双噻吩基四硫富瓦烯富勒烯C60几何构型与电子结构的理论研究

利用半经验AM1法研究双噻吩基四硫富瓦烯富勒烯-C60(BTTTF-C60)和四硫富瓦烯-C60(TTF-C60)的几何构型、电子结构和前线轨道.计算结果显示,两化合物的TTF面发生弯曲,形成独特的空间构型,电子结构的分析表明其原因是由C60与TTF或BTTTF的相互作用引起的.C60的LUMO能与BTTTF的HOMO能接近,易发生D-A反应,形成BTTTF-C60.BTTTF-C60和TTF-C60的LUMO能仍较低.LUMO分布集中在C60部分, 表明BTTTF-C60的C60母体仍可接受电子.另外对两分子的电荷分布、 HOMO及LUMO的分析比较,表明所设计的BTTTF-C60分子可能产生与TTF-C60分子类似的电荷分离态.     

Photoinduced charge separation and charge recombination in [60]fullerene-ethylcarbazole and [60]fullerene-triphenylamines in polar solvents

Molecules of C60 covalently connected with N-ethylcarbazole (EtCz) and triphenylamine (TPA) have been synthesized. Photoinduced electron transfer in C60-EtCz and C60-TPA has been studied in polar and nonpolar solvents using time-resolved transient absorption and fluorescence measurements. From the fluorescence lifetimes, the excited singlet state of the C60 moiety (1C60) of C60-TPA generates predominantly C60*--TPA*+, which decays quickly to the ground state within 6 ns even in polar solvents. In the case of C60-EtCz, on the other hand, about half of the 1C60 moiety generates short-lived C60*--EtCz*+, while the other half of the 1C60 moiety is transferred to the 3C60 moiety via intersystem crossing in dimethylformamide, in which the energy level of C60*--EtCz*+ is lower than that of 3C60. Thus, the charge separation takes place via 3C60 generating C60*--EtCz*+, having a lifetime as long as 300 ns, probably because of the triplet spin character of C60*--EtCz*+. A special property of the EtCz moiety to stabilize the hole in the charge-separated state was revealed.     

C60氢胺化反应及其在制备含C60功能材料中的应用

C60与胺类化合物的反应是C60衍生化的重要方法。 本文介绍了C60氢胺化反应的一般规律和特点,对C60氢胺化反应在制备含C60高分子功能材料、含C60自组装单分子膜(SAM)、含C60有机/无机纳米材料和C60生物功能材料等方面应用的研究进展作了综述。     

A comparison of the photochemical reactivity of N@C60 and C60: photolysis with disilirane

N@C60 has a lower photochemical reactivity toward disilirane than C60, although N@C60 does not differ from C60 in its thermal reactivity; theoretical calculations reveal that N@C60 and C60 have the same orbital levels and that N@3C60* has a shorter lifetime than 3C60*.     

Alteration of nC60 in the presence of environmentally relevant carboxylates

C(60) forms colloidally stable nanoscale particles (nC(60)) when mixed with water for extended periods. Past studies have shown that macromolecules such as natural organic matter (NOM) and proteins accelerate nC(60) formation and stabilize the resulting nanoparticles. To better elucidate the mechanisms underlying this behavior, nC(60) was produced via extended mixing in the presence of sodium citrate and other carboxylates. Carboxyl groups are a predominant functional group in many environmentally relevant macromolecules, thus studies examining carboxyl-C(60) interactions are merited. nC(60) produced in the presence of citrate (cit/nC(60)) and other carboxylates differs from nC(60) produced in water alone (aq/nC(60)), exhibiting enhanced negative surface charge, smaller particle size, and different spectroscopic characteristics. Importantly, the simultaneous detection of irregular nC(60) nanoparticles and small, regularly shaped nC(60) suggests that mixing-mediated "top-down" and carboxyl group-mediated "bottom-up" processes occur concurrently when nC(60) is produced in the presence of carboxylates and, by extension, in the presence of carboxylate-containing macromolecules. The "bottom-up" process is expected to involve molecular C(60) or small clusters of C(60) molecules as an important intermediate.     

Self-organization of double-C60 end-capped poly(ethylene oxide) in chloronaphthalene and benzene solvent mixtures

Well-defined and narrowly distributed double-C60 end-functionalized poly(ethylene oxide) (C60-PEO-C60) was prepared by reacting azido-terminated PEO with C60. The self-organization behavior of such C60-modified copolymers in different mixtures of chloronaphthalene (CN) and benzene (BN) was studied by a combination of static and dynamic laser light scattering. For C60-PEO-C60 in pure CN, a selective solvent only for C60, self-organization occurred to form a large micelle-like core-shell aggregate, probably with some C60 interlocking with each other with the collapsed PEO chains as the core. The addition of BN, a second selective solvent for core-forming PEO chains, has a significant effect on the structures and compactness of the resultant aggregates because the introduction of BN increases the stretching of the PEO chains inside the core and modifies the interfacial energy of the core-corona interface. On the other hand, for C60-PEO-C60 in pure BN, a non-solvent of C60, several smaller flower-like micelles may self-organize to form a large spherical-like aggregation complex.     

Study of photoinduced electron transfer between [60]fullerene and proton-sponge by laser flash photolysis: addition effects of organic acid

Photoinduced electron-transfer processes between fullerene (C60) and 1,8-bis(dimethylamino)naphthalene, which is called a proton-sponge (PS), have been investigated by means of laser flash photolysis in the presence and absence of CF3CO2H. For a mixture of C60 and PS, the transient absorption spectra showed the rise of the C60 radical anion with concomitant decay of the C60 triplet (3C60), suggesting that photoinduced intermolecular electron transfer occurs via 3C60 in high efficiency in polar solvent. For a covalently bonded C60-PS dyad, photoinduced intramolecular charge-separation process takes place via the excited singlet state of the C60 moiety, although charge recombination occurs within 10 ns. For both systems, electron-transfer rates were largely decelerated by addition of a small amount of CF3CO2H, leaving the long-lived 3C60. These observations indicate that the energy levels for charge-separated states of the protonated PS and C60 become higher than the energy level of the 3C60 moiety, showing low donor ability of the protonated PS. Thus, intermolecular electron-transfer process via 3C60 for C60-PS mixture and intramolecular charge-separation process via 1C60-PS for C60-PS dyad were successfully controlled by the combination of the light irradiation with a small amount of acid.     

Cu_xC_(60)薄膜紫外-可见吸收光谱研究

近来,有关 C60的研究主要集中在有关晶格动力学 [1]、电子结构 [2～ 4]和 MxC60（ M代表碱金属或碱土金属）的超导电性研究 [5].但由于 MxC60在大气中不能稳定存在,制约了 MxC60的深入研究和实际应用 .最近, Masterov等人报导了他们对 Cu/C60的超导特性研究 [6～ 7],认为其转变温度 Tc在 80～ 120 K之间,这个转变温度比现有的 MxC60的转变温度（ Tc～ 40 K）要高得多 .但有关更进一步的研究未见报导 .因此,我们拟对 CuxC60体系作较为详尽的研究,这对于进一步研究其超导机理是有必要的 .本工作是在成功地制备了 CuxC60薄膜的…     

Photoinduced charge separation and charge recombination in the [60]fullerene-diphenylbenzothiadiazole-triphenylamine triad: role of diphenylbenzothiadiazole as bridge

Photoinduced electron-transfer processes of the newly synthesized [60]fullerene-diphenylbenzothiadiazole-triphenylamine (C60-PBTDP-TPA) triad in polar and nonpolar solvents have been studied by using time-resolved transient absorption and fluorescence measurements from picosecond to microsecond regions. By fluorescence lifetime measurements in picosecond time regions, excitation of the charge-transfer transition of the PBTDP-TPA moiety in C60-PBTDP-TPA induces energy transfer to the C60 moiety generating 1C60*-PBTDP-TPA, competitively with charge separation generating C60*--PBTDP-TPA*+. From 1C60*-PBTDP-TPA, which is generated directly and indirectly, charge separation occurs generating C60*--PBTDP-TPA*+ in polar solvents. The C60*--PBTDP-TPA*+ formed via the singlet excited states decayed within a few nanoseconds as revealed by the picosecond transient absorption spectra. In the nanosecond time region, C60*--PBTDP-TPA*+ is produced slowly, probably via 3C60*-PBTDP-TPA. Lifetimes of such slowly generated C60*--PBTDP-TPA*+ were longer than 1 micros, which are the longest values among the C60-bridge-TPA triad systems reported hitherto at room temperature. Roles of the PBTDP-TPA moiety with twisted intermolecular charge-transfer character playing as energy donor and electron donor in addition to the bridge have been disclosed.     

含水溶性碳笼烯的水凝胶

含水溶性碳笼烯的水凝胶陈立桅郑磊洪瀚李子臣周锡煌李福绵（北京大学化学系北京１００８７１）关键词水溶性碳笼烯，水凝胶，超氧负离子随着碳笼烯（Ｃ６０，Ｃ７０，ｆｕｌｅｒｅｎｅｓ）的简便制取方法［１］的问世，其应用，特别是其材料化自然被提到日程上来．...     

Modulating charge separation and charge recombination dynamics in porphyrin-fullerene linked dyads and triads: Marcus-normal versus inverted region.

Photoinduced charge separation (CS) and charge recombination (CR) processes have been examined in various porphyrin-fullerene linked systems (i.e., dyads and triads) by means of time-resolved transient absorption spectroscopy and fluorescence lifetime measurements. The investigated compounds comprise a homologous series of rigidly linked, linear donor-acceptor arrays with different donor-acceptor separations and diversified donor strength: freebase porphyrin-C60 dyad (H2P-C60), zincporphyrin-C60 dyad (ZnP-C60), ferrocene-zincporphyrin-C60 triad (Fc-ZnP-C60), ferrocene-freebase porphyrin-C60 triad (Fc-H2P-C60), and zincporphyrin-freebase porphyrin-C60 triad (ZnP-H2P-C60). Most importantly, the lowest lying charge-separated state of all the investigated systems, namely, that of ferrocenium ion (Fc+) and the C60 radical anion (C60.-) pair in the Fc-ZnP-C60 triad, has been generated with the highest quantum yields (close to unity) and reveals a lifetime as long as 16 micros. Determination of CS and CR rate constants, together with the one-electron redox potentials of the donor and acceptor moieties in different solvents, has allowed us to examine the driving force dependence (-DeltaG0ET) of the electron-transfer rate constants (kET). Hereby, the semilogarithmic plots (i.e., log kET versus -DeltaG0ET) lead to the evaluation of the reorganization energy (lambda) and the electronic coupling matrix element (V) in light of the Marcus theory of electron-transfer reactions: lambda = 0.66 eV and V = 3.9 cm(-1) for ZnP-C60 dyad and lambda = 1.09 eV and V = 0.019 cm(-1) for Fc-ZnP-C60, Fc-H2P-C60, and ZnP-H2P-C60 triads. Interestingly, the Marcus plot in Fc-ZnP-C60, Fc-H2P-C60, and ZnP-H2P-C60 has provided clear evidence for intramolecular CR located in both the normal and inverted regions of the Marcus parabola. The coefficient for the distance dependence of V (damping factor: betaCR = 0.58 A(-1) is deduced which depends primarily on the nature of the bridging molecule.     

Wavelength-dependent fragmentation and clustering observed after femtosecond laser ablation of solid C60

We report here the resonance effect in femtosecond laser ablation of solid C60 by investigating wavelength and fluence dependence of product ion species. When the ablation laser wavelength is far from the molecular absorption band of C60, we observe both C60-2n+ fragment ions and C60+2n+ cluster ions as well as C60+ parent ion. Delayed ionization of C60 is not significant. When the ablation laser wavelength is near resonant with the molecular absorption, we observe C60+ and some amount of C60-2n+ fragment ions depending on the laser fluence. Delayed ionization of C60 is significant in this case, which indicates high internal energy of C60 molecule. From the observations, we confirm the strong coupling of femtosecond laser energy with C60 molecule when the molecular absorption is high at the ablation laser wavelength.     

Self-assembly of well-defined mono and dual end-capped C(60) containing polyacrylic acids in aqueous solution

Well-defined stimuli-responsive mono and dual fullerene (C(60)) end-capped poly(acrylic acid)s (PAA-C(60) and C(60)-PAA-C(60)) were synthesized by reacting C(60) with well-defined mono and dual azide end-functionalized poly(tert-butyl acrylate)s, followed by hydrolysis. The aggregation behaviors of these C(60) end-capped polymers in aqueous solution were examined using potentiometric and conductometric titrations and static and dynamic light scattering as well as transmission electron microscopy (TEM). Both PAA-C(60) and C(60)-PAA-C(60) show pH-responsive and water-soluble properties at high pH. Both polymers self-assemble to form large compound micelles (LCMs) in aqueous solutions. The LCMs of PAA-C(60) exist as "compact aggregates", whereas the LCMs of C(60)-PAA-C(60) possess a "core-shell" structure with a larger size and aggregation number. The micelles for both polymers swell upon neutralization, where the R(h) of PAA-C(60) micelles increases from approximately 44 to approximately 102 nm and the R(h) of C(60)-PAA-C(60) aggregates varies from approximately 89 to approximately 128 nm with increasing degree of neutralization. The lower swelling of the dual end-capped C(60)-PAA-C(60) system is related to its higher C(60) content, which enhances the interpolymer chain hydrophobic association that restrains the swelling of micellar aggregates.     

C60掺杂物超导性EHMO晶体轨道研究

本文对晶态C60, K3C60, K6C60, Rb3C60, Rb6C60, RbCs2C60, Rb2CsC60,KRb2C60, K2RbC60, K2CsC60, Na2CsC60, Li2CsC60, Na2RbC60, Na2KC60进行了EHMO三维晶体轨道的能带结构计算。计算结果除了得到能带结构外, 还得到了这类掺杂物的总态密度, 原子与轨道净电荷, 晶体轨道矢量, 单胞内外原子与轨道投影态密度等。利用上述结果不仅可以从理论上说明A3C60的超导性以及C60和A6C60的绝缘性; 而且还得到ln(1/Tc)和-1/NEf之间一种近似的线性关系, 这个结论与BCS理论的预测非常吻合。     

C60-地塞米松的激光激发

利用激光光解装置检测了C60-地塞米松(C60-DE)的苯溶液在355 nm激光照射下产生的激发三重态, 3C60-DE*出现四个吸收峰, 分别位于700、440、350 和310 nm. 在330 nm处观察到了它的漂白吸收最大值, 这与其基态吸收最大值相对应. 3C60-DE*能够将能量转移给O2分子而淬灭. 与3C60*相比, 3C60-DE*的三重态鄄三重态(T-T)淬灭速率常数减小(3C60*为(5.03±1.31)×109 L·mol-1·s-1, 3C60-DE*为(3.53±0.87)×109 L·mol-1·s-1), 而寿命增加了(3C60*为(12.0±2.6) μs, 3C60-DE*为(18.0±3.3) μs), 这可能是C60分子上连接了地塞米松分子后减小了C60球之间碰撞的几率所致.     

Is This a Chemical Bond? A Theoretical Study of Ng2@C60 (Ng=He,Ne, Ar,Kr, Xe)

Quantum-chemical calculations using DFT (BP86) and ab initio methods (MP2, SCS-MP2) have been carried out for the endohedral fullerenes Ng2@C60 (Ng=He-Xe). The nature of the interactions has been analyzed with charge- and energy-partitioning methods and with the topological analysis of the electron density (Atoms-in-Molecules (AIM)). The calculations predict that the equilibrium geometries of Ng2@C60 have D3d symmetry when Ng=Ne, Ar, Kr, while the energy-minimum structure of Xe2@C60 has D5d symmetry. The precession movement of He2 in He2@C60 has practically no barrier. The Ng--Ng distances in Ng2@C60 are much shorter than in free Ng2. All compounds Ng2@C60 are thermodynamically unstable towards loss of the noble gas atoms. The heavier species Ar2@C60, Kr2@C60, and Xe2@C60 are high energy compounds which are at the BSSE corrected SCS-MP2/TZVPP level in the range 96.7-305.5 kcal mol(-1) less stable than free C60+2 Ng. The AIM method reveals that there is always an Ng--Ng bond path in Ng2@C60. There are six Ng--C bond paths in (D3d) Ar2@C60, Kr2@C60, and Xe2@C60, whereas the lighter D3d homologues He2@C60 and Ne2@C60 have only three Ng--C2 paths. The calculated charge distribution and the orbital analysis clearly show that the bonding situation in Xe2@C60 significantly differs from those of the lighter homologues. The atomic partial charge of the [Xe2] moiety is +1.06, whereas the charges of the lighter dimers [Ng2] are close to zero. The a2u HOMO of (D3d) Xe2@C60 in the 1A1g state shows a large mixing of the highest lying occupied sigma* orbital of [Xe2] and the orbitals of the C60 cage. There is only a small gap between the a2u HOMO of Xe2@C60 and the eu LUMO and the a2u LUMO+1. The calculations show that there are several triplet states which are close in energy to each other and to the 1A1g state. The bonding analysis suggests that the interacting species in Xe2@C60 are the charged species Xe2q+ and C60q-, where 1相似文献   

CuxC60薄膜紫外-可见吸收光谱研究

近来,有关C60的研究主要集中在有关晶格动力学、电子结构和MxC60（M代表碱金属或碱土金属）的超导电性研究。但由于MxC60在大气中不能稳定存在,制约了MxC60的深入研究和实际应用。最近,Masterov等人报导了他们对Cu/C60的超导特性研究,认为其转变温度Tc在80－120K之间,这个转变温度比现有的MxC60的转变温度Tc-40K）要高得多,但有关更进一步的研究未见报导,因此,我们拟对CuxC60体系作较为详尽的研究,这对于进一步研究其超导机理是有必要的,本工作是在成功地制备了CuxC60薄膜的基础上,对其紫外－可见吸收光谱进行了初步的研究。定性地分析了CuxC60薄膜的电子结构,利用XPS谱分析了CuxC60薄膜中Cu的化学价态。     

Detection of Hydrogen Peroxide and Glucose Based on Immobilized C60‐Catalase Enzyme

The interaction between fullerene C60 and catalase enzyme was studied with a fullerene C60‐coated piezoelectric (PZ) quartz crystal sensor. The partially irreversible response of the C60‐coated PZ crystal sensor for catalase was observed by the desorption study, which implied that C60 could chemically react with catalase. Thus, immobilized fullerene C60‐catalase enzyme was synthesized and applied in determining hydrogen peroxide in aqueous solutions. An oxygen electrode detector with the immobilized C60‐catalase was also employed to detect oxygen, a product of the hydrolysis of hydrogen peroxide which was catalyzed by the C60‐catalase. The oxygen electrode/C60‐catalase detection system exhibited linear responses to the concentration of hydrogen peroxide and amount of immobilized C60‐catalase enzyme that was used. The effects of pH and temperature on the activity of the immobilized C60‐catalase enzyme were also investigated. Optimum pH at 7.0 and optimum temperature at 25 °C for activity of the insoluble immobilized C60‐catalase enzyme were found. The immobilized C60‐catalase enzyme could be reused with good repeatability of the activity. The lifetime of the immobilized C60‐catalase enzyme was long enough with an activity of 93% after 95 days. The immobilized C60‐catalase enzyme was also applied in determining glucose which was oxidized with glucose oxidase resulting in producing hydrogen peroxide, followed by detecting hydrogen peroxide with the oxygen electrode/C60‐catalase detection system.     

Piezoelectric crystal/surface acoustic wave biosensors based on fullerene C60 and enzymes/antibodies/proteins

The development of piezoelectric (PZ) quartz crystal and surface acoustic wave (SAW) biosensors based on fullerene C60 and immobilized C60-enzymes/antibodies/proteins for the detection of various biological species are reported. The C60 coated piezoelectric crystal sensors can be applied to the study of interactions between fullerene C60 and some biological species, such as enzymes, antibodies, proteins and heparin. The partial irreversible responses for some biospecies from C60 molecules were observed by the desorption study which implied that C60 could chemically react with these biological species. Thus, immobilized biological species, e.g. C60-GOD, C60-catalase, C60-urease, C60-lipase, C60-anti IgG, C60-heparin, C60-Hb, C60-Mb and C60-anti-Hb were successfully prepared. The immobilized C60-GOD, C60-catalase, C60-urease, C60-anti-IgG and C60-anti-Hb were employed as adsorbents onto quartz crystal of various piezoelectric biosensors to detect glucose, H₂O₂, urea, IgG, and hemoglobin respectively. The immobilized C60-lipase was applied to distinguishably catalyze the hydrolysis of some optical isomers such as L- and D-phenyalanine methyl ester and to determine these optical isomers. The immobilized C60-heparin was employed as a good inhibitor for blood clotting like solvated heparin. The H₂O₂ bio-sensor was set up with the immobilized C60-catalase to detect oxygen, the product of the hydrolysis of H₂O₂ by C60-catalase. The immobilized C60-GOD enzyme piezoelectric glucose sensor exhibited a good sensitivity and a good lower limit for glucose. A piezoelectric crystal urea biosensor based on immobilized C60-urease was also prepared to detect urea. Comparison between solvated and immobilized enzymes used for biosensors was also made. The C60-anti IgG or C60-anti-Hb coated IgG piezoelectric crystal sensors exhibited good sensitivity, selectivity and repeatability for IgG or hemoglobin. Fullerene C60-Hb and C60-myoglobin (C60-Mb) coated surface acoustic wave (SAW) immunosensors were prepared to detect the anti-hemoglobin (anti-Hb) and anti-myoglobin (anti-Mb) antibody, respectively. An electrochemical SAW (ESAW) detection system was also developed to detect glucose in aqueous solutions.     

Phase Behavior of Oleyl Oleate with Nonionic Surfactants

Oleyl oleate (OE), a liquid wax ester, has been reported as a potential raw material for cosmetic and pharmaceutical uses but little is known about its phase behavior in ternary systems. Two types of nonionic surfactants were selected, namely, Tween‐60 (T60) and Span 20 (S20). Phase diagrams of OE/T60/water and OE/S20/water systems were constructed at 25.0±0.5°C. Ternary phase diagrams of OE/T60∶S20 (20∶80 and 60∶40)/water systems were then constructed at the same temperature. The ratios of 80∶20 and 60∶40 of T60∶S20 were selected due to different solubility points of the surfactants in water. The results showed that the oleyl oleate with mixed surfactants system, OE/T60∶S20 (20∶80 and 60∶40)/water, gave better performance than the individual surfactant systems. The high percent of T60 of 80∶20 in the T60∶S20 system contributes to enlargement of the isotropic region. In contrast, by increasing the percent of S20 of 60∶40 in T60∶S20 contributes to a larger liquid crystalline region.