Facile and scalable synthesis of a highly hydroxylated water-soluble fullerenol as a single nanoparticle

A water-soluble polyhydroxylated fullerene, i.e. a fullerenol, with 44 hydroxyl groups and 8 secondary bound water molecules, C₆₀(OH)₄₄·8H₂O (estimated average structure), has been synthesized in a facile one step reaction from pristine C₆₀ by hydroxylation with hydrogen peroxide in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydroxide (TBAH), under organic/aqueous bilayer conditions. The fullerenol exhibited high water solubility, up to 64.9 mg/mL, under neutral (pH = 7) conditions. Dynamic light-scattering (DLS) analysis showed a narrow particle size distribution, of 1–2 nm, indicating that the fullerenol had high dispersion properties in water. The results of particle size analyses, which both focused on a single nanoregion and were conducted using a novel induced grating (IG) method and a scanning probe microscope (SPM), were consistent with the DLS results. A plausible reaction mechanism, which includes fullerene oxide intermediates detected by liquid chromatography-mass spectrometry (LC-MS), has been proposed.     

TEMPERATURE-DEPENDENT AGGREGATION STRUCTURES OF FULLERENE-BASED IONOMERS IN ELECTROLYTE SOLUTIONS

We have synthesized fullerene derivatives, C₆₀[CO(CH₂)₅O(CH₂)₄SO₃Na]₆ (FC₁₀S), which consists of a C₆₀ cage covalently bonded with six sulfonated arms for a high water solubility. We study the aggregation structures of the novel C60-derivatives in 0.1 M NaCl aqueous solutions by small angle X-ray scattering (SAXS). In the concentration range studied, 0.5 wt% to 2 wt %, the rod-like structure of FC₁₀S aggregates has a radius of 20 Å and a rod-length about 150 Å at 25°C, and the aggregation structure is insensitive to the concentration change. The aggregates, however, grow in length as the temperature increases, while the radius increases slightly with increasing temperature.     

Morphology-tailored synthesis of tungsten trioxide (hydrate) thin films and their photocatalytic properties

Tungsten trioxide hydrate (3WO(3)·H(2)O) films with different morphologies were directly grown on fluorine doped tin oxide (FTO) substrate via a facile crystal-seed-assisted hydrothermal method. Scanning electron microscopy (SEM) analysis showed that 3WO(3)·H(2)O thin films composed of platelike, wedgelike, and sheetlike nanostructures could be selectively synthesized by adding Na(2)SO(4), (NH(4))(2)SO(4), and CH(3)COONH(4) as capping agents, respectively. X-ray diffraction (XRD) studies indicated that these films were of orthorhombic structure. The as-prepared thin films after dehydration showed obvious photocatalytic activities. The best film grown using CH(3)COONH(4) as a capping agent generated anodic photocurrents of 1.16 mA/cm(2) for oxidization of methanol and 0.5 mA/cm(2) for water splitting with the highest photoconversion efficiency of about 0.3% under simulated solar illumination.     

Photocatalytic decomposition of acephate in irradiated TiO2 suspensions

In the present study, the photocatalytic degradation of acephate (O,S-dimethyl acetyl phosphoramidothioate ((CH(3)O)(CH(3)S)P(O)NHCOCH(3))) in aqueous TiO2 suspensions is extensively investigated, pertaining to the concentration of photocatalyst and substrate on degradation rate of acephate. It is found that the acephate can be degradated and mineralized. The high-degradation rate is obtained with 4 g/L concentration of TiO2. Moreover, Langmuir-Hinshelowood rate expression is employed for the degradation of acephate with adsorption constant and rate constant, i.e., 2.0 L/mmol and 0.6 mmol/(min L), respectively. The main target is to identify the products by a number of analytical techniques, such as HPLC, IC, ESR and GC-MS. Under acidic condition, the primary products are phosphorothioic acid, O,O',S-trimethyl ester (CH(3)O(CH(3)S)P(O)OCH(3)) and phosphoramidothioic acid, O,S-dimethyl ester (CH(3)O(CH(3)S)P(O)NH(2)), etc. It indicates that the decomposition of acephate begin from the destruction of C-N and P-N bonds. Subsequently, the P-S, P-O, P-C bonds may be oxidized gradually or simultaneously, and the final products such as CO(2), H(3)PO(4), were formed. About 100% sulfur atoms are transformed into SO(4)(2-) in 180 min, however; only 3% nitrogen atoms and 2% phosphorus atoms were transformed into NO(3)(-) and PO(4)(3-).     

Physical and chemical modification of distillery sludge for Pb(II) biosorption

The waste distillery sludge from sugar-cane industry was pretreated physically (boiled, heated and autoclaved) as well as chemically (HCl, H(2)SO(4), H(3)PO(4), NaOH, Ca(OH)(2), Al(OH)(3), C(6)H(6), HCHO, CH(3)OH and C1(2)H(25)OSO(3)Na (sodium dodecyl sulphate (SDS)) for assessing the comparative sorption capacity of untreated and modified distillery sludge for Pb(II) biosorption from aqueous solutions. Experiments were conducted in shake flasks on a batch basis to access the effect of different experimental parameters such as pH, biosorbent dosage, biosorbent size, initial Pb(II) concentration and contact time. The uptake capacity 'q' (mg/g) of untreated and pretreated distillery sludge was in following order: NaOH (51.29+/-1.21)>HCl (49.82+/-1.22)>HCHO (49.56+/-1.14)>H(2)SO(4) (47.71+/-1.20)>HgCl(2) (45.32+/-1.06)>Ca(OH)(2) (44.01+/-1.18)>MeOH (43.73+/-1.23)>C(6)H(6) (42.72+/-1.19)>H(3)PO(4) (42.01+/-1.17)>SDS (40.87+/-1.27)>autoclaved (40.23+/-1.24)>Boiled (39.95+/-1.19)>heated (38.87+/-1.32)>Al (OH)(3) (38.30+/-1.14)>untreated (37.76+/-1.21). In further parameter studies, the optimized biosorbent size was 0.250 mm at pH 5 and best dose was 0.05 g of biosorbent. The applicability of the Langmuir and Freundlich models for sorption process was tested and best fitted model was Langmuir with the coefficient of determination (R(2)) value, 0.97, the process followed second order kinetic mechanism.     

Preparation and photocatalytic activity of iron oxide-loaded potassium titanate layered compounds

Iron oxide-loaded hydrous potassium tetratitanate (K0.3Ti4O7.3(OH)1.7) compounds consisting of 1.48 wt% (sample 'B'), 1.87 wt% (sample 'C') and 5.60 wt% (sample 'D') of iron oxide were synthesized by suspending the K0.3Ti4O7.3(OH)1.7 (sample 'A') in Fe2(SO4)3 solution for 24 h, followed by washing several times with deionized water and then dried at 120 degrees C for 24 h. The K0.3Ti4O7.3(OH)1.7 was synthesized by refluxing the K2Ti4O9 x 2H2O in 1 M HNO3 solution. Band-gap energies of the K0.3Ti4O7.3(OH)1.7 and the iron oxide-loaded samples are 3.12 +/- 0.6 eV and 2.23 +/- 0.09 eV, respectively. Photooxidation activity towards methylene blue decomposition under fluorescence irradiation was found to decrease as follow: sample 'B' > sample 'C' > Sample 'A' > sample 'D' > commercial Fe2O3-Blank. The photoactivity under sunlight irradiation was found to decrease as follow: sample 'B' > sample 'A' > Sample 'C' > sample 'D' > commercial Fe2O3-Blank.     

Synthesis of a lithium-encapsulated fullerenol and the effect of the internal lithium cation on its aggregation behavior

A lithium-encapsulated fullerenol Li@C₆₀(OH)₁₈, as an example of a polar solvent-soluble endohedral fullerene derivative, has been synthesized and fully characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, UV spectroscopy, electron spin resonance (ESR) spectroscopy, matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF-MS), elemental analysis, thermogravimetric analysis, and inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and the particle size was determined using the induced grating (IG) method, and scanning probe microscopy. The encapsulated Li⁺ was clearly detected by ⁷Li NMR at very high field in the range −15 to −19 ppm, an intermediate lithium-encapsulated fullerenol was detected by MALDI-TOF-MS, and the molar ratio of lithium-encapsulated fullerenol to empty fullerenol was quantitatively determined to be 12:88 by ICP-AES. The solid-state ESR and particle size measurements using the IG method showed the characteristic anionic behavior with no external counter cations, in what can be called a “cation-encapsulated anion nanoparticle”, revealing the drastic differences between its properties and those of empty C₆₀(OH)₁₆.      

Fullerenol spin probe containing isoindoline nitroxide and porphyrin groups

A water-soluble fullerenol containing porphyrin and isoindoline nitroxide groups APTSPP-C₆₀(OH)₁₀-(TMIO)₃ was synthesized by the incorporation of 5-(4-amino-phenyl)-10,15,20-tris(4-sulfonatophenyl)-porphyrin (APTSPP) as a tumor-targeting group and 5-formyl-1,1,3,3-tetramethylisoindolin-2-yloxyl (FTMIO) into fullerenol C₆₀(OH)₁₁. This nonmaterial was further characterized by FT-IR, UV, MS, TEM, fluorescence, etc. and its properties in vitro were also evaluated. Electrochemical experiments indicated that APTSPP-C₆₀(OH)₁₀-(TMIO)₃ retained similar electrochemical properties and redox reaction mechanisms as 5-carboxy-1,1,3,3-tetramethylisoindolin-2-yloxyl (CTMIO). Electron paramagnetic resonance (EPR) spectra of APTSPP-C₆₀(OH)₁₀-(TMIO)₃ exhibited the hyperfine splittings and characteristic spectra of CTMIO, with typical nitroxide g-values and nitrogen isotropic hyperfine coupling constants. In vitro cytotoxicity assay showed APTSPP-C₆₀(OH)₁₀-(TMIO)₃ possessed low cytotoxicities to human renal tubular epithelial 293T cells and HepG-2 cells. Therefore APTSPP-C₆₀(OH)₁₀-(TMIO)₃ may be considered as a potential candidate for novel biological spin probe using EPR spectroscopy.     

Recovery of ammonium alum from waste solutions with a varying ratio of NH4 to Al in groundwater remediation after underground uranium leaching

Experiments with cooling crystallization of ammonium alum, (NH(4)Al(SO(4))2.12H(2)O), were performed with concentrated multicomponent acidic solutions (originating from underground uranium leaching in Stráz pod Ralskem area, Czech Republic, and containing as the principal components Al3+, NH4+, and SO4(2-) ions) as well as with similar solutions prepared in the laboratory. The yield of NH(4)Al(SO(4))2.12H(2)O crystals increased significantly with the increasing NH4+/Al3+ molar ratio, in accordance with pertinent solubility data. The purifying effect of crystallization was quantified by means of the distribution coefficients, characterizing the uptake of ionic impurities to alum crystals; the tendency of cationic impurities to crystallize with NH(4)Al(SO(4))2.12H(2)O decreased in the following order: K+ > Cr3+ >Na+ approximately Fe3+ >Mg2+ approximately Zn2+ >Fe2+. Additionally, gypsum (CaSO4.2H(2)O) solubilities at 25 degrees C, in mother liquors after NH(4)Al(SO(4))2.12H(2)O crystallization, were determined.     

The Solubility of Some Azafullerene Derivatives

Several fulleroaziridines, azafulleroids and chiral cage-opened ketolactams were synthesized from alkyl azides and C₆₀. Their solubility in various solvents was evaluated by HPLC. It depends both on the starting azide and the linker group. Moreover, the formation of two sp³ carbons (entries 2) and then of carbonyl derivatives (entries 3) induces a decrease of the polarizability of the C₆₀ moiety and an enhancement of the solubility in lipophilic solvents.     

纳米级碳酸钙粉末材料的制备研究

利用CO2-Ca(OH)2-H2O体系制备了纳米级碳酸钙粒子,探讨了无添加剂制备过程中CO2流量对粒子大小和分散性能的影响.碳化前,在体系中引入了能与Ca2 生成沉淀的化合物,研究了硅酸钠、草酸钾、硼酸等对促进碳酸钙成核的效果.利用TEM、XRD和粒度分布测试对产品进行了表征.结果表明:CO2的最佳流量为6～7mL/s.添加草酸钾后制得的产品,具有粒度均匀、分散性好等优点,粒子的平均粒径为60～70 nm.     

Low Temperature Synthesis of Single-crystal Alpha Alumina Platelets by Calcining Bayerite and Potassium Sulfate

Single-crystal alpha alumina (α-Al2O3) platelets were synthesized by calcining a powder mixture of bayerite (α-Al(OH)3) and potassium sulfate (K2SO4) at 900℃. The crystalline phase evolutions and morphologies of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The synthesized samples mainly consisted of single-crystal α-Al2O3 platelets with a diameter of 0.5-1.5 μm and a thickness of 50-150 nm. Moreover, with 3, 5, and 8 wt% (referred to the obtained alumina) α-Al2O3 seeds adding into the powder mixture of bayerite and potassium sulfate, the average diameter of α-Al2O3 platelets can be reduced to 450, 240, and 220 nm, respectively. It is found that the sequence of the phase transformation is the bayerite (α-Al(OH)3) → boehmite (γ-AlOOH) →γ-Al2O3 →α-Al2O3. Further analysis indicated that K2SO4 can promote the phase transformation from γ-Al2O3 to α-Al2O3 and the formation of single-crystal α-Al2O3 platelets might be attributed to the liquid phase K3Al(SO4)3.     

Cytotoxicity and TNF-alpha secretion in RAW264.7 macrophages exposed to different fullerene derivatives

Fullerene derivatives have been reported as potential nanomedicines, however the role of surface chemical modification on the biological effects remains unclear. In this study, five kinds of water soluble C60 derivatives with different surface chemical modification, C60-(OH)20 (HFD), C60-(beta-Ala)10.1 (AFD), C60-(Lys)8.7 (KFD), C60-(Arg)8.6 (RFD) and C60-(NH(CH2)2NH2)8.8 (NFD) were synthesized. Their cytotoxicity as well as TNF-alpha secretions were evaluated in RAW264.7 macrophage cell line. The results show that no significant cytotoxicity can be observed upon 24 h exposure to C60 derivatives at less than 50 microg/mL. However, higher concentration (> 100 microg/mL) of these C60 derivatives decreases the proliferation of RAW264.7. The cytotoxicity of these fullerene derivatives is probably through the apoptosis pathway, while the extent of cytotoxicity varies with the different surface charges. Higher celluar uptake of HFD was observed in RAW264.7 cells than AFD, which correlates with the more toxic effect of HFD over AFD. The secretion of cytokine tumor necrosis factor alpha (TNF-alpha) was determined to evaluate the immunostimulating activity of these fullerene derivatives. The data show that the fullerene derivatives with negative surface charges secrete more TNF-alpha, whereas derivatives with positive charges show insignificant effect. The possible influence of various surface charge property on the observed biological effects is discussed.     

层状硫化锌的溶剂热法制备

以乙酸锌Zn(CH3COO)2.2H2O为锌源、硫脲SC(NH2)2为硫源、水与乙二胺的混合溶液为反应溶剂、十二烷基磺酸钠C12H25SO3Na形成的胶束为模板,利用溶剂热法制备了具有层状微观形貌的ZnS粉体材料。利用XRD、SEM、EDS等测试手段进行表征,结果表明,所得ZnS粉体材料结晶良好,层状形貌明显;层状ZnS粉体材料在435nm附近有较宽的发射峰,且发光性能明显优于球状ZnS粉体材料。     

The Solubility of Some Azafullerene Derivatives

Abstract

Several fulleroaziridines, azafulleroids and chiral cage-opened ketolactams were synthesized from alkyl azides and C₆₀. Their solubility in various solvents was evaluated by HPLC. It depends both on the starting azide and the linker group. Moreover, the formation of two sp³ carbons (entries 2) and then of carbonyl derivatives (entries 3) induces a decrease of the polarizability of the C₆₀ moiety and an enhancement of the solubility in lipophilic solvents.     

Synthesis of Fullerenols from Halofullerenes

Halogenated fullerenes were used as reagents to prepare fullerenols. Depending on reaction conditions two types of substances (complex mixtures of products with average compositions C₆₀O_nH_m, n=10-26, m=14-30 and C₆₀O_nH_mM_k, M=K, Na; n=17-24, m=16-28, k=3-8) possessing essentially different water solubility were obtained. Highly soluble metal-containing species are most likely ionic compounds similar to metal derivatives of alcohols-alcoholates. An electron withdrawing effect of the carbon cage could make alkali metal fullerenolates (C₆₀(OH)_x(OM)_y) inert towards hydrolysis. Halogens were selectively substituted when fullerene bromides and chlorides were treated with silver trifluoroacetate. Fullerenol esters C₆₀(OOCCF₃)_n formed were then hydrolyzed to form C₆₀(OOCCF₃)_x(OH)_y. Attempts to cleave all ester groups in C₆₀(OOCCF₃)_x(OH)_y failed in acidic media, while alkaline hydrolysis was accompanied by unselective polyhydroxylation of the fullerene cage.     

CH3COONa·3H2O相变储能性能研究

三水醋酸钠(CH3COONa.3H2O)由于潜热较高而常作为相变储能材料被众多学者研究;而其适宜的熔点,使其能适用于家用热水储能系统等。然而,三水合醋酸钠在相变过程中存在着严重的过冷和相分离的问题。本文以三水合醋酸钠作为相变基体材料,经研究、比较分别以羧甲基纤维素、明胶作为增稠剂,添加各种成核剂后的各体系的相变储能性能,从而得出羧甲基纤维素比明胶作为该体系的增稠剂的效果好得多,Na2SiO3.9H2O、Na2B4O7.10H2O的成核效果较好。     

Growth mechanism of titanium dioxide nanowires for dye-sensitized solar cells

Mesoporous films made of titanium dioxide nanowires are desirable for dye-sensitized solar cells because nanowires provide direct conduction pathways for photogenerated electrons. Anatase titanium dioxide nanowires with polycrystalline microstructure were synthesized on titanium foil using a three-step process. First, the top surface of the titanium foil was transformed to Na(2)Ti(2)O(4)(OH)(2) nanotubes through hydrothermal oxidation in NaOH. Next, the Na(2)Ti(2)O(4)(OH)(2) nanotubes were converted to H(2)Ti(2)O(4)(OH)(2) nanotubes by ion exchange. Finally, the H(2)Ti(2)O(4)(OH)(2) nanotubes were converted to polycrystalline anatase nanowires through a topotactic transformation. The film morphology evolution, crystal structure transformations and growth mechanism are described in detail. Titanium foil reacts with NaOH to form Na(2)Ti(2)O(4)(OH)(2) sheets, which exfoliate and spiral into nanotubes. The Na(2)Ti(2)O(4)(OH)(2) nanotubes are immersed in HCl solution to replace the Na(+) ions with H(+) ions. During the topotactic transformation of H(2)Ti(2)O(4)(OH)(2) nanotubes to anatase TiO(2) nanowires, the sheets made of edge bonded TiO(6) octahedra in the H(2)Ti(2)O(4)(OH)(2) nanotubes dehydrate and move towards each other to form anatase crystals oriented along the nanotube axis which creates a polycrystalline nanowire. These mesoporous TiO(2) nanowire films were suitable for use as dye-sensitized solar cell photoanodes.     

阳离子聚丙烯酰胺P(AM-DMC)的合成与表征

以丙烯酰胺(AM)和甲基丙烯酰氧乙基三甲基氯化铵(DMC)为单体,通过水溶液聚合法合成了P(AM-DMC)。研究了不同引发体系对聚合反应的影响,探讨了络合剂、助溶剂及表面活性剂的种类和质量分数对产物特性黏数和溶解性的影响。得到的较佳工艺条件是:在氧化还原剂[(NH4)2S2O8,CH3NaO3S.2H2O]和偶氮类化合物组成的复合引发体系作用下(氧化还原剂总质量分数0.0150%,偶氮类化合物质量分数0.0125%),EDTA.2Na质量分数0.0002%,尿素质量分数0.005%,表面活性剂B质量分数0.05%,在上述条件下,所得产物的特性黏数为10.7 dL/g,溶解时间100 min。用红外光谱技术对聚合物的结构进行了表征。     

Use of a water-soluble fullerene derivative as precipitating reagent and matrix-assisted laser desorption/ionization matrix to selectively detect charged species in aqueous solutions

A starlike water-soluble fullerene derivative, hexa(sulfonbutyl)fullerene (C60[(CH2)4SO3-]6; HSBF), consisting of a C60 cage covalently bonded with six negatively charged sulfonate arms, was synthesized and used to selectively precipitate positively charged surfactants, amino acids, peptides, and proteins. The affinity of HSBF to the analytes depends on the charge, structure, and hydrophobic characteristics of the analytes. The ion pair precipitate was easily removed from the solution by centrifugation. After washing, the precipitate was redissolved in the solvent or buffer solution and the analyte was characterized by laser desorption ionization-time-of-flight mass spectrometry (LD-TOF). HSBF shows strong optical absorbance in the UV range, so no additional organic matrix was required to conduct LD-TOF analysis of small analytes. For the solution that contained five quaternary amines differing only in alkyl chain length, HSBF exhibits the highest affinity to the amine with the longest alkyl chain. Only the arginine signal was detected from the solution that contained 14 amino acids. The peptides with arginine as the end groups interacted most strongly with HSBF and could be selectively precipitated from a solution of a mixture of five peptides. The signals associated with a trace amount of charged peptides derived from the digestion of proteins by trypsin were greatly enhanced after concentration with HSBF. Among eight proteins in the sample solution, insulin had the strongest affinity to the HSBF and exhibited the strongest signal on the matrix-assisted laser desorption/ionization mass spectrum.