Inhibition of DNA restrictive endonucleases and Taq DNA polymerase by trimalonic acid C60

Activities of trimalonic acid fullerene (TMA C_60) on DNA restrictive enzymatic reaction were investigated by using two restrictive endonucleases Hind III and EcoR I and plasmid pEGFP-N1 with single restric-tive site for both enzymes. Meanwhile, TMA C60 was also tested to clarify its effects on polymerase chain reaction (PCR) with the catalyst of Taq DNA polymerase and the template of plasmid pEGFP-N1. The products from restrictive reactions or PCR were detected by agarose gel electrophoresis. It was found that the product amounts from restrictive reactions or PCR decreased significantly with addition of TMA C60. The inhibition by TMA C60 was dose-dependent and IC50 values for reactions of Hind III, EcoR I and PCR were 16.3, 6.0 and 6.0 μmol/L, respectively. Addition of two scavengers of reactive oxygen species (ROS), L-ascorbic acid-2-phosphate ester magnesium and sodium azide at the con-centrations of 2―10 mmol/L did not antagonize the activities of TMA C60 against PCR and two restrictive reactions. However, increase of Taq DNA polymerase amounts in PCR system antagonized the activities of TMA C60. These data implied that TMA C60 was able to inhibit the activities of the three above-mentioned enzymes involved in DNA metabolism, and that this inhibition probably did not correlate to ROS.     

Tunable tribological properties in water-based lubrication of water-soluble fullerene derivatives via varying terminal groups

In this paper,three kinds of water-soluble fullerene derivatives were synthesized via electrophilic addition reaction and cycloaddition reaction,respectively.The chemical composition characterizations of these derivatives indicated the successful preparation of C60(OH)x,C60(C(COOH)2)x and C60(OH)x(NHCH2COOH)y fullerene derivatives.The aggregation and morphology characterizations showed that the three kinds of derivatives had an ideal spherical aggregating structures and excellent dispersibility in water,especially C60(OH)x and C60(C(COOH)2) x.The lubrication performance of the fullerene derivatives acted as lubricant additives were investigated at different concentrations in the range of 0-1 wt%.The results indicated that the addition of polyhydroxyl and carboxylic derivatives could improve the lubrication properties,which led to the reduction of wear to about 40% at most.It is attributed that the optimized substitutions of fullerene molecules may be of benefit to their distribution properties and lubricating behaviors in water based lubrication.     

Synthesis of fullerene hydrazine derivatives

C₆₀/C₇₀ mixture reacts with hydrazine hydrate catalysed by tetrabutylammonium bromide (TBAB) in the presence of air to afford fullerene hydrazine derivatives C₆₀(OH) _n (NHNH₂) _n and C₇₀(OH) _n (NHNH₂) _n , which are characterized by means of MS and FTIR. A possible reaction mechanism is discussed. Shen Shengwen: born in 1971, Master     

Biodistribution of fullerene derivative C60(OH)x(O)y

The biological behavior of fullerene derivatives shows their considerable potential application in medicine field. To understand the biodistribution of C₆₀ derivatives as drugs or drug carriers, a simple water-soluble derivative C₆₀(OH)_x(O)_y was labeled with^99mTc. A γ-counter and a single photo emission computed tomography (SPECT) were used to assess the biodistribution and metabolism of the labeled compound in mice and rabbits, respectively. The results showed that the compound could be absorbed rapidly by tissues, especially by coronal bone, breastbone, backbone, extremity honeycomb, liver and spleen. The clearance was slow from all tissues except for brain. The compound might be excreted through urine and enteron. The biodistribution shows some difference from that of Yamago et al. In this note, we discuss the possible reason leading to the difference. Further study is needed to find out to what extent the C₆₀ itself determines the biodistribution of derivatives.     

Ferric perchlorate-promoted reaction of [60]fullerene with β-keto esters

The ferric perchlorate-promoted reaction of [60]fullerene (C60) with ethyl 2-methylacetoacetate generates fullerenyl hemiketal as a mixture of trans and cis isomers,while the reaction with ethyl acetoacetate gives a C 60-fused dihydrofuran derivative.A possible reaction mechanism for the formation of these products is proposed.     

Theoretical study on photophysical property of C60M（CO）5 （M=Cr,Mo and W）

Configurations of three η2 models of transition-metal [60]fullerene derivatives C60M（CO）5（M=Cr, Mo and W） have been optimized at B3LYP/LanL2DZ level. On the basis of the optimized geometrical structures, their electronic spectra and the frequency dependence of third-order nonlinear optical polarizabilities γ in different optical processes of third-harmonic generation （THG）, electric-field-induced second-harmonic generation （EFISHG） and degenerate four-wave mixing （DFWM） are calculated by using TDB3LYP model based on LanL2DZ level coupled with the SOS （sum-over-state） method. The obtained results show that their electronic spectra have a red shift compared with that of [60]fullerene and different transition-metal functional groups added to C60 cage may result in different spectrum properties. For the three studied species, （η^2-C60）Mo（CO）5 has the largest third-order nonlinear optical polarizability.     

嘧啶环二炔氮桥C60衍生物的合成及非线性光学性质

合成了嘧啶环二炔氮桥C₆₀衍生物C₆₀NPD ,研究了在532nm、脉宽 8ns条件下的非线性光学特性。通过Z-扫描实验发现C₆₀NPD有很强的非线性吸收和非线性折射,并获得了三阶非线性光学系数χ⁽³⁾ 。同时也研究了光限幅特性，实验结果表明C₆₀NPD有较低的光限幅箝位值。     

In situ observation of C60（C（COOH）2）2 interacting with living cells using fluorescence microscopy

1 Introduction In recent years, studies on biological effects of thenanoscale materials have become the cornerstone of rapidly developed nanomedical and nanobiological technologies. Moreover, studies on the bio-effects when the different kinds of nanoscal…     

Transmission electron microscopy study on microstructure in Langmuir-Blodgett films of fullerene derivatives

Surface pressure-area isotherms of two C₆₀ derivatives, ethoxycarbonyldecylentfullerene and bis(ethoxycarbonyldecylene) fullerene, have been investigated. The molecular aggregation at the air-water interface was reduced and the transfer behavior to various substrates was enhanced as compared with those of pure C₆₀. Structural characterization of the LB films was carried out using high resolution transmission electron microscopy (HRTEM). The HRTEM images revealed regular stacking of the densest packed rows of molecules in the LB films.     

Manganese(III) acetate-mediated radical reaction of [60]fullerene with bromoacetic acid, 3-chloropropionic acid or 1-naphthylacetic acid

The manganese(III) acetate-mediated radical reaction of [60]fullerene (C₆₀) with three carboxylic acids, that is, bromoacetic acid, 3-chloropropionic acid, and 1-naphthylacetic acid, was investigated. The reaction of C₆₀ with bromoacetic acid in the presence of 4-(dimethylamino)pyridine afforded the anticipated C₆₀-fused lactone, while the reaction with 3-chloropropionic acid unexpectedly led to the formation of a novel C₆₀-fused lactone with the loss of one molecule of HCl. Interestingly, the reaction with 1-naphthylacetic acid under similar conditions gave both C₆₀-fused lactone and 1,4-adduct, yet each of them could be selectively obtained by controlling reaction conditions. It was also observed that the C₆₀-fused lactone bearing a bulky naphthyl group existed as two isomers.     

水溶性C60-脱氢枞胺衍生物的合成及生物活性

以C60-脱氢枞胺吡咯烷衍生物和C60-脱氢枞胺氮烯加成物为原料,通过两种不同的水性化途径分别合成了两种水溶性的C60-脱氢枞胺富勒醇衍生物和两种水溶性的C60-脱氢枞胺甘氨酸衍生物。产物经TEM、FT-IR、ESI-MS、1H NMR和HPLC等分析方法检测确认为目标产物,且为加成度不同的混合物。对合成出的4种水溶性C60-脱氢枞胺衍生物进行了生物活性测试。结果表明,4种水溶性C60-脱氢枞胺衍生物对rTaq DNA聚合酶和HIV-1反转录酶均表现出一定的抑制作用,对卵巢癌细胞株几乎不表现出抑制活性。     

Degradation of a fullerene end-capped polycaprolactone by lipase AK

Using titrimetric method, enzymatic behavior of lipase AK against fullerene end-capped polycaprolactone (C₆₀-PCL) was studied for the first time, compared with polycaprolactone (PCL). The results showed that degradation of both C₆₀-PCL and PCL by lipase followed Mechaelis-Menten equation, with the degradation parameters of PCL and C₆₀-PCL were 0.75 mg mL^–1 and 0.16 mg mL^–1 for Km, and 0.90 mL h^–1 and 0.43 mL h^–1 for Vmax, respectively. C₆₀-PCL had a slower degradation rate than PCL under the same conditions. These data indicated that the introduction of fullerene enabled PCL hard to be degraded by lipase.     

Photoluminescence of fullerene[60] in ultrathin ordered multilayers: The dissociation of molecular aggregation

The aggregation behavior of a substituted fullerene compound, 1-benzyl-2-hydro[60]fullerene (C₆₀-Be), in Z-type ultrathin ordered (e.g. LB) multilayers has been studied by UV-vis absorption, steady state and time-resolved fluorescence spectroscopies. The LB multilayers of pure C₆₀-Be showed J-aggregate formation, characterized by a large red-shift of two absorption peaks (ΔE∼2 098 cm¹ from 260→275 nm and ΔE∼1 076 cm^-1 from 328→340 nm, respectively). The main fluorescence emission bands were found at 710, 646, 603, 600 and 595 nm for pure (C₆₀-Be, mixed C₆₀-Be (molar percentage 50%, 25% and 20%. respectively) multilayers and monomeric C₆₀-Be in solution, respectively. The aggregates were dissociated by mixing with some inert materials. The fluorescence decay profiles of C₆₀-Be, mixed C₆₀-Be (molar percentage 50%, 25% and 20%, respectively) in LB films could be best-fitted by using a bi-exponential decay model.     

Formation of substitutional metallofullerenes by laser ablation of externally doped fullerenes C60M x (M=Sm, Pt, Ni and Rh)

Photofragmentation study of metal fullerides C₆₀M _x (M = Sm, Pt, Ni and Rh) by excimer laser ablation-TOF mass spectrometry shows that metallofullerenes C_2n M and C_2n+1M formed in both the positive and negative ionic modes. The isotopic distributions of the metallofullerenes C_2n M and C_2n+1M are consistent with the calculated spectra based on the natural abundance of isotopes of C and M, confirming the formation of metallofullerenes. The metal atom is supposed to be incorporated into the network of the fullerene cage to replace one carbon atom of the cage forming substitutional metallofullerene. Odd-numbered high carbon clusters are observed in our laser ablation study of all the metal fullerides in the negative ion channel. Evolution of mass spectrum with irradiation laser shots shows that the formation of the substitutionally doped fullerenes is closely related to the production of metal carbide (MC). The structures, as well as formation mechanism, of metallofullerenes C_2n+1M and C_2n M with even and odd numbers of total atoms respectively are discussed based on the structural optimization of the odd-numbered high carbon clusters.     

Synthesis of monosubstituted N-arylamidines by divalent diaminobisphenolate ytterbium complex catalyzed addition of amines to nitriles

Divalent ytterbium complex YbL^（ONNO）（THF）2 （L^（ONNO）= Me2NCH2CH2N（CH2-2-O-3,5-C6H2（^1Bu）2）2） （1） has first been found to serve as a catalyst for addition of amines to nitriles to give monosubstituted N-arylamidine in moderate to good yields. The aromatic amines and nitriles showed better activity. The outcome of the addition reaction was greatly affected by the structure of divalent ytterbium complexes. The reaction mechanism was proposed and the benzonitrile-coordinated divalent ytterbium phenoxide Yb（OAr）2（C6H5CN）（THF）2 （Ar = 2,6-di^tBu-4-MeC6H3） was isolated as one of the intermediates.     

纳米管TUC_4C_8(S)和纳米环TC_4C_8(S)的拓扑指数

化合物、材料和药物的生物化学性质与其分子结构有密切的关联,通过化学拓扑指数的计算可了解化合物的性质.作为一类重要的化学参数,Szeged指数和修改的Szeged指数并广泛用于各类化学与制药学工程应用中.通过边划分方法,给出纳米管TUC_4C_8(S)和纳米环TC4C8(S)的若干基于距离的拓扑指数.     

Kinetics of C2(a3Πu) radical reactions with NO, N2O, O2, H2 and NH3

Pulsed laser photolysis/laser-induced fluorescence (LP-LIF) is utilized to measure rate constants for C₂(a³Π_u) reactions with NO, N₂O, O₂, H₂ and NH₃. Multiphoton dissociation of C₂Cl₄ at 266 nm is employed for the generation of C₂(a³Π_u) radicals. The C₂(a³Π_u) concentration is monitored by the fluorescence of the (0, 0) band of the (d³Π_g&#8596;a³Π_u) transition at 516.5 nm. C₂(a³Π_u) removal rate constants for the reactions are determined as k_NO = (5.46 ± 0.10) × 10^-11 cm³ molecule^-1 s^-1 , k_N2O = (1.63 ± 0.20) × 10^-13 cm³ molecule^-1 s^-1 , k_N2O = (1.58 ± 0.16) × 10^-11 cm³ molecule^-1 s^-1, k_O2 = (5.92 ± 1.00) × 10^-14 cm³ molecule^-1 s^-1, k_H2< 1.0× 10^-14 cm³ molecule^-1 s^-1. Based on the data analysis and theoretical calculation, we suggest that the C₂(a³Π_u) reactions with H₂ and NH₃ proceed via the hydrogen abstraction mechanism, barriers exist at the entrance channel of the reactions of C₂(a³Π_u) with H₂ and NH₃.     

Low temperature thermodynamic study of the stable and metastable phases of vanadium

The low temperature thermodynamics of the stable phase of vanadium has been assessed by the polynomial and Debye models from the experimental data available in literature. By means of the con-strained nonlinear least squares curve fitting arithmetic,two sets of parameter values have been de-termined. Expressions of the thermodynamic functions Cp(T) and G(T)-H(298.15 K) at 0―298.15 K are presented. The low temperature thermodynamics of the metastable phase of vanadium can only be extrapolated by the Debye model. The expression of the thermodynamic function Cp(T) at 0―298.15 K is presented.