子自由基[(CO_2H-APPC)Gd]~(+)产生,加入还原剂可促使[(CO_2H-APPCGd]~+生成.经由5,5-Dimethyl-1-pyrroline N-oxide(DMPO)对超氧阴离子(O_2~-)和羟基自由基(·OH)的自旋捕捉及对该自旋加合物[DMPO-O_2~-]和[DMPO-OH]的ESR测定,证实有O_2~-和·OH产生,并用SOD清除O_2~-和甲酸钠清除·OH的实验,进一步证实O_2~-和·OH的产生.上述结果说明[(CO_2H-APPC)Gd]Cl_2光敏反应存在着产生[(CO_2H-APPC)Gd]~+和活性氧自由基的Ⅰ型机制.     

脂氧合酶催化双高-γ-亚麻酸脂质过氧化产生的碳自由基的结构确证

采用液相色谱-电子自旋共振波谱(LC/ESR)联用技术、液相色谱-质谱(LC/MS)联用技术结合自旋捕集技术,研究了脂氧合酶(LOX)催化双高-γ-亚麻酸(DGLA)脂质过氧化过程中产生的碳自由基.以α-[4-吡啶基-1-氧]-N-叔丁基氮酮(POBN)为自旋捕集剂,在LOX-DGLA反应混合物中与碳自由基形成自旋加合物后,根据各加合物在LC/UV/ESR和LC/MS中对应的保留时间,确定加合物的分子量,进一步根据加合物质谱裂解方式确定其结构.结果表明,在LOX催化DGLA脂质过氧化过程中产生的碳自由基主要包括~·C_7H_(13)O_2,~·C_(10)H_(17)O_2和~·C_5H_(11),分别来自DGLA脂氧自由基(8-,11-,15-LO~·)的β-裂解.此结果有利于进一步研究DGLA在体内的脂质过氧化过程及该过程中产生的碳自由基的生理作用.     

γ射线辐照的多晶态嘧啶核苷类中自旋捕捉自由基的ESR研究——Ⅱ.胸苷和脱氧胞苷盐酸盐

本文以NtB(亚硝基特丁烷)为捕捉剂,利用自旋捕捉(Spin Trapping)和ESR方法,研究了γ射线辐照的多晶态胸苷和脱氧胞苷盐酸盐中产生的室温自由基。对它们分别确定了三种类型与两种类型的碱基自由基,此与单晶ESR研究结果完全一致,从而获得它们R·自旋加合物的标准ESR波谱。此外,对脱氧胞苷盐酸盐还确定了在单晶ESR研究中未被鉴别的核糖自由基HO(5′)HC(4′)H<及由其演变而成的—(5′)H_2自由基。     

多氯代菲分子结构和热力学性质的密度泛函理论研究

采用密度泛函理论方法在B3LYP/6-311G(d, p)水平上对527个多氯代菲分子的几何结构进行了全优化并计算得到它们的热力学性质(等容热容( )、熵(S$)、标准生成焓(ΔfH$)和标准生成Gibbs自由能(ΔfG$)), 研究了这些性质与取代的氯原子数目和位置的关系, 根据各异构体的相对标准生成Gibbs自由能(Δr,fG$)的大小, 得到它们的热力学稳定性顺序. 计算结果表明: 绝大多数多氯代菲分子具有非平面的几何构型, 在多氯代菲分子中存在三种类型的分子内弱相互作用(H…H、C—H…Cl和Cl…Cl相互作用), 随着分子中取代的氯原子数目的增加, 多氯代菲最稳定异构体的ΔfH$和ΔfG$开始时逐渐减小, 然后又快速增加. 具有相同数目氯原子的多氯代菲异构体的ΔfH$和ΔfG$与氯原子的取代位置有很大的关系. 多氯代菲异构体的相对热力学稳定性主要由分子内的离域π键和Cl…Cl核排斥作用的强弱决定.     

水相中·OH, ·H和e-aq与2-氯酚反应机理研究

利用脉冲电子束辐解水产生*OH自由基、 *H及水合电子(e-aq), 研究了这些活性粒子在多种条件下与水相中2-氯酚的微观反应机理, 对其瞬态光谱中的主要吸收峰做了归属, 并初步考察了这些瞬态物种的生长、衰减等行为. 研究表明, *OH自由基与2-氯酚在碱性条件下可直接反应生成邻氯代酚氧自由基, 速率常数为1.0×109 L*mol-1*s-1, 也有部分*OH自由基与2-氯酚反应先生成OH-加合物, 再进一步消除水分子生成邻氯代酚氧基; 在酸性条件下要经过OH-加合物. *H则与2-氯酚反应生成H-加合物; e-aq可直接从2-氯酚分子夺氯, 在近中性和碱性环境中, 该反应的速率常数分别为1.25×109 L*mol-1*s-1和6.3×108 L*mol-1*s-1.     

导电高聚物的EXAFS 研究(Ⅰ)铂氯酸(H2PtCl6·6H2O)掺杂的聚乙炔

在实验室EXAFS装置上测量了一种导电高聚物——H_2PtCl_6·6H_2O掺杂聚乙炔和模型化合物(K_2PtCl_6)的PtL_Ⅲ吸收谱。用高功率的施转阳极靶X射线发生器(RigakuRU-1000)作为X射线源。观测到的EXAFS数据分析表明, Pt原子在试样中有两种配位状态。一种是PtCl_6~(2-)离子, Pt—Cl键长为0.233 nm, 另一种是Pt在0.228 nm附近有两个最近邻的Cl原子。实验结果提供了支持下述观点的直接结构信息: 随着电子从(CH)_x链向铂盐的转移, 发生下列反应:2H_2PtCl_6+2e~-→PtCl_6~(2-)+PtCl_2+4HCl     

2,5‐Dichloro‐2,5‐dihydro­thio­phene 1‐oxide: determinaton of the complete stereochemistry

The title five‐membered heterocycle, C₄H₄Cl₂OS, adopts an envelope conformation with the S atom at the tip of the flap. All three ring substituents, viz. the sulfoxide O atom and the two Cl atoms, are cis to each other. The two C atoms α to the sulfoxide group are also bonded to chlorine. The electron‐withdrawing chlorine substituents give rise to weak C—H·O hydrogen bonds with the sulfoxide O atom of a symmetry‐related mol­ecule [H·O = 2.44 (2) and 2.61 (2) Å, C·O = 3.143 (3) and 3.302 (2) Å and C—H·O = 129.9 (19) and 135.1 (19)°]. There is also a possible weak C—H·Cl inter­action. Chains of mol­ecules held together by these weak inter­actions run parallel to the a axis.     

On the weak O-H···halogen hydrogen bond: a rotational study of CH3CHClF···H2O

We measured the molecular beam Fourier transform microwave spectra of six isotopologues of the 1?:?1 adduct of CH(3)CHClF with water. Water prefers to form an O-H···F rather than an O-H···Cl hydrogen bond. This is just the contrary of what was observed in the chlorofluoromethane-water adduct, where an O-H···Cl link was formed (W. Caminati, S. Melandri, A. Maris and P. Ottaviani, Angew. Chem., Int. Ed., 2006, 45, 2438). The water molecule is linked with an O-H···F bridge to the fluorine atom, with r(F···H(w)) = 2.14 ?, and with two C-H···O contacts to the alkyl hydrogens with r(C(1)-H(1)···O(w)) = 2.75 ? and r(C(2)-H(2)···O(w)) = 2.84 ?, respectively. Besides the rotational constants, the quadrupole coupling constants of the chlorine atom have been determined. In addition, information on the internal dynamics has been obtained.     

Hydrogen-atom tunneling in isomerization around the C-O bond of 2-chloro-6-fluorophenol in low-temperature argon matrixes

Infrared spectra of 2-chloro-6-fluorophenol in argon matrixes at 20 K revealed the presence of a "Cl-type" isomer, which has the OH···Cl hydrogen bond, but no "F-type" isomer with OH···F bonding, in striking contrast to the existence of both isomers in the gas and liquid phases at room temperature. This finding suggests that the F-type isomer changes to the more stable Cl-type one by hydrogen-atom tunneling in the matrixes. Similar experiments on the OD···X analog species were performed to confirm the tunneling isomerization, resulting in an O-D stretching band of the F-type isomer appearing as well as that of the Cl type, like the spectra reported in the gas and liquid phases. This implies that tunneling migration of the D atom is inhibited in the argon matrix. In addition, UV-induced photoreactions of 2-chloro-6-fluorophenol were studied by a joint use of matrix-isolation IR spectroscopy assisted by density functional theory calculations. It was found that 2-fluorocyclopentadienylidenemethanone and 4-chloro-2-fluorocyclohexadienone were produced from the Cl type; the former was by the Wolff rearrangement after dissociation of the H atom in the OH group and the Cl atom, and the latter was by intramolecular migration of the H and Cl atoms. As for the deuterated F-type isomer, however, 2-chlorocyclopentadienylidenemethanone was produced by the Wolff rearrangement after dissociation of the D atom in the OD group and the F atom, besides other photoproducts of the deuterated Cl-type isomer. It is thus concluded that the tunneling isomerization around the C-O bond occurs in the OH···X species but not in the OD···X species.     

Time-resolved spectroscopic study of the reaction Cl + n-C5H12 --> HCl + C5H11 in solution

We study the hydrogen abstraction reaction from pentane by chlorine radicals using four different experimental approaches. We use two different solvents (CH2Cl2 and CCl4) and two different chlorine atom sources (photodissociation of dissolved Cl2 and two-photon photolysis of the solvent) to investigate their effects on the recombination and reactivity of the chlorine radical. All four experimental schemes involve direct probing of the transient chlorine population via a charge transfer transition with a solvent molecule. In one of the four approaches, photolysis of Cl2 in dichloromethane, we also monitor the nascent reaction products (HCl) by transient vibrational spectroscopy. Probing both the reactants and the products provides a comprehensive view of this bimolecular reaction in solution. Between one-third and two-thirds of the chlorine radicals that initially escape the solvent cage undergo diffusive geminate recombination with their partner radical (either another chlorine atom or the solvent radical). The rest react with pentane with the bimolecular rate constants k(bi) = (9.5 +/- 0.7) x 10(9) M(-1) s(-1) in CH2Cl2 and k(bi) = (7.4 +/- 2) x 10(9) M(-1) s(-1) in CCl4. The recombination yield phi(rec) depends on both the chlorine atom precursor and the solvent and is larger in the more viscous carbon tetrachloride solutions. The bimolecular reaction rate k(bi) depends only on the solvent and is consistent with a nearly diffusion-limited reaction.     

Substituent effects on CL···N, S···N, and P···N noncovalent bonds

Cl, S, and P atoms have previously been shown as capable of engaging in a noncovalent bond with the N atom on another molecule. The effects of substituents B on the former atoms on the strength of this bond are examined, and it is found that the binding energy climbs in the order B = CH(3) < NH(2) < CF(3) < OH < Cl < NO(2) < F. However, there is some variability in this pattern, particularly for the NO(2) group. The A···N bonds (A = Cl, S, P) can be quite strong, amounting to as much as 10 kcal/mol. The binding energy arises from approximately equal contributions from its induction and electrostatic components, although the former becomes more dominant for the stronger bonds. The induction energy is due in large measure to the transfer of charge from the N lone pair to a B-A σ* antibonding orbital of the electron-acceptor molecule containing Cl, S, or P. These A···N bonds typically represent the lowest-energy structure on each potential energy surface, stronger than H-bonds such as NH···F, CH···N, or SH···N.     

Characterisation of H2S···CuCl and H2S···AgCl isolated in the gas phase: a rigidly pyramidal geometry at sulphur revealed by rotational spectroscopy and ab initio calculations

Pure rotational spectra of the ground vibrational states of eight isotopologues of H(2)S···CuCl and twelve isotopologues of H(2)S···AgCl have been analysed allowing rotational constants and hyperfine coupling constants to be determined. The molecular structures have been determined from the measured rotational constants and are presented alongside the results of calculations at the CCSD(T) level. Both molecules have C(s) symmetry at equilibrium and are pyramidal at the sulphur atom. The chlorine, metal, and sulphur atoms are collinear while the local C(2) axis of the hydrogen sulphide molecule intersects the axis defined by the heavy atoms at an angle, φ = 74.46(2)° for Cu and φ = 78.052(6)° for Ag. The molecular geometries are rationalised using simple rules that invoke the electrostatic interactions within the complexes. Centrifugal distortion constants, Δ(J), and nuclear quadrupole coupling constants, χ(aa)(Cu) and χ(aa)(Cl) for H(2)S···CuCl are presented for the first time. The geometry of H(2)S···AgCl is determined with fewer assumptions and greater precision than previously.     

Structure and properties of the (HCl)2H2O cluster observed by chirped-pulse Fourier transform microwave spectroscopy

The rotational spectrum of the cyclic (HCl)(2)H(2)O cluster has been identified for the first time in the chirped pulse, Fourier transform microwave spectrum of a supersonically expanded HCl/H(2)O/Ar mixture. The spectrum was measured at frequencies 6-18.5 GHz, and transitions in two inversion-tunneling states, at close to 1?:?3 relative intensity, have been assigned for the parent species. The two single (37)Cl isotopic species, and the double (37)Cl species have been assigned in the natural abundance sample, and the (18)O and HDO species of the cluster were identified in isotopically enriched samples. The rich nuclear quadrupole hyperfine structure due to the presence of two chlorine nuclei has been satisfactorily fitted and provided useful information on the nonlinearity of intermolecular bonds in the cluster. The r(s) heavy atom geometry of the cluster was determined and the strongest bond in the intermolecular cycle r(O···HCl) = 3.126(3) ?, is found to be intermediate in length between the values in H(2)O···HCl and (H(2)O)(2)HCl. The fitted spectroscopic constants and derived molecular properties are compared with ab initio predictions, and a discussion of complexation effects in these three clusters is made.     

C-Cl bond fission dynamics and angular momentum recoupling in the 235 nm photodissociation of allyl chloride

The photodissociation dynamics of allyl chloride at 235 nm producing atomic Cl((2)P(J);J=1/2,3/2) fragments is investigated using a two-dimensional photofragment velocity ion imaging technique. Detection of the Cl((2)P(1/2)) and Cl((2)P(3/2)) products by [2+1] resonance enhanced multiphoton ionization shows that primary C-Cl bond fission of allyl chloride generates 66.8% Cl((2)P(3/2)) and 33.2% Cl((2)P(1/2)). The Cl((2)P(3/2)) fragments evidenced a bimodal translational energy distribution with a relative weight of low kinetic energy Cl((2)P(3/2))/high kinetic energy Cl((2)P(3/2)) of 0.097/0.903. The minor dissociation channel for C-Cl bond fission, producing low kinetic energy chlorine atoms, formed only chlorine atoms in the Cl((2)P(3/2)) spin-orbit state. The dominant C-Cl bond fission channel, attributed to an electronic predissociation that results in high kinetic energy Cl atoms, produced both Cl((2)P(1/2)) and Cl((2)P(3/2)) atomic fragments. The relative branching for this dissociation channel is Cl((2)P(1/2))/[Cl((2)P(1/2))+Cl((2)P(3/2))]=35.5%. The average fraction of available energy imparted into product recoil for the high kinetic energy products was found to be 59%, in qualitative agreement with that predicted by a rigid radical impulsive model. Both the spin-orbit ground and excited chlorine atom angular distributions were close to isotropic. We compare the observed Cl((2)P(1/2))/[Cl((2)P(1/2))+Cl((2)P(3/2))] ratio produced in the electronic predissociation channel of allyl chloride with a prior study of the chlorine atom spin-orbit states produced from HCl photodissociation, concluding that angular momentum recoupling in the exit channel at long interatomic distance determines the chlorine atom spin-orbit branching.     

溴化稀土冠醚配合物LnBr3(18-C-6)·nH2O的振动光谱与结构

本文合成了溴化稀土冠醚配合物, 测定了3500—100 cm~(-1)的付里叶红外和激光喇曼光谱, 并由振动光谱推断LnBr_3(18-C-6)·nH_2O的可能分子结构。