酸碱解聚玉米秸秆分子结构的实验研究

以玉米秸秆为研究对象,分别采用5%H2SO4和5%NaOH溶液对秸秆进行解聚处理,并对解聚前后秸秆结构、化学组成、热稳定性等进行分析和表征。结果表明,与未处理前相比,经酸或碱解聚处理后,秸秆纤维结晶度由51.8%分别提高到63.5%和67.0%,秸秆中大部分半纤维素和部分木质素组分被脱除,半纤维素由29.10%分别降至7.02%和6.86%,木质素由38.12%分别降至32.21%和16.52%,而纤维素则由31.54%分别升至60.54%和76.15%。经酸碱处理后,秸秆表面形态结构变得疏松,出现小孔和裂缝,降解温度达到350℃,热稳定性能增加。上述结果说明,稀酸或稀碱均对玉米秸秆分子结构有一定程度的解聚作用,但就解聚溶出木质素而言,稀碱的解聚溶出效果要优于稀酸的。     

Synthesis, crystal, molecular, and electronic structures of hydride carbonyl ruthenium(II) complexes with pseudohalide ligands

Two pseudohalide hydride carbonyl ruthenium(II) complexes with formulae: [RuH(N₃)(CO)(PPh₃)₃] (1) and [RuH(NCO)(CO)(PPh₃)₃] (2) have been synthesized by the reactions of [RuHCl(CO)(PPh₃)₃] with sodium azide or sodium cyanate, respectively, and are compared with the previously described thiocyanate analog [RuH(NCS)(CO)(PPh₃)₃]. The molecular structures of the new compounds were determined by X-ray crystallography and their spectroscopic properties have been studied. Based on the crystal structures, computational investigations have been carried out in order to determine the electronic structures of the complexes. The electronic spectra were calculated with the use of time-dependent DFT methods, and the electronic spectra of the transitions were correlated with the molecular orbitals of the complexes.     

Enhancement inhibition efficiency of PBTCA depending on the inclusion complex with hydroxypropyl-β-cyclodextrin

For the first time, hydroxypropyl-β-cyclodextrin (HP-β-CD) has been brought in to include 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) in order to enhance inhibition efficiency of PBTCA, which leads a new approach to study oil–gas field corrosion inhibition in the process of acid treatment. Based on the host–guest inclusion reaction, the inclusion complex of PBTCA with HP-β-CD has been prepared in the laboratory. UV–Vis absorption spectrum was applied to study the inclusion behavior of PBTCA with HP-β-CD. The results revealed that PBTCA with HP-β-CD can form a 1:1 stoichiometry inclusion complex. The 1:1 inclusion complex synthesized by using lyophilization was further characterized by Fourier transform infrared spectroscopy. Besides, inhibition effect of the inclusion complex on the corrosion inhibition of Q235 carbon steel has been investigated in 0.1 M sulfuric acid (H₂SO₄) solution using potentiodynamic polarization, electrochemical impedance spectroscopy techniques and scanning electron microscopy (SEM). It was found that the presence of the inclusion complex better achieved the anti-corrosion property in aggressive medium than was the case with alone PBTCA and the highest inhibition efficiency of the inclusion complex over 90 % was obtained, which are suggestive of the active effect of the inclusion complex for improving inhibition efficiency of PBTCA. Meanwhile, the results obtained from SEM further showed that the inclusion complex acts as a more efficient corrosion inhibitor for Q235 carbon steel in H₂SO₄ medium.     

The importance of molecular complexity in the design of screening libraries

The one-dimensional model of Hann et al. (J Chem Inf Comput Sci 41(3):856–864) has been extended to include reverse binding and wrap-around interaction modes between the protein and ligand to explore the complete combinatorial matrix of molecular recognition. The cumulative distribution function of the Maxwell–Boltzmann distribution has been used to calculate the probability of measuring the sensitivity of the interactions as the asymptotic limits of the distribution better describe the behavior of the interactions under experimental conditions. Based on our model, we hypothesized that molecules of lower complexity are preferred for target based screening campaigns, while augmenting such a library with moieties of moderate complexities maybe better suited for phenotypic screens. The validity of the hypothesis has been assessed via the analysis of the hit rate profiles for four ChemBL datasets for enzymatic and phenotypic screens.     

Biomimetic synthesis of calcium carbonate with different morphologies under the direction of different amino acids

Using three different amino acids (AAs) as organic matrices, including the highly nonpolar hydrophobic l-valine, the positively charged l-arginine and the less polar uncharged l-serine, calcium carbonate (CaCO₃) with different morphologies and polymorphs were synthesized by a facile gas diffusion reaction based on biomimetic strategy. Compared with the control cubic calcite obtained in the absence of AAs, the product from l-valine was cubic calcite aggregates assembled by nano-platelets. The product from l-arginine was spherical vaterite aggregates assembled by spherical nanoparticles. The product from l-serine was the mixture of cubic calcite and spherical vaterite. The structures and properties of the side chains of the AAs exerted the significant effects on the nucleation and growth of the CaCO₃. The formation mechanisms of the CaCO₃ in the presence of AAs are preliminarily discussed. The results suggest that the polymorphs and morphologies of the inorganic nanomaterials might be easily adjusted through the careful selection of the organic matrices.     

Microenvironment Effects in Electrocatalysis: Ionic‐Liquid‐Like Coating on Carbon Nanotubes Enhances the Pd‐Electrocatalytic Alcohol Oxidation

A new catalyst consisting of ionic liquid (IL)‐functionalized carbon nanotubes (CNTs) obtained through 1,3‐dipolar cycloaddition support‐enhanced electrocatalytic Pd nanoparticles (Pd@IL(Cl^?)‐CNTs) was successfully fabricated and applied in direct ethanol alkaline fuel cells. The morphology, structure, component and stability of Pd@IL(Cl^?)‐CNTs were systematic characterized by transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), Raman spectra, thermogravimetric analysis (TGA) and X‐ray diffraction (XRD). The new catalyst exhibited higher electrocatalytic activity, better tolerance and electrochemical stability than the Pd nanoparticles (NPs) immobilized on CNTs (Pd@CNTs), which was ascribed to the effects of the IL, larger electrochemically active surface area (ECSA), and greater processing performance. Cyclic voltammograms (CVs) at various scan rates illustrated that the oxidation behaviors of ethanol at all electrodes were controlled by diffusion processes. The investigation of the different counteranions demonstrated that the performance of the IL‐CNTs hybrid material was profoundly influenced by the subtly varied structures of the IL moiety. All the results indicated that the Pd@IL(Cl^?)‐CNTs catalyst is an efficient anode catalyst, which has potential applications in direct ethanol fuel cells and the strategy of IL functionalization of CNTs could be available to prepare other carbonaceous carrier supports to enhance the dispersivity, stability, and catalytic performance of metal NPs as well.     

Synthesis and Properties of Oval‐Shaped Iron Oxide/Ethylene Glycol Mesostructured Nanosheets

We have demonstrated a new and facile bottom‐up protocol for the effective synthesis of oval‐shaped iron oxide/ethylene glycol (FeO_x/EG) mesostructured nanosheets. Deprotonated ethylene glycol molecules are intercalated into iron oxide layers to form an interlayer distance of 10.6 Å. These materials display some peculiar magnetic properties, such as the low Morin temperature T_M and ferromagnetism below this T_M value. CdSe/ZnS nanoparticles can be loaded onto these mesostructured nanosheets to produce nanocomposites that combine both magnetic and fluorescence functions. In addition, iron oxide/propanediol (or butanediol) mesostructured materials with increased interlayer distances can also be synthesized. The developed synthetic strategy may be extended toward the creation of other ultrathin mesostructured nanosheets.     

Exploring the Reactivity of Multicomponent Photocatalysts: Insight into the Complex Valence Band of BiOBr

The band structure of multicomponent semiconductor photocatalysts, as well as their reactivity distinction under different wavelengths of light, is still unclear. BiOBr, which is a typical multicomponent semiconductor, may have two possible valence‐band structures, that is, two discrete valence bands constructed respectively from O 2p and Br 4p orbitals, or one valence band derived from the hybridization of these orbitals. In this work, aqueous photocatalytic hydroxylation is applied as the probe reaction to investigate the nature and reactions of photogenerated holes in BiOBr. Three organic compounds (microcystin‐LR, aniline, and benzoic acid) with different oxidation potentials were selected as substrates. Isotope labeling (H₂¹⁸O as the solvent) was used to determine the source of the O atom in the hydroxyl group of the products, which distinguishes the contribution of different hydroxylation pathways. Furthermore, a spin‐trapping ESR method was used to quantify the reactive oxygen species (^.OH and ^.OOH) formed in the reaction system. The different isotope abundances of the hydroxyl O atom of the products formed, as well as the reverse trend of the ^.OH/^.OOH ratio with the oxidative resistance of the substrate under UV and visible irradiation, reveal that BiOBr has two separate valence bands, which have different oxidation ability and respond to UV and visible light, respectively. This study shows that the band structure of semiconductor photocatalysts can be reliably analyzed with an isotope labeling method.     

Protein‐Directed Synthesis of Mn‐Doped ZnS Quantum Dots: A Dual‐Channel Biosensor for Two Proteins

Proteins typically have nanoscale dimensions and multiple binding sites with inorganic ions, which facilitates the templated synthesis of nanoparticles to yield nanoparticle–protein hybrids with tailored functionality, water solubility, and tunable frameworks with well‐defined structure. In this work, we report a protein‐templated synthesis of Mn‐doped ZnS quantum dots (QDs) by exploring bovine serum albumin (BSA) as the template. The obtained Mn‐doped ZnS QDs give phosphorescence emission centered at 590 nm, with a decay time of about 1.9 ms. A dual‐channel sensing system for two different proteins was developed through integration of the optical responses (phosphorescence emission and resonant light scattering (RLS)) of Mn‐doped ZnS QDs and recognition of them by surface BSA phosphorescent sensing of trypsin and RLS sensing of lysozyme. Trypsin can digest BSA and remove BSA from the surface of Mn‐doped ZnS QDs, thus quenching the phosphorescence of QDs, whereas lysozyme can assemble with BSA to lead to aggregation of QDs and enhanced RLS intensity. The detection limits for trypsin and lysozyme were 40 and 3 nM , respectively. The selectivity of the respective channel for trypsin and lysozyme was evaluated with a series of other proteins. Unlike other protein sensors based on nanobioconjugates, the proposed dual‐channel sensor employs only one type of QDs but can detect two different proteins. Further, we found the RLS of QDs can also be useful for studying the BSA–lysozyme binding stoichiometry, which has not been reported in the literature. These successful biosensor applications clearly demonstrate that BSA not only serves as a template for growth of Mn‐doped ZnS QDs, but also impacts the QDs for selective recognition of analyte proteins.