不同含羧酸纤维与铁离子的配位反应动力学及配合物的催化降解性能

分别使用具有相似羧基含量的海藻纤维、 丙烯酸接枝改性聚四氟乙烯纤维和聚丙烯纤维(PAA-g-PP 和PAA-g-PTFE)3种含羧酸纤维与Fe³⁺进行配位反应, 研究和比较了反应的动力学特性及影响因素. 将3种含羧酸纤维铁配合物分别作为非均相Fenton反应催化剂应用于染料降解反应中, 分析和评价了其配位结构和表面性能对催化活性的影响. 结果表明, 在所涉及的温度和浓度范围内, 3种含羧酸纤维与Fe³⁺的反应均很好地符合Langmuir等温吸附模型和Lagergren准二级动力学方程. Fe³⁺初始浓度的增加会降低反应速率常数, 而反应温度的升高则会增加配合物中Fe³⁺的配合量. 在相同反应条件下, 海藻纤维比PAA-g-PP和PAA-g-PTFE更容易与Fe³⁺发生反应, 且反应速率常数和Fe³⁺配合量按照下列顺序排列: 海藻纤维>PAA-g-PP>PAA-g-PTFE. 3种含羧酸纤维铁配合物都能够在染料氧化降解反应中作为非均相Fenton催化剂, 且紫外光比可见光更能够提高其催化活性. 海藻纤维铁配合物比其它2种含羧酸纤维铁配合物具有更好的催化作用, 这与三者在配位结构和表面性能之间的显著差异有关.     

Direct Synthesis of Phenol from Benzene on an Activated Carbon Catalyst Treated with Nitric Acid

Commercially available coal-based activated carbon was treated by nitric acid with different concentrations and the resultant samples were used as catalysts for the direct hydroxylation of benzene to phenol in acetonitrile. Boehm titration, X-ray photoelectron spectroscopy, scanning electron microscope coupled with an energy dispersive X-ray microanalyzer, and Brunauer-Emmett-Teller method were used to characterize the samples. The number of carboxyl groups on the surface was found to be the main factor affecting the catalytic activity. An optimum catalytic performance with a yield of 15.7% and a selectivity of 87.2% to phenol was obtained.     

羧基化氧化石墨烯的可控合成及血液相容性

采用自由基引发剂偶氮二异丁腈(AIBN)作为功能改性剂, 通过AIBN分解产生的异丁腈自由基进攻氧化石墨烯上五元环与七元环的缺陷点, 形成氰基改性氧化石墨烯中间体, 再通过水解反应制得羧基化氧化石墨烯[GeneO-C(CH₃)₂-COOH]纳米材料. 采用傅里叶变换红外光谱(FTIR), X射线衍射(XRD), 热重分析(TGA)和原子力显微镜(AFM)等方法对合成的材料进行了表征, 并采用复钙时间测试考察了材料的血液相容性. 研究结果表明, 氧化石墨烯中羧基的含量可以通过调整AIBN和GeneO的投料比来控制. 本方法不但可提高氧化石墨烯的羧基含量, 而且可使其具有良好的血液相容性.     

Identification of a chemical substructure that is immobilized to ferrite nanoparticles (FP)

Despite the wide utility of ferrite nanoparticles (FP), a methodology to conjugate heterologous molecules to FP is still limited and characterization of small molecule-conjugated FP is not well known. Here, we describe what kinds of proteins and amino acids are selectively immobilized onto FP when FP is synthesized in the presence of these molecules. Two-dimentional gel electrophoresis (2D SDS-PAGE) showed that proteins with low pI value were selectively bound to FP. Quantitative analyses using HPLC suggested that L-aspartic acid (Asp) and L-cysteine (Cys) were bound to FP selectively among natural amino acids examined. Additional analysis of compounds-conjugated FP revealed that selective binding of Asp to FP was attributed with its molecular structure. It was found that the substructure of amino acid-bound to FP specifically was composed of a defined chelation of two carboxyl groups separated by two carbon atoms as deduced from FT-IR measurement. Thus, we concluded that molecules possessing two carboxyl groups separated by two carbons were bound to FP spontaneously and selectively, which might enable the attachment of free functional groups onto the FP surface if their molecules have functional groups other than carboxyl groups. The resulting complex might be applicable as a chemical tag to immobilize various molecules onto FP.     

Proton Conductor of Propylene Carbonate–Plasticized Carboxyl Methylcellulose–Based Solid Polymer Electrolyte

Carboxyl methylcellulose (CMC) solid polymer electrolytes were prepared by utilizing oleic acid (OA) and different wt.% of propylene carbonate (PC) by using the solution casting technique. An ionic conductivity study of the films was done by using impedance spectroscopy. The highest ionic conductivity gained is 2.52 × 10^?7 S cm^?1 at ambient temperature for sample CMC-OA-PC 10 wt.%. From transference number measurement (TNM), the value of cation diffusion coefficient, D₊, and ionic mobility, μ₊, was higher than the value of anion diffusion coefficient, D_?, and ionic mobility, μ_?. Thus, the results prove that the present samples were proton conductors.     

Improvement of electronic properties of carboxylated zigzag single wall carbon nanotubes by interaction with benzene derivatives

In this article, we reported the structural and conductive properties of benzene derivatives/carboxylated zigzag SWCNTs. It was noticed that the carboxylated carbon nanotubes were appropriate adsorbents for benzene derivatives. We presented novel density of states and band structures for modified SWCNTs by both carboxylic group and benzene derivatives. The result showed that nitrobenzene/COOH-SWCNT comprising superb electronic properties can be effectually applied for electronic devices and solar cells, instead of aniline/SWCNT combined system.     

Carboxyl modified multi-walled carbon nanotubes as solid-phase extraction adsorbents combined with high-performance liquid chromatography for analysis of linear alkylbenzene sulfonates

Recently, multi-wall carbon nanotubes (MWCNTs) as adsorbents of solid-phase extraction are attractive because they can be used for enrichment of organic compounds and metal ions at trace levels. In this study, we use the carboxyl modified multi-wall carbon nanotubes (CMMWCNTs) as adsorbents of solid-phase extraction for extraction of linear alkylbenzene sulfonates (LAS), which are widely used anion surfactant with different homologues, and detected by HPLC-UV. The effect of eluent and its volume, sample pH and flow rate, sample volume and the ultrasonic time of sample, the content of the electrolyte (NaCl) were investigated and optimized. The detection limit for LAS homologues was 0.02-0.03 μg L⁻¹ with R.S.D. (n = 6) ranging from 2.04 to 10.03%. The recoveries of LAS homologues in the spiked environmental water samples ranged from 84.8 to 106.1%. The proposed method has been applied successfully to the analysis of LAS in aqueous environmental samples, which demonstrates that CMMWCNTs-based solid-phase extraction is a precision and convenient enrichment method and can be used for analysis of LAS homologues in water samples.     

Theoretical study of formic acid: A new look at the origin of the planar Z conformation and C–O rotational barrier

The E and Z rotamers of formic acid (HCOOH) and its barrier to internal rotation about the C–O bond were computationally explored at the HF/6-311 + G^∗∗, B3LYP/cc-pVTZ, and CCSD(T)/cc-pVTZ levels of theory. All calculations yielded similar results consistent with experimental observations. Subsequent analysis of the interaction between formate ion (HCOO⁻) and proton (H⁺) within formic acid demonstrated a direct correlation between the changes in fragment interaction energy and the total energy of formic acid upon rotation. To obtain further insights into the interaction, energy decomposition analysis based on the reactive bond orbital (RBO) method was carried out using the 6-311 + G^∗∗ basis set. The analysis showed the electrostatic effect constitutes a major component that gives rise to the interaction energy variation along the rotation path. Thus, the electrostatic environment of HCOO⁻ can be viewed as the key factor determining the Z ground state and C–O rotational barrier of formic acid. The anisotropic electrostatic environment of formate that favors planar conformations of formic acid may be due to the in-plane distribution of carbonyl lone pairs, and the larger electrostatic attraction in the Z form appears to come from a secondary electrostatic interaction between the proton and the distal oxygen. At the rotational transition state, the O–H bond was not exactly perpendicular to the molecular plane, but slightly tilted toward the E side, which can also be explained by the electrostatic hypothesis. Charge-transfer stabilization was smallest in the Z conformation, but it gradually increased upon rotation to a maximum at the E conformation. Therefore, charge - transfer does not explain the geometry of formic acid. The important role of the electrostatic effect was also observed in in-plane rotation of the O–H bond.