Oxygen-vacancy-enhanced Catalytic Activity of Au@Co3O4/CeO2 Yolk-shell Nanocomposite to Electrochemically Detect Hydrogen Peroxide

Biomimetic electrochemical sensors are very promising not only due to their lower expense and longer stability than conventional enzymatic ones, but they also often suffer from simultaneously achieving high sensitivity and good selectivity. Here we present a well-defined Au@Co₃O₄/CeO₂ yolk-shell nanostructure (YSN) that is first synthesized and exploited as highly efficient electrocatalysts for hydrogen peroxide (H₂O₂) detection. The introduced CeO₂ in Co₃O₄ matrix greatly facilitates the migration of lattice oxygen, which increases the concentration of surface oxygen vacancies (O_a), remarkably enhancing the adsorption ability of H₂O₂ and promoting the decomposition of H₂O₂ for faster electron transfer than pristine Au@Co₃O₄ core-shell nanostructure (CSN). The abundant O_a of Au@Co₃O₄/CeO₂ YSN is confirmed by X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). The as-prepared biomimetic sensor delivers a wide dynamic range (5.0 nM to 5.4 μM), a low limit of detection (LOD) (2.74 nM), and a high sensitivity (35.67 μA μM⁻¹ cm⁻²), paving a new way to construct an ultrasensitive and selective enzyme-free biomimetic electrochemical sensor. Furthermore, the sensor is used to real-time monitor H₂O₂ released from human cervical cancer cells (HeLa) and human umbilical vein endothelial cells (HUVEC), demonstrating its great potential in practical applications.     

ABC三嵌段共聚物胶束从多间隔结构到多核结构转变的Monte Carlo模拟

采用Monte Carlo模拟方法研究了疏水-亲水-疏水(H-P-H)型ABC三嵌段共聚物在B嵌段的选择性溶剂中的自组装行为. 模拟结果表明, 通过调节A嵌段和C嵌段的疏水性和二者之间的不相容性, 体系中可以形成多种形貌各异的胶束. 根据胶束中疏水核结构的特点, 这些胶束大体上可以被分为多核型胶束和多间隔型胶束两种类型. 通过增强疏水嵌段的疏水性或降低A嵌段和C嵌段间的不相容性, H-P-H型ABC三嵌段共聚物胶束能够发生从多核型胶束向多间隔型胶束的转变. 进一步分析胶束中聚合物的链构象等微观结构信息发现, A嵌段和C嵌段间的排斥作用和疏水作用之间存在竞争关系, 而这种竞争关系是影响体系中形成多核型胶束还是多间隔型胶束的决定性因素.     

Enhanced conversion of α-cellulose to 5-HMF in aqueous biphasic system catalyzed by FeCl_3-CuCl_2

This study was to investigate the optimal additions of the cellulose decomposition reaction to obtain the most yield of 5-HMF and other furan derivatives in various biphasic systems with FeCl_3-CuCl_2 mixed catalysts,and explore its depolymerization kinetics.A series of controllable reactions have been performed under mild environmentally friendly atmosphere.The experiment results showed that49.13 wt% of 5-HMF was the maximum production along with 2.98 wt% other furan derivatives catalyzed by mixed Lewis acid FeCl_3-CuCl_2 under the two phases which included high concentration NaCl aqueous phase and n-butanol organic phase at 190℃ for 45 min.The conclusion suggested that two-phase systems benefited the yield of 5-HMF,furan derivatives via extracting the target products from reaction phase to organic phase to avoid rehydration of 5-HMF.The kinetic calculation revealed the conversion with mixed catalysts had lower reaction apparent activation energy(21.65 kJ/mol,190-230℃) and the reaction rate was faster than that with acid-based catalysts.Based on experiment exploration,the probable mechanism of cellulose decomposition with FeCl_3-CuCl_2 was proposed.     

An Electron Paramagnetic Resonance Study of the Orbital Ordering Compound MgTi<Subscript>2</Subscript>O<Subscript>4</Subscript>

We report the electron paramagnetic resonance (EPR) studies of MgTi₂O₄ in the 300–140 K range. Above the transition temperature T _t (~258 K), the EPR results indicate that MgTi₂O₄ is paramagnetic. The parameters of the EPR spectra show an anomalous change at T _t. The clear EPR lines can be observed in temperature between T _t and 220 K. Besides that the EPR intensity, g value, and EPR linewidth increase with decreasing temperature; in temperature range below 220 K, no clear EPR line can be detected. The EPR spectra results demonstrate that magnetic spin-singlet state and the orbital density wave of MgTi₂O₄ system are formed gradually with decreasing temperature at low temperature range.     

A Novel L‐Cysteine Electrochemical Sensor Using Sulfonated Graphene‐poly(3,4‐Ethylenedioxythiophene) Composite Film Decorated with Gold Nanoparticles

By exploiting the electrostatic interaction between positively charged 3,4‐ethylenedioxythiophene cation radicals and negatively charged sulfonated graphene (SG) sheets, we prepared a poly(3,4‐ethylenedioxythiophene)‐sulfonated graphene (SG‐PEDOT) composite film by a one‐step electrochemical process. The composite was further decorated with gold nanoparticles (AuNPs) and employed as an electrode material for the detection of L ‐cysteine (Cys). The SG‐PEDOT composite film is shown to provide a rough surface for the electrodeposition of AuNPs and to improve substrate accessibility and interaction with Cys. Moreover, the AuNPs‐decorated composite exhibits better electrocatalytic performance than that of a SG‐PEDOT composite only. Under optimum experimental conditions, the amperometric current of the sensor is linearly related to the concentration of Cys in the 0.1 to 382 µM range, and the detection limit is 0.02 µM (at S/N=3). The modified electrode displays favorable selectivity, good stability and high reproducibility. The method was successfully applied to the detection of Cys in spiked human urine.     

Peptide Dimethylation: Fragmentation Control via Distancing the Dimethylamino Group

Direct reductive methylation of peptides is a common method for quantitative proteomics. It is an active derivatization technique; with participation of the dimethylamino group, the derivatized peptides preferentially release intense a₁ ions. The advantageous generation of a₁ ions for quantitative proteomic profiling, however, is not desirable for targeted proteomic quantitation using multiple reaction monitoring mass spectrometry; this mass spectrometric method prefers the derivatizing group to stay with the intact peptide ions and multiple fragments as passive mass tags. This work investigated collisional fragmentation of peptides whose amine groups were derivatized with five linear ω-dimethylamino acids, from 2-(dimethylamino)-acetic acid to 6-(dimethylamino)-hexanoic acid. Tandem mass spectra of the derivatized tryptic peptides revealed different preferential breakdown pathways. Together with energy resolved mass spectrometry, it was found that shutting down the active participation of the terminal dimethylamino group in fragmentation of derivatized peptides is possible. However, it took a separation of five methylene groups between the terminal dimethylamino group and the amide formed upon peptide derivatization. For the first time, the gas-phase fragmentation of peptides derivatized with linear ω-dimethylamino acids of systematically increasing alkyl chain lengths is reported. Figure

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Metal‐Free Aminosulfonylation of Aryldiazonium Tetrafluoroborates with DABCO⋅(SO2)2 and Hydrazines

The coupling of aryldiazonium tetrafluoroborates, DABCO?(SO₂)₂, and hydrazines under metal‐free conditions leads to the formation of aryl N‐aminosulfonamides. The reaction proceeds smoothly at room temperature and shows broad functional‐group tolerance. A radical process is proposed for this transformation.     

Sequence-Dependent DNA Functionalization of Upconversion Nanoparticles and Their Programmable Assemblies

DNA-modified lanthanide-doped upconversion nanoparticles (DNA-UCNPs) that combine the functions of DNA and the optical features of UCNPs have shown great promise in a wide range of fields. However, challenges remain in precisely tethering and orienting the DNA strands on the UCNP surface. Herein, we systematically investigate the sequence dependence of DNAs in their interactions with UCNPs, and reveal that poly-cytosine (poly-C) has high affinity for the UCNP surface. A general approach to synthesize monodispersed DNA-UCNP conjugates is developed using poly-C-containing diblock DNA strands. The poly-C segment of the DNA strand binds to the surfaces of UCNPs and the second segment is oriented perpendicularly on the UCNP surface, making the DNA-UCNPs highly stable and monodispersed in aqueous solution. The dense layer of DNA on the UCNP surface enables the programmable assembly of UCNPs with other DNA-functionalized nanoparticles or DNA origamis through hybridization, resulting in the formation of well-organized complex structures.     

An E1-Catalyzed Chemoenzymatic Strategy to Isopeptide-N-Ethylated Deubiquitylase-Resistant Ubiquitin Probes

Triazole-based deubiquitylase (DUB)-resistant ubiquitin (Ub) probes have recently emerged as effective tools for the discovery of Ub chain-specific interactors in proteomic studies, but their structural diversity is limited. A new family of DUB-resistant Ub probes is reported based on isopeptide-N-ethylated dimeric or polymeric Ub chains, which can be efficiently prepared by a one-pot, ubiquitin-activating enzyme (E1)-catalyzed condensation reaction of recombinant Ub precursors to give various homotypic and even branched Ub probes at multi-milligram scale. Proteomic studies using label-free quantitative (LFQ) MS indicated that the isopeptide-N-ethylated Ub probes may complement the triazole-based probes in the study of Ub interactome. Our study highlights the utility of modern protein synthetic chemistry to develop structurally and new families of tool molecules needed for proteomic studies.     

Tailoring A Poly(ether sulfone) Bipolar Membrane: Osmotic-Energy Generator with High Power Density

Osmotic energy, obtained through different concentrations of salt solutions, is recognized as a form of a sustainable energy source. In the past years, membranes derived from asymmetric aromatic compounds have attracted attention because of their low cost and high performance in osmotic energy conversion. The membrane formation process, charging state, functional groups, membrane thickness, and the ion-exchange capacity of the membrane could affect the power generation performance. Among asymmetric membranes, a bipolar membrane could largely promote the ion transport. Here, two polymers with the same poly(ether sulfone) main chain but opposite charges were synthesized to prepare bipolar membranes by a nonsolvent-induced phase separation (NIPS) and spin-coating (SC) method. The maximum power density of the bipolar membrane reaches about 6.2 W m⁻² under a 50-fold salinity gradient, and this result can serve as a reference for the design of bipolar membranes for osmotic energy conversion systems.