平菇多糖稀溶液行为的研究

平菇多糖属生物高分子, 文章对平菇多糖稀溶液性质进行了研究。实验系采用Elias浊点滴定法测定平菇多糖溶液的θ组成, 用快速动态膜渗透计和粘度法测定平菇多糖的数均分子量、维利系数与分子链的构型参数。探讨其在θ条件下的分子形态及用Tung函数法等处理分级数据, 从而获得平菇多糖的分子量分布。     

气相二茂铁双电荷离子的动能谱研究

The unimolecular charge separation reactions of the doubly charged ions FeC_(10)H_(10)~(2+)、FeC_(10)H_9~(2+)、FeC_(10)H_8~(2+) produced in the ion source by electron impact from ferrocene have been studied using Mass analyzed Ion Kinetic Energy Spectrometry (MIKES) technique. From the values of the kinetic energy releases (T), the intercharge distances (R) of the exploding doubly charged ions in their transition structures have been estimated and some structural informations about the transition states can be obtained. The collision induced reactions of the FeC_(10)H_(10)~(2+) ion with Ar have been studied using MIKES, we postulate a new type of continuing reaction which may be "collisional charge separation induced dissociation".     

铁(Ⅲ)-邻菲啰啉体系流动注射-分光光度法测定药品中的抗坏血酸

本文基于抗坏血酸还原铁(Ⅲ)-邻菲啰啉为红色铁(Ⅱ)-邻菲啰啉,建立了流动注射分光光度法测定药品中抗坏血酸的方法。本法体系简单,操作方便、快速,标准加入试验的回收率为92～103％。     

Trace mild acid-catalysed Z → E isomerization of norbornene-fused stilbene derivatives: intelligent chiral molecular photoswitches with controllable self-recovery

Stilbene derivatives have long been known to undergo “acid-catalyzed” Z → E isomerization, where a strong mineral acid at high concentration is practically necessary. Such severe reaction conditions often cause undesired by-reactions and limit their potential application. Herein, we present a trace mild acid-catalyzed Z → E isomerization found with stilbene derivatives fused with a norbornene moiety. By-reactions, such as the migration of the C C double bond and electrophilic addition reactions, were completely inhibited because of the ring strain caused by the fused norbornene component. Direct photolysis of the E isomers at selected wavelengths led to the E → Z photoisomerization of these stilbene derivatives and thus constituted a unique class of molecular switches orthogonally controllable by light and acid. The catalytic amount of acid could be readily removed, and the Z → E isomerization could be controlled by turning on/off the irradiation of a photoacid, which allowed repeated isomerization in a non-invasive manner. Moreover, the Z isomer produced by photoisomerization could spontaneously self-recover to the E isomer in the presence of a catalytic amount of acid. The kinetics of Z → E isomerization were adjustable by manipulating catalytic factors and, therefore, unprecedented molecular photoswitches with adjustable self-recovery were realized.

Quantitative Z → E isomerization was catalyzed by trace mild acids to offer molecular switches orthogonally controllable by acid and light.     

A rationally designed two-dimensional MoSe2/Ti2CO2 heterojunction for photocatalytic overall water splitting: simultaneously suppressing electron–hole recombination and photocorrosion

Electron–hole recombination and photocorrosion are two challenges that seriously limit the application of two-dimensional (2D) transition metal dichalcogenides (TMDs) for photocatalytic water splitting. In this work, we propose a 2D van der Waals MoSe₂/Ti₂CO₂ heterojunction that features promising resistance to both electron–hole recombination and photocorrosion existing in TMDs. By means of first-principles calculations, the MoSe₂/Ti₂CO₂ heterojunction is demonstrated to be a direct Z-scheme photocatalyst for overall water splitting with MoSe₂ and Ti₂CO₂ serving as photocatalysts for hydrogen and oxygen evolution reactions, respectively, which is beneficial to electron–hole separation. The ultrafast migration of photo-generated holes from MoSe₂ to Ti₂CO₂ as well as the anti-photocorrosion ability of Ti₂CO₂ are responsible for photocatalytic stability. This heterojunction is experimentally reachable and exhibits a high solar-to-hydrogen efficiency of 12%. The strategy proposed here paves the way for developing 2D photocatalysts for water splitting with high performance and stability in experiments.

The two challenges of electron–hole recombination and photocorrosion for two-dimensional transition metal dichalcogenides in the application of photocatalytic water splitting are simultaneously suppressed by rational design of heterojunctions.     

Cooperatively assembled liquid crystals enable temperature-controlled Förster resonance energy transfer

Balancing the rigidity of a π-conjugated structure for strong emission and the flexibility of liquid crystals for self-assembly is the key to realizing highly emissive liquid crystals (HELCs). Here we show that (1) integrating organization-induced emission into dual molecular cooperatively-assembled liquid crystals, (2) amplifying mesogens, and (3) elongating the spacer linking the emitter and the mesogen create advanced materials with desired thermal–optical properties. Impressively, assembling the fluorescent acceptor Nile red into its host donor designed according to the aforementioned strategies results in a temperature-controlled Förster resonance energy transfer (FRET) system. Indeed, FRET exhibits strong S-curve dependence as temperature sweeps through the liquid crystal phase transformation. Such thermochromic materials, suitable for dynamic thermo-optical sensing and modulation, are anticipated to unlock new and smart approaches for controlling and directing light in stimuli-responsive devices.

A temperature-sensitive Förster resonance energy transfer system was constructed using a highly emissive liquid crystal co-assembled with Nile red, enabling thermo-optical modulation for controlling and directing light in stimuli-responsive devices.     

还原氧化石墨烯@泡沫镍载CoO纳米花电极制备及催化CO2性能

本文以氧化石墨烯包覆泡沫镍电极(GO@NF)作为基底,采用水热法在GO@NF基底上原位生长CoO纳米花,同时GO在水热过程中被同步热还原为还原氧化石墨烯(RGO),从而一步制得还原氧化石墨烯包覆泡沫镍负载CoO纳米花电极(CoO/RGO@NF)。使用XRD和SEM对CoO/RGO@NF电极进行表征,发现CoO纳米花均匀生长在泡沫镍三维网络结构上,CoO纳米花为大量针状纳米棒围绕一个中心而成的花状结构,纳米棒的长度约为10 ~ 15 μm,直径约为100 ~ 200 nm。使用循环伏安和线性扫描法测试了CoO/RGO@NF电极电催化CO₂的还原性能,在-0.76 V（vs. SHE）电位下,CoO/RGO@NF电极电催化CO₂还原的电流效率达到70.9%,产甲酸法拉第效率达到65.2%,甲酸产率为59.8 μmol·h^-1·cm^-2,且电极可持续稳定电催化还原CO₂ 4 h,表明CoO/RGO@NF电极对CO₂电还原有着优良的催化活性、选择性和稳定性。     

Mixing of Racemic Poly(L-lactide)/Poly(D-lactide) Blend with Miscible Poly(D,L-lactide):Toward All Stereocomplex-type Polylactide with Strikingly Enhanced SC Crystallizability

Stereocomplex-type polylactide (SC-PLA) consisting of alternatively arranged poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) chains has gained a good reputation as a sustainable engineering plastic with outstanding heat resistance and durability,however its practical applications have been considerably hindered by the weak SC crystallizability.Current methods used to enhance the SC crystallizability are generally achieved at the expense of the precious bio-renewability and/or bio-degradability of PLAs.Herein,we demonstrate a feasible method to address these challenges by incorporating small amounts of poly(D,L-lactide) (PDLLA) into linear high-molecular-weight PLLA/PDLA blends.The results show that the incorporation of the atactic PDLLA leads to a significant enhancement in the SC crystallizability because its good miscibility with the isotactic PLAs makes it possible to greatly improve the chain mixing between PLLA and PDLA as an effective compatibilizer.Meanwhile,the melt stability (i.e.,the stability of PLLA/PDLA chain assemblies upon melting) could also be improved substantially.Very intriguingly,SC crystallites are predominantly formed with increasing content and molecular weight of PDLLA.More notably,exclusive SC crystallization can be obtained in the racemic blends with 20 wt％ PDLLA having weight-average molecular weight of above 1 ×10s g/mol,where the chain mixing level and intermolecular interactions between the PLA enantiomers could be strikingly enhanced.Overall,our work could not only open a promising horizon for the development of all SC-PLA-based engineering plastic with exceptional SC crystallizability but also give a fundamental insight into the crucial role of PDLLA in improving the SC crystallizability of PLLA/PDLA blends.     

Reactive TiO2 Nanoparticles Compatibilized PLLA/PBSU Blends:Fully Biodegradable Polymer Composites with Improved Physical,Antibacterial and Degradable Properties

The fully biodegradable polymer blends remain challenges for the application due to their undesirable comprehensive performance.Herein,remarkable combination of superior mechanical performance,bacterial resistance,and controllable degradability is realized in the biodegradable poly(L-lactide)/poly(butylene succinate) (PLLA/PBSU) blends by stabilizing the epoxide group modified titanium dioxide nanoparticles (m-TiO2) at the PLLA-PBSU interface through reactive blending.The m-TiO2 can not only act as interfacial compatibilizer but also play the role of photodegradation catalyst:on the one hand,binary grafted nanoparticles were in situ formed and stabilized at the interface to enhance the compatibility between polymer phases.As a consequence,the mechanical properties of the blend,such as the elongation at break,notched impact strength and tensile yield strength,were simultaneously improved.On the other hand,antibacterial and photocatalytic degradation performance of the composite films was synergistically improved,it was found that the m-TiO2 incorporated PLLA/PBSU films exhibit more effective antibacterial activity than the neat PLLA/PBSU films.Moreover,the analysis of photodegradable properties revealed that that m-TiO2 nanoparticles could act as a photocatalyst to accelerate the photodegradation rate of polymers.This study paves a new strategy to fabricate advanced PLLA/PBSU blend materials with excellent mechanical performance,antibacterial and photocatalytic degradation performance,which enables the potential utilization of fully degradable polymers.