厌氧消化过程化学变化的教学研究

有氧和无氧分解是生物体代谢有机物的2种途径,前者一直是生物化学课程中物质代谢的教学核心和重点。厌氧消化是有机物经无氧分解生成甲烷和二氧化碳的途径,相比于有氧分解,其具有化学反应众多、中间产物多、途径复杂等特点,同时对维护自然生态平衡、物质循环和人类社会的绿色健康发展等具有重要作用。如此重要的途径长期以来一直没有在生物化学教材与教学内容中体现,亟需进行教学改革。利用布鲁姆教学目标分类理论将厌氧消化过程中的主要反应、氧化还原过程及电子传递、热力学变化及串联反应等知识进行系统介绍,对物质代谢的另一条无氧路径进行补充,丰富了学生代谢网络的知识框架,完善了生物化学教学体系,相关教学内容和经验可供同行参考借鉴,对相关课程教学改革具有重要价值。     

Rich-defect carbon nanotubes for highly sensitive detection of Dopamine

Dopamine (DA) plays an essential role in the central nervous, renal, hormonal and cardiovascular systems. Various modified carbon nanotubes (CNT)-based dopamine sensors have been reported, but inexpensive, highly sensitive plain CNT-based ones are seldom studied. In this work, a facile and inexpensive CNT-based DA sensor is made by rich-defect multi-walled carbon nanotubes (RD-CNT) via an ultrasound method. The defect and elemental states of the RD-CNT are systematically studied by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), Raman spectroscopy, X-ray powder diffraction (XRD) and X-ray-photoelectron spectroscopy (XPS). Results show that massive holes and cracks exist in RD-CNT. The level of defects increases from the additional exposed edges. The electrochemical characterizations indicate that the electrochemical sensor has the highest sensitivity of 438.4 μA/(μM ⋅ cm²) among all carbon materials-based DA sensors while well meeting the clinically required detection range and selectivity. The DA sensor was further used to detect live healthy human serum and live PC12 cells with satisfactory results, thus holding great promise for an inexpensive but sensitive DA sensor in practical applications of clinical diagnosis and biological research.     

Amperometric sandwich-type aptasensor based on peroxidase mimetic Au@Pt for the carcinoembryonic antigen

For sensitive analysis of cancer biomarker carcinoembryonic antigen (CEA), an amperometric sandwich-type aptasensor is proposed based on a signal amplification strategy of Au@Pt bimetallic nanoprobes. As the excellent catalytic activity to hydrogen peroxide (H₂O₂), core-shell Au@Pt nanoparticles are employed as nanoprobes by conjugating directly with the secondary aptamer of CEA (Apt-II). Due to the synergic recognition effect of dual aptamers and the excellent catalytic activity of nanoprobes, this amperometric sandwich-type aptasensor for CEA exhibits high specificity and good sensitivity with a limit of detection of 0.31 ng/mL, along with a wide linear range from 0.1 ng/mL to 100 ng/mL.     

Radiation-sensitive nanogel-incorporated Fricke hydrogel dosimeters with reduced diffusion rates

Fricke gel dosimeters have great potential for three-dimensional (3D) dose verification in radiation therapy; however, they suffer from time-dependent ion diffusion after irradiation, severely affecting their stability and reliability. In this work, a pullulan-based amphiphilic molecule was synthesized, characterized, and self-assembled into nanogels. Nanogel structures were embedded into gel dosimeters to reduce the diffusion rates, and radiation-sensitive nanogel-incorporated Fricke hydrogel nanocomposites were prepared successfully. The results demonstrated that the diffusion coefficient of improved dosimeters was reduced to 0.125 ± 0.001 mm² h⁻¹, while maintaining the high optical dose sensitivity (0.0410 ± 0.0004 Gy⁻¹ cm⁻¹). It provides a powerful tool toward the practical application of 3D dosimeters.     

Thermosensitive acetylated carboxymethyl chitosan gel depot systems sustained release caffeic acid phenethyl ester for periodontitis treatment

Periodontitis is a chronic inflammatory disease of tooth support tissues leading to progressive destruction of periodontal soft tissues as well as alveolar bone, and can be treated with anti-inflammatory and bone-protective agents to prevent disease progression. Caffeic acid phenethyl ester (CAPE) is a natural polyphenolic compound with anti-inflammation, anti-oxidation and bone tissue repair efficacy. In this work, we synthesized a thermosensitive hydrogel matrix of acetylated carboxymethyl chitosan (A-CC), and firstly applied for periodontal local drug delivery. The biocompatible CAPE-loaded A-CC hydrogel (CAPE-A-CC) has the advantages of forming a drug depot in situ, sustained release and precisely improving the drug concentration in the lesion sites compared with traditional systemic administration. In addition, CAPE-A-CC could significantly inhibit the expression of inflammatory cytokines of TNF-α, IL-1β, IL-6, and IL-17 in macrophages, and increased the expression of alkaline phosphatase (ALP) in human periodontal ligament stem cells (hPDLSC) related to osteogenesis. This study develops a novel in situ thermosensitive hydrogel delivery system to improve the therapeutic potential of natural active ingredient for periodontitis therapy.     

Synergistic Porosity and Charge Effects in a Supramolecular Porphyrin Cage Promote Efficient Photocatalytic CO2 Reduction**

We present a supramolecular approach to catalyzing photochemical CO₂ reduction through second-sphere porosity and charge effects. An iron porphyrin box ( PB ) bearing 24 cationic groups, FePB-2(P) , was made via post-synthetic modification of an alkyne-functionalized supramolecular synthon. FePB-2(P) promotes the photochemical CO₂ reduction reaction (CO₂RR) with 97 % selectivity for CO product, achieving turnover numbers (TON) exceeding 7000 and initial turnover frequencies (TOF_max) reaching 1400 min⁻¹. The cooperativity between porosity and charge results in a 41-fold increase in activity relative to the parent Fe tetraphenylporphyrin ( FeTPP ) catalyst, which is far greater than analogs that augment catalysis through porosity ( FePB-3(N ), 4-fold increase) or charge (Fe p-tetramethylanilinium porphyrin ( Fe-p-TMA ), 6-fold increase) alone. This work establishes that synergistic pendants in the secondary coordination sphere can be leveraged as a design element to augment catalysis at primary active sites within confined spaces.     

Oxidation-Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H2O2

The full reaction photosynthesis of H₂O₂ that can combine water-oxidation and oxygen-reduction without sacrificial agents is highly demanded to maximize the light-utilization and overcome the complex reaction-process of anthraquinone-oxidation. Here, a kind of oxidation-reduction molecular junction covalent-organic-framework (TTF-BT-COF) has been synthesized through the covalent-coupling of tetrathiafulvalene (photo-oxidation site) and benzothiazole (photo-reduction site), which presents visible-light-adsorption region, effective electron-hole separation-efficiency and photo-redox sites that enables full reaction generation of H₂O₂. Specifically, a record-high yield (TTF-BT-COF, ≈276 000 μM h⁻¹ g⁻¹) for H₂O₂ photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation-reduction molecular junction COFs for full reaction photosynthesis of H₂O₂, which might extend the scope of COFs in H₂O₂ production.     

Spatially Directed Pyrolysis via Thermally Morphing Surface Adducts

Combustion is often difficult to spatially direct or tune associated kinetics—hence a run-away reaction. Coupling pyrolytic chemical transformation to mass transport and reaction rates (Damköhler number), however, we spatially directed ignition with concomitant switch from combustion to pyrolysis (low oxidant). A ‘surface-then-core’ order in ignition, with concomitant change in burning rate,is therefore established. Herein, alkysilanes grafted onto cellulose fibers are pyrolyzed into non-flammable SiO₂ terminating surface ignition propagation, hence stalling flame propagating. Sustaining high temperatures, however, triggers ignition in the bulk of the fibers but under restricted gas flow (oxidant and/or waste) hence significantly low rate of ignition propagation and pyrolysis compared to open flame (Liñán's equation). This leads to inside-out thermal degradation and, with felicitous choice of conditions, formation of graphitic tubes. Given the temperature dependence, imbibing fibers with an exothermically oxidizing synthon (MnCl₂) or a heat sink (KCl) abets or inhibits pyrolysis leading to tuneable wall thickness. We apply this approach to create magnetic, paramagnetic, or oxide containing carbon fibers. Given the surface sensitivity, we illustrate fabrication of nm- and μm-diameter tubes from appropriately sized fibers.     

Ultralow-loss Optical Waveguides through Balancing Deep-Blue TADF and Orange Room Temperature Phosphorescence in Hybrid Antimony Halide Microstructures

Harnessing the potential of thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) is crucial for developing light-emitting diodes (LEDs), lasers, sensors, and many others. However, effective strategies in this domain are still relatively scarce. This study presents a new approach to achieving highly efficient deep-blue TADF (with a PLQY of 25 %) and low-energy orange RTP (with a PLQY of 90 %) through the fabrication of lead-free hybrid halides. This new class of monomeric and dimeric 0D antimony halides can be facilely synthesized using a bottom-up solution process, requiring only a few seconds to minutes, which offer exceptional stability and nontoxicity. By leveraging the highly adaptable molecular arrangement and crystal packing modes, the hybrid antimony halides demonstrate the ability to self-assemble into regular 1D microrod and 2D microplate morphologies. This self-assembly is facilitated by multiple non-covalent interactions between the inorganic cores and organic shells. Notably, these microstructures exhibit outstanding polarized luminescence and function as low-dimensional optical waveguides with remarkably low optical-loss coefficients. Therefore, this work not only presents a pioneering demonstration of deep-blue TADF in hybrid antimony halides, but also introduces 1D and 2D micro/nanostructures that hold promising potential for applications in white LEDs and low-dimensional photonic systems.