~(64)Cu-NOTA-Herceptin的设计、活性测定及肿瘤靶向分子显像研究

利用双功能螯合剂2-[(4-异硫氰基苯基)甲基]-1,4,7-三氮杂环九烷-1,4,7-三乙酸(NCS-Bz-NOTA)对Herceptin单抗表面的氨基进行修饰获得了NOTA-Herceptin,通过基质辅助激光解吸电离飞行时间质谱(MALDI-TOF)对该偶联物进行了表征.利用酶联免疫吸附测定了偶联前后Herceptin抗体效价的改变.利用新型正电子核素~(64)Cu标记,获得可用于肿瘤放射靶向精准诊疗的~(64)Cu-NOTA-Herceptin探针,其标记率为90%,放化纯度98%,比活度185 MBq/nmol.分别进行了该探针在HER2过表达胃癌细胞NCI-N87及HER2低表达胃癌细胞BGC823等肿瘤细胞中的摄取实验,测定了该探针的肿瘤特异性.建立了荷人胃癌BGC823裸鼠模型,通过微型正电子断层显像(Micro-PET)设备观察了探针在模型动物体内的代谢情况:在静脉注射7.4 MBq~(64)Cu-NOTA-Herceptin探针后,分别于4和60 h进行正电子断层显像(PET)的显像,观察到其在肿瘤部位的摄取有所富集,且随着代谢时间的延长,肝脏部位摄取得到明显降低.研究结果表明,~(64)Cu-NOTAHerceptin探针有望应用于肿瘤放射性靶向诊疗.     

Free energies for degradation reactions of 1,2,3-trichloropropane from ab initio electronic structure theory

Electronic structure methods were used to calculate the gas and aqueous phase reaction energies for reductive dechlorination (i.e., hydrogenolysis), reductive β-elimination, dehydrochlorination, and nucleophilic substitution by OH? of 1,2,3-trichloropropane. The thermochemical properties ΔH(f)°(298.15 K), S°(298.15 K, 1 bar), and ΔG(S)(298.15 K, 1 bar) were calculated by using ab initio electronic structure calculations, isodesmic reactions schemes, gas-phase entropy estimates, and continuum solvation models for 1,2,3-trichloropropane and several likely degradation products: CH3?CHCl?CH2Cl, CH2Cl?CH2?CH2Cl, C?H2?CHCl?CH2Cl, CH2Cl?C?H?CH2Cl, CH2═CCl?CH2Cl, cis-CHCl═CH?CH2Cl, trans-CHCl═CH?CH2Cl, CH2═CH?CH2Cl, CH2Cl?CHCl?CH2OH, CH2Cl?CHOH?CH2Cl, CH2═CCl?CH2OH, CH2═COH?CH2Cl, cis-CHOH═CH?CH2Cl, trans-CHOH═CH?CH2Cl, CH(═O)?CH2?CH2Cl, and CH3?C(═O)?CH2Cl. On the basis of these thermochemical estimates, together with a Fe(II)/Fe(III) chemical equilibrium model for natural reducing environments, all of the reactions studied were predicted to be very favorable in the standard state and under a wide range of pH conditions. The most favorable reaction was reductive β-elimination (ΔG(rxn)° ≈ ?32 kcal/mol), followed closely by reductive dechlorination (ΔG(rxn)° ≈ ?27 kcal/mol), dehydrochlorination (ΔG(rxn)° ≈ ?27 kcal/mol), and nucleophilic substitution by OH? (ΔG(rxn)° ≈ ?25 kcal/mol). For both reduction reactions studied, it was found that the first electron-transfer step, yielding the intermediate C?H2?CHCl?CH2Cl and the CH2Cl?C?H?CH2Cl species, was not favorable in the standard state (ΔG(rxn)° ≈ +15 kcal/mol) and was predicted to occur only at relatively high pH values. This result suggests that reduction by natural attenuation is unlikely.     

黄芪药渣中阿拉伯木聚糖(AX-Ⅰ-1)的提取纯化、结构分析及体外抗氧化作用

黄芪药渣经分级提取,再通过二乙氨乙基(DEAE)-纤维素52阴离子交换柱层析和Sephacryl S-400HR凝胶柱层析分离纯化,得到4个多糖组分AX-Ⅰ-1~AX-Ⅰ-4.对多糖AX-Ⅰ-1的理化性质和结构进行研究发现,AX-Ⅰ-1含有鼠李糖、阿拉伯糖、木糖、甘露糖、葡萄糖和半乳糖(摩尔比为0.006∶14.113∶8.284∶0.116∶0.468∶1),主链由阿拉伯糖和木糖通过β-(1→2),(1→3)和(1→4)苷键组成,支链由(1→4)βArap,(1→3)βGalp和(1→2)βMan组成,非还原末端由αRhap,βGclp和βGalp组成.对多糖AX-Ⅰ-1~AX-Ⅰ-4的抗氧化研究结果表明,这4个组分对羟基自由基、超氧阴离子自由基和1,1-二苯基-2-三硝基苯肼(DPPH)自由基均有一定的清除作用;当浓度为0.1 mg/m L时,多糖AX-Ⅰ-2~AX-Ⅰ-4对超氧阴离子的清除率是阳性对照维生素C(Vc)的2倍.     

Antifungal effect of the essential oil of Thymus broussonetii Boiss endogenous species of Morocco

The aim of the study was to determine the antifungal effects of the essential oil of Thymus broussonetii Boiss (EOT), an endemic plant in Morocco against Candida albicans, Aspergillus fumigatus and the dermatophytes. EOT was extracted by steam distillation. A suspension of up to 500?μL of C. albicans at a concentration of 10??CFU?mL?1 and A. fumigatus at a concentration of 101??spores?mL?1 were inhibited by 20?μL of EOT incorporated in tubes containing 4 mL of Sabouraud broth. In Sabouraud-chloramphenicol agar slants containing different concentrations of essential oil, 5?×?10? A. fumigatus spores were inhibited by 6?μL (0.0015?mL?mL?1) of the EOT. It has shown good anti-C. albicans and anti-A. fumigatus activity. All the dermatophytes tested were inhibited by 3?μL (0.00075?mL?mL?1) of EOT; the latter has the potential to be a good alternative to the conventional antifungal drugs which are usually expensive and with high toxicity.     

Electrogenerated chemiluminescence in mechanistic investigations of electroorganic reactions: Part III. Reduction of some disulfides at the dropping mercury electrode

In the simultaneous cathodic reduction of diphenyl disulfide (Ph?S?S?Ph) or dibenzoyl disulfide (Ph?CO?S?S?CO?Ph) and a series of fluorescent aromatic hydrocarbons A at the dropping mercury electrode in dimethylformamide the emission of A is observed. This electrogenerated chemiluminescence (ECL) originates from the electron transfer between A^? and the radicals Ph?S or Ph?COS, which are formed in a one-electron reductive cleavage of the disulfide bond by A^?. As an intermediate the anion radical Ph?S?S?Ph^? or Ph?CO?S?S?CO?Ph^? is assumed. In the case of Ph?S?S?Ph the ECL intensity is enhanced by proton donors (water or benzoic acid), which increase the cleavage rate of Ph? S?S?Ph^? in an electrophilic attack by the proton. The relatively negative threshold reduction potential of A (?1.4 to ?1.6 V) for the ECL in comparison with the half-wave potential (?0.85 V) supports a mercury-assisted heterogeneous reduction mechanism of Ph?S?S?Ph. The intensity-potential curves and the intensity—time curves at the mercury drop were measured for different concentrations of Ph?S?S?Ph and A and for different mercury pressures. No luminescence could be detected with o,o′-dinitrodiphenyl disulfide and diethyl disulfide.     

Chemical composition of essential oil and in vitro antioxidant activities of the essential oil and methanol extracts of Eucalyptus loxophleba

This study was designed to examine the chemical composition of the essential oil and the antioxidant activity of the essential oil and methanol extracts of Eucalyptus loxophleba Benth. subsp. The chemical composition of the essential oil of the leaves of E. loxophleba was analysed by GC and GC/MS. The main constituents of the oil were found to be 1,8-cineole (39.4%), methyl amyl acetate (19.8%) and aromadendrene (10%). Antioxidant activities of the samples were determined by two different test systems namely DPPH and β-carotene/linoleic acid. In the DPPH system, the highest radical-scavenging activity was shown by the polar subfraction of the methanol extract (15.2?±?1.7?μg?mL?1). Also, in the second case, the inhibition capacity (%) of the polar subfraction (94.1?±?1.3) was found to be stronger. In addition, the amounts of total phenol components in the polar subfraction (273.0?±?2.6?μg?mg?1) and nonpolar subfraction (146.3?±?2.5?μg?mg?1) were determined.     

反式-/顺式-1,4-聚异戊二烯共混体系的结晶动力学

采用差示扫描量热(DSC)法对反式-/顺式-1,4-聚异戊二烯共混体系的等温及非等温结晶动力学进行了研究,分别采用Avrami方程和莫志深法对其动力学参数进行了解析.研究结果表明,在反式-/顺式-1,4-聚异戊二烯共混体系的等温及非等温结晶过程中,顺式-1,4-聚异戊二烯(CPI)组分的存在会降低反式-1,4-聚异戊二烯(TPI)组分的结晶速率;在等温结晶过程中,CPI组分会提高TPI组分自身的结晶度;而非等温结晶过程中,CPI则提高了共混物中β晶型的相对含量.     

Evaluation of different light-curing lamps

The aim of this study has been to evaluate light-curing composites polymerization quality carried out by halogen and new-diode lamps through the thermal analysis (TG?CDTA). Samples have been polymerized at 3?C20?C40?C60?s by halogen lamp and 1?C3?C6?C9?s by new-diode lamp. The TG/DTA analysis shows that different light-curing times affect the degree of conversion of the composite, since by increasing the curing time the quantity of the monomer that has not reacted (residual) decreases. The new-diode lamp, according to the manufacturer, can cure composite restorations in few seconds; but at the conditions used in this study, the samples cured by the halogen lamp at the standard times of exposure, compared to the samples cured in few seconds by the new-diode lamp, show a lower mass loss.     

微波消解和电感耦合等离子体发射光谱法同时测定煤灰中的14种元素

应用微波消解和电感耦合等离子体发射光谱法同时测定煤灰中的常量、少量和微量元素Si、Al、Ca、Fe、Mg、Ti、K、Ba、Mn、V、Pb、Cr、Cu和Zn。考察了微波消解体系和消解条件，0．1g煤灰用10mL硝酸和1mL氢氟酸分解，加入10mL4％硼酸溶液分解氟化物沉淀。用本法测定煤飞灰标准参考物质的结果与标准值一致。方法准确，快速，回收率为94．2％～102．3％；RSD均小于5％。     

In vitro antimycobacterial activity and HPLC-DAD screening of phenolics from Ficus benjamina L. and Ficus luschnathiana (Miq.) Miq. leaves

The total phenolic content (Folin-Ciocalteu) of the leaves of Ficus benjamina and Ficus luschnathiana was evaluated and screened by HPLC-DAD. Ficus luschnathiana crude extract (CE) presented phenolic content higher than that of F. benjamina (149.92?±?3.65 versus 122.63?±?2.79?mg of GAE). Kaempferol (1.63?±?0.16?mg?g(-1) dry weight of CE) and chlorogenic acid (17.77?±?0.57?mg?g(-1) of butanolic fraction) were identified and quantified in F. benjamina, whereas rutin (1.39?±?0.20?mg?g(-1)), caffeic (1.14?±?0.13?mg?g(-1)) and chlorogenic (3.73?±?0.29?mg?g(-1)) acids were quantified in the CE of F. luschnathiana. Additionaly, rutin (15.55?±?1.92?mg?g(-1)) and quercetin (3.53?±?0.12?mg?g(-1)) were quantified in ethyl acetate and butanolic fractions, respectively. Antimycobacterial activity of CEs and fractions was evaluated against Mycobacterium smegmatis by broth microdilution method. Ethyl acetate fraction from F. benjamina and n-butanol fraction from F. luschnathiana displayed the highest inhibitory activity (MIC?=?312.50?μg?mL(-1) and 156.25?μg?mL(-1), respectively). Further studies are required to identify the compounds directly related to antimycobacterial activity.     

Site‐Selective Remote Radical C−H Functionalization of Unactivated C−H Bonds in Amides Using Sulfone Reagents

A general and practical strategy for remote site‐selective functionalization of unactivated aliphatic C?H bonds in various amides by radical chemistry is introduced. C?H bond functionalization is achieved by using the readily installed N‐allylsulfonyl moiety as an N‐radical precursor. The in situ generated N‐radical engages in intramolecular 1,5‐hydrogen atom transfer to generate a translocated C radical which is subsequently trapped with various sulfone reagents to afford the corresponding C?H functionalized amides. The generality of the approach is documented by the successful remote C?N₃, C?Cl, C?Br, C?SCF₃, C?SPh, and C?C bond formation. Unactivated tertiary and secondary C?H bonds, as well as activated primary C?H bonds, can be readily functionalized by this method.     

The Synthesis of Chitosan Decorated Reduced Graphene Oxide‐Ferrocene Nanocomposite and its Application in Electrochemical Detection Rhodamine B

Chitosan (CS) decorated reduced graphene oxide‐Ferrocene nanocomposite (RGO?Fc?CS) was synthesized by a one‐pot reaction. In the synthesis process of RGO?Fc?CS, GO?Fc was successfully self‐assembled via the π–π interaction, which had the features of large surface area and the high load. Then GO‐Fc and CS linked via one‐pot under alkaline conditions. The FT?IR, TGA, SEM were employed to characterize the successful synthesis of RGO?Fc?CS composites. A miniature electrochemical system was fabricated by RGO?Fc?CS modified glassy carbon electrode (expressed as RGO?Fc?CS/GCE) for the sensitive detection of RhB enantiomers via DPV. Electrochemical results revealed that the RGO?Fc?CS/GCE exhibited high molecular recognition toward RhB. Due to the synergy between the RGO?Fc and CS, the RGO?Fc?CS/GCE showed a linear range of 0.001–70 μM with a LOD of 0.5 nM, indicating that RGO?Fc?CS/GCE has broad application prospects to simplify monitor RhB real‐time.     

Substituent effects in cation-π interactions: a unified view from inductive, resonance, and through-space effects

The quantification of inductive (I), resonance (R), and through-space (TS) effects of a variety of substituents (X) in cation-π interactions of the type C?H?X···Na? is achieved by modeling C?H?-(Φ?)(n)-X···Na? (1), C?H?-(Φ?)(n)-X···Na? (2), C?H?-(Φ(2perpendicular))(n)-X···Na? (2'), and C?H? ···HX···Na? (3), where Φ? = -CH?CH?-, Φ? = -CHCH-, Φ(2perpendicular) indicates that Φ? is perpendicular to the plane of C?H?, and n = 1-5. The cation-π interaction energies of 1, 2, 2', and 3, relative to X = H and fitted to polynomial equations in n have been used to extract the substituent effect E?1, E?2, E?(2'), and E?3 for n = 0, the C?H?X···Na? systems. E?1 is made up of inductive (E(I)) and through-space (E(TS)) effects while the difference (E?2 - E?(2')) is purely resonance (E(R)) and E?3 is attributed to the TS contribution (E(TS)) of the X. The total interaction energy of C?H?X···Na? is nearly equal to the sum of E(I), E(R), and E(TS), which brings out the unified view of cation-π interaction in terms of I, R, and TS effects. The electron-withdrawing substituents contribute largely by TS effect, whereas the electron-donating substituents contribute mainly by resonance effect to the total cation-π interaction energy.     

Palladium‐Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

Palladium on carbon catalyzes C?O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by alcohols (R?OH) in H₂. The aromatic C?O bond is cleaved by reductive solvolysis, which is initiated by Pd‐catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with alcohols to form a ketal, which generates 1‐cyclohexenyl?O?R by eliminating phenol or an alkanol. Subsequent hydrogenation leads to cyclohexyl?O?R.     

Preparation of chlorofluoromethylene olefins via phosphine dechlorination of dichlorofluoromethyltris?dimethylamino?phosphonium chloride

The reaction of dichlorofluoromethyltris?dimethylamino?phosphonium chloride with tertiary phosphines provides a convenient preparation of the chlorofluoromethylenetris?dimethylamino?phosphonium ylide. This ylide provides reasonable yields of chlorofluoroolefins from aldehydes, activated ketones, non-activated ketones, and activated esters. The mechanism of phosphonium salt formation was shown to involve positive chlorine abstraction from CFCl₃ by (Me₂N)₃P followed by recombination of the intermediate ion pair. Dechlorination of the resulting dichlorofluoromethyltris?dimethylamino?phosphonium chloride by triphenylphosphine gave an olefinating solution of reasonable stability. In contrast, the solution obtained by dechlorination of the phosphonium salt by tris?dimethylamino?-phosphine showed no stability.     

Determination of trace elements in Rheum moorcroftianum by AAS

Micro and macro elements such as Zn, Cu, Mn, Fe, Co, Na, K, Ca and Li were detected from Rheum moorcroftianum Royle, a plant used in folk medicines. Altitudinal and seasonal variation of these trace elements in cultivated and wild roots and leaves of R. moorcroftianum were quantified by atomic absorption spectroscopy. The highest concentrations of Zn, Cu, Mn, Fe, Co, Na, K, Ca and Li were found to be 376.0?±?0.9, 83.0?±?4.6, 322.0?±?6.0, 920.0?±?1.9, 72.0?±?1.5, 402.0?±?7.8, 10,235.0?±?7.0, 12,336.0?±?2.6 and 59.9?±?0.3 mg?kg(-1), respectively, in all the samples analysed.     

Electron Capture Dissociation of Disulfide, Sulfur–Selenium, and Diselenide Bound Peptides

To examine the electron capture dissociation (ECD) behavior of disulfide (S?CS), sulfur?Cselenium (S?CSe), and diselenide (Se?CSe) bonds-containing peptides, a series of free cysteine (Cys) and selenocysteine (Sec) containing peptides were reacted to form interchain S?CS, S?CSe, and Se?CSe bonds, and then studied using ECD with Fourier transform ion cyclotron mass spectrometry (FTICR MS). These results demonstrate that the radical has higher tendency to stay at selenium rather than sulfur after the cleavage of Se?CS bonds by ECD. In addition, ?CSH (?C33), ?CS (?C32), and ?CS + H (?C31) small neutral losses were all observed from the cleavage of C?CS bonds of a disulfide bound peptide. Similar, but minor, fragments were also detected in S?CSe bound peptides. In contrast, the cleavage of C?CSe bonds of the Se?CSe species mainly forms fragments with neutral loss of ?CSe + H (?C78.90868), and the radical tends to stay on the selenium of its corresponding complementary pair. Although the electron affinities of S atom (2.07?eV) and Se atom (2.02?eV) are very close; they have very different reactivity towards electrons. The replacement of sulfur with selenium greatly increases the electron affinities of S?CSe and Se?CSe bonds comparing to S?CS bonds (with an increase of electron affinity by about 0.20?eV by replacing a sulfur with a selenium) (Int J Quantum Chem 110:513-523, 2010), which in turn leads to different ECD fragmentation behavior and mechanisms. Our results are in good agreement with previously published ab initio calculations on Se?CSe compounds by other groups.     

Phosphor(III)- Thiohalogenide: SP?F und SP?Br. Massenspektrometrische Untersuchungen

Phosphorus(III) Thiohalides: Sd?P? F and S?P? Br. Mass Spectrometric Investigations The compounds S?P? F and S?P? Br are formed by reaction of P(S)FBr₂ and P(S)Br₃, respectively, with silver at temperatures of about 800 K. S?P? Br is also formed by pyrolysis of P(S)Br₃ at temperatures above 298 K. Mass spectrometric equilibrium measurements lead to the heat of formation of S?P? F: ΔH°₂₉₈(SPFg) = ?260.8 kJ/mol.     

Structure,stability, and aromaticity of M?SubPc (MB,Al, and Ga): Computational study

A theoretical investigation on the structure, stability, and aromaticity of M‐subphthalocyanine (M? SubPc; M?B, Al, and Ga) was performed at the B3LYP/6‐31+G*//B3LYP/6‐31G* level. The comparison between M? SubPc and the corresponding M? phthalocyanine (M? Pc) was considered. The geometry optimization of the M? SubPc shows that in the Al? SubPc and Ga? SubPc, the steric repulsions among the three azacoupled isoindole moieties increase, as to their macrocycles tend to be far from planarity. The binding energies of Cl? M … aza‐coupled isoindole corrected by the basis set superposition error (BSSE), and the nucleus‐independent chemical shift (NICS) values at the ring center, which are a simple and effective local aromaticity probe, were calculated. The results show that Al? SubPc is less stable than both B? SubPc and Al? Pc for larger steric repulsion, smaller binding energy, and weaker aromaticity. In the same way, Ga? SubPc is less stable than both B? SubPc and Ga? Pc. In addition, the ring expansion reactivity occurring in B? SubPc was confirmed by the global aromaticity mirrored by the electrophilicity index ω values. Therefore, the Al? SubPc and Ga? SubPc remain unknown, while the corresponding compounds Al? Pc and Ga? Pc are known experimentally. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Über Chalkogenolate. 149. Reaktion von Formamid mit Kohlenstoffdisulfid 3. N-Formyldithiocarbamidsäure H?CO?NH?CS?SH

On Chalcogenolates. 149. Reaction of Formamide with Carbon Disulfide. 3. N-Formyl Dithiocarbamic Acid H? CO? NH? CS? SH The reaction of a suspension of K[S₂C? NH? CO? H] in diethyl ether with a solution of HCl(g) in ether at ?15°C forms H? CO? NH? CS? SH. The acid has been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra.