Properties of water-soluble carboxymethyl chitosan film modified by hydrophobic poly(propylene glycol)

A series of water-soluble carboxymethyl chitosan (CMCS)/poly(propylene glycol) (PPG) blend films with various CMCS/PPG mole ratios were prepared by the solution casting method. Morphology of the CMCS/PPG blend films was investigated by scanning electron microscopy (SEM). Thermal, mechanical, and chemical properties of the CMCS/PPG blend films were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile tests, and contact angle tests. It was found that the introduction of PPG can markedly affect the morphology and the properties of CMCS films.     

羟基磷灰石及其复合材料对重金属的吸附研究进展

羟基磷灰石具有特殊的晶体结构,对二价的重金属离子有很强的结合力,是一种可用于环境污染治理的新型功能性材料。它可有效地吸附去除水中的Pb2+,Cd2+,Cu2+,Zn2+,Co2+,Ni2+等重金属离子,但其粉体的结构却限制了它在水环境中的实际应用。随着纳米技术、复合材料技术的发展,在羟基磷灰石的基础上开发出的具有高效吸附性能或分离特性的新型材料在重金属吸附研究中显示了潜在的优势。本文综述了羟基磷灰石及其复合材料对水中重金属去除方面的研究进展,探讨了它对重金属吸附机理,并对羟基磷灰石进一步的研究提出了展望。     

埃罗替尼的合成

以N,N-二甲基甲酰胺和硫酸二甲酯反应生成的亚胺盐与3-乙炔基苯胺进行亲核反应及甲醇的消去,获得了制备埃罗替尼所需的重要中间体N’-(3-乙炔基苯基)-N,N-二甲基甲脒,收率为75.8%。再以此中间体与2-氨基-4,5-二(2-甲氧基乙氧基)苯甲腈通过Dimroth重排反应方便地制得了抗肿瘤药物埃罗替尼,总收率(以3-乙炔基苯胺计)为56.5%。与以往合成埃罗替尼的方法相比,该方法更经济、更绿色。     

Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

A detailed chemical kinetic model for oxidation of CH₃OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for , , , and . The experiments, involving CH₃OH/O₂ mixtures diluted in N₂, were carried out in a high‐pressure flow reactor at 600–900 K and 20–100 bar, varying the reaction stoichiometry from very lean to fuel‐rich conditions. Under the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were generally satisfactory. The governing reaction pathways have been outlined based on calculations with the kinetic model. Unlike what has been observed for unsaturated hydrocarbons, the oxidation pathways for CH₃OH under the investigated conditions were very similar to those prevailing at higher temperatures and lower pressures. At the high pressures, the modeling predictions for onset of reaction were particularly sensitive to the reaction.     

Preparation and characterization of ZrCO/C composite aerogels

Zr-containing organic aerogels were synthesized by ligand substitution reaction of polyzirconoxone and 2, 4-dihydroxybenzoic acid, followed by polymerization with formaldehyde, and then supercritical drying using CO₂. After carbonization and carbothermal reduction under an argon atmosphere, ZrCO/C composite aerogels with controllable zirconium content (47.8–78.6 wt%) were obtained. The carbothermal reduction was substantially completed at 1,500 °C, and the obtained ZrCO/C composite aerogels exhibit low oxygen contents (9.4–6.7 wt%) and high surface areas (589–147 m²/g). Pore morphologies of the ZrCO/C composite aerogels were investigated in detail by nitrogen sorption measurements, scanning electron microscopy and its associated energy-dispersive X-ray microanalysis measurements. The results show that the aerogels are composed of carbon framework and Zr-conglomerations, and the surface area of aerogel is severely affected by its zirconium content. The presence of reductive ZrC crystals can greatly enhance the oxidation resistance ability of amorphous carbon framework and prevent collapse.     

Self‐Assembled Poly(N‐methylaniline)–Lignosulfonate Spheres: From Silver‐Ion Adsorbent to Antimicrobial Material

Self‐assembled poly(N‐methylaniline)–lignosulfonate (PNMA–LS) composite spheres with reactive silver‐ion adsorbability were prepared from N‐methylaniline by using lignosulfonate (LS) as a dispersant. The results show that the PNMA–LS composite consisted of spheres with good size distribution and an average diameter of 1.03–1.27 μm, and the spheres were assembled by their final nanofibers with an average diameter of 19–34 nm. The PNMA–LS composite spheres exhibit excellent silver‐ion adsorption; the maximum adsorption capacity of silver ions is up to 2.16 g g^?1 at an adsorption temperature of 308 K. TEM and wide‐angle X‐ray results of the PNMA–LS composite spheres after absorption of silver ions show that silver ions are reduced to silver nanoparticles with a mean diameter of about 11.2 nm through a redox reaction between the PNMA–LS composite and the silver ions. The main adsorption mechanism between the PNMA–LS composite and the silver ions is chelation and redox adsorption. In particular, a ternary PNMA–LS–Ag composite achieved by using the reducing reaction between PNMA–LS composite spheres and silver ions can be used as an antibacterial material with high bactericidal rate of 99.95 and 99.99 % for Escherichia coli and Staphylococcus aureus cells, respectively.     

Single‐Molecule Detection Reveals Knot Sliding in TrmD Denaturation

An increasing number of proteins are found to contain a knot in their polypeptide chain. Although some studies have looked into the folding mechanism of knotted proteins, why and how these complex topologies form are still far from being fully answered. Moreover, no experimental information about how the knot moves during the protein‐folding process is available. Herein, by combining single‐molecule fluorescence resonance energy transfer (smFRET) experiments with molecular dynamics (MD) simulations, we performed a detailed study to characterize the knot in the denatured state of TrmD, a knotted tRNA (guanosine‐1) methyltransferase from Escherichia coli, as a model system. We found that the knot still existed in the unfolded state of TrmD, consistent with the results for two other knotted proteins, YibK and YbeA. More interestingly, both smFRET experiments and MD simulations revealed that the knot slid towards the C‐terminal during the unfolding process, which could be explained by the relatively strong interactions between the β‐sheet core at the N terminal of the native knot region. The size of the knot in the unfolded state is not larger than that in the native state. In addition, the knot slid in a “downhill” mode with simultaneous chain collapse in the denatured state.     

Dynamic Electrosorption Analysis as an Effective Means to Characterise the Structure of Bulk Graphene Assemblies

Restacking of graphene sheets to a graphite‐like structure is a prevailing problem that is known to compromise the performance of individual graphene sheets in an assembled bulk form. To address this common problem efficiently and monitor the structure and quality of graphene products comprehensively, it is highly desirable to develop reliable metrology techniques for characterising graphene‐based materials on a bulk assembly level and in a quantitative manner. Here, by revisiting the physicochemical principle of electrosorption, we propose a simple electrochemical approach, namely dynamic electrosorption analysis (DEA), as an easily accessible and effective technique for evaluation of the self‐stacking behaviour of graphene. Taking multilayered chemically converted graphene films as a model, we demonstrate that the DEA technique can effectively reveal very subtle variation in accessible surface area and pore size of graphene assemblies in the liquid phase and thus can provide useful insights to the experimental design relating to restacking control. This work also reveals the huge effect some routine processing conditions, such as heat treatment and drying, can have on the structure and performance of graphene‐based bulk materials, providing useful guidance for future manufacturing of this class of materials.     

Syntheses and Properties of Graphyne Fragments: Trigonally Expanded Dehydrobenzo[12]annulenes

We present herein the synthesis and properties of the largest hitherto unknown graphyne fragment, namely trigonally expanded tetrakis(dehydrobenzo[12]annulene)s (tetrakis‐DBAs). Intramolecular three‐fold alkyne metathesis reactions of hexakis(arylethynyl)DBAs 9 a and 9 b using Fürstner’s Mo catalyst furnished tetrakis‐DBAs 8 a and 8 b substituted with tert‐butyl or branched alkyl ester groups in moderate and fair yields, respectively, demonstrating that the metathesis reaction of this protocol is a powerful tool for the construction of graphyne fragment backbones. For comparison, hexakis(arylethynyl)DBAs 9 c – g have also been prepared. The one‐photon absorption spectrum of tetrakis‐DBA 8 a bearing tert‐butyl groups revealed a remarkable bathochromic shift of the absorption cut‐off (λ_cutoff) compared with those of previously reported graphyne fragments due to extended π‐conjugation. Moreover, in the two‐photon absorption spectrum, 8 a showed a large cross‐section for a pure hydrocarbon because of the planar para‐phenylene‐ethynylene conjugation pathways. Hexakis(arylethynyl)‐DBAs 9 c – e and 9 g and tetrakis‐DBA 8 b bearing electron‐withdrawing groups aggregated in chloroform solutions. Comparison between the free energies of 9 e and 8 b bearing the same substituents revealed the more favorable association of the latter due to stronger π–π interactions between the extended π‐cores. Polarized optical microscopy observations, DSC, and XRD measurements showed that 8 b and 9 e with branched alkyl ester groups displayed columnar rectangular mesophases. By the time‐resolved microwave conductivity method, the columnar rectangular phase of 8 b was shown to exhibit a moderate charge‐carrier mobility of 0.12 cm² V^?1 s^?1. These results indicate that large graphyne fragments can serve as good organic semiconductors.