The oxygen sensitive properties of (LaBa)Co2O5+δ thin films fabricated by polymer-assisted deposition technique

(LaBa)Co₂O_5+δ (LBCO) thin films were successfully fabricated on Si (001) substrates by polymer-assisted deposition method. Microstructures were examined by X-ray diffraction technique, which confirmed the films were a single phase, pseudo cubic structure. The electrical transport properties of the films were investigated by the temperature dependence of films resistance, which suggested that LBCO films have typical semiconductor properties. After circle tests, the oxygen–hydrogen response rate did not show obvious variation in the specific temperature environment of 580 °C. This demonstrates that the LBCO thin films have a superior stability in both oxygen and hydrogen (6 % H₂, 94 % N₂) environment. Simultaneously, the drastic changes of films resistance (from ~10⁶ to ~10² Ω) with the switch of redox (O₂–H₂) environment within such a short time (~2.2 s) indicated that LBCO films have an excellent oxygen sensitive property and extraordinary fast surface exchange rate.     

紫外荧光硫分析仪用燃烧管的结构改进研究

对紫外荧光硫分析仪用石英燃烧管进行了结构改进,在原结构设计的基础上,增加了裂解氧预热管、挡板和氧气反吹口等。实验表明,相比于原结构设计的石英燃烧管进样量20μL和检出限0.2 mg/L,改进后的燃烧管进样量提高到了100μL,检出限达0.05 mg/L,线性范围为0.1～600 mg/L,相关系数大于0.999。采用改进后的燃烧管测定10.0 mg/L硫含量标准物质,其相对偏差为–1.5%～3.1%,测定结果的相对标准偏差为1.77%(n=10),两者均符合油品硫含量检测要求。改进后的燃烧管可替代市场上的其它国产石英燃烧管,进行油品中硫含量的测定。     

水浴加热密闭溶样石墨炉原子吸收光谱法测定化探样品中的痕量金

以王水、氟化钾、Fe3+溶液为溶剂,对化探样品进行水浴加热分解1.5 h,经泡沫塑料吸附后,于90℃以上硫脲溶液中解吸20 min,然后采用石墨炉原子吸收光谱仪测定其中的金含量。对仪器分析条件进行了优化。金的质量分数在0.1~100.0 ng/g范围内与吸光度呈良好的线性,线性相关系数r2=0.999 3,检出限为0.100 ng/g。该方法对金标准物质测定结果的相对标准偏差为5.96%~9.25%(n=12),对国家一级标准物质进行分析,测定结果与标准值相符合。该方法满足1∶50 000化探样品中痕量金的分析要求。     

Helical Toroids Self-Assembled from a Binary System of Polypeptide Homopolymer and its Block Copolymer

Toroids and helices are fundamental geometrical structures in nature. Polymers can self-assemble into various nanostructures, including both toroids and helices; however, nanostructures combining toroidal and helical morphologies (that is, helical toroids) are rarely observed. A binary system is reported containing polypeptide homopolymer and its block copolymer, which can hierarchically self-assemble into uniform helical nanotoroids in solution. The formation of the helical toroids is a successive two-step process. First, the homopolymers aggregate into fibrils and convolve into toroids, thereby resembling the toroidal condensation of deoxyribonucleic acid (DNA) chains. Second, the block copolymers self-assemble on the homopolymer toroids and result in helical surface patterns. Additionally, the chirality of the surface helical patterns can be varied by the chirality of the polypeptide block copolymers.     

A Biomimetic Nanoparticle to “Lure and Kill” Phospholipase A2

Inhibition of phospholipase A2 (PLA2) has long been considered for treating various diseases associated with an elevated PLA2 activity. However, safe and effective PLA2 inhibitors remain unavailable. Herein, we report a biomimetic nanoparticle design that enables a “lure and kill” mechanism designed for PLA2 inhibition (denoted “L&K-NP”). The L&K-NPs are made of polymeric cores wrapped with modified red blood cell membrane with two inserted key components: melittin and oleyloxyethyl phosphorylcholine (OOPC). Melittin acts as a PLA2 attractant that works together with the membrane lipids to “lure” in-coming PLA2 for attack. Meanwhile, OOPC acts as inhibitor that “kills” PLA2 upon enzymatic attack. Both compounds are integrated into the L&K-NP structure, which voids toxicity associated with free molecules. In the study, L&K-NPs effectively inhibit PLA2-induced hemolysis. In mice administered with a lethal dose of venomous PLA2, L&K-NPs also inhibit hemolysis and confer a significant survival benefit. Furthermore, L&K-NPs show no obvious toxicity in mice. and the design provides a platform technology for a safe and effective anti-PLA2 approach.     

Regulating Charge Transfer of Lattice Oxygen in Single-Atom-Doped Titania for Hydrogen Evolution

Single-atom catalysts have attracted much attention. Reported herein is that regulating charge transfer of lattice oxygen atoms in serial single-atom-doped titania enables tunable hydrogen evolution reaction (HER) activity. First-principles calculations disclose that the activity of lattice oxygen for the HER can be regularly promoted by substituting its nearest metal atom, and doping-induced charge transfer plays an essential role. Besides, the realm of the charge transfer of the active site can be enlarged to the second nearest atom by creating oxygen vacancies, resulting in further optimization for the HER. Various single-atom-doped titania nanosheets were fabricated to validate the proposed model. Taking advantage of the localized charge transfer to the lattice atom is demonstrated to be feasible for realizing precise regulation of the electronic structures and thus catalytic activity of the nanosheets.     

Monochromophore-Based Phosphorescence and Fluorescence from Pure Organic Assemblies for Ratiometric Hypoxia Detection

Hypoxia is a parameter related to many diseases. Ratiometric hypoxia probes often rely on a combination of an O₂-insensitive fluorophore and an O₂-sensitive phosphor in a polymer matrix, which require high cost and multi-step synthesis of transition metal complexes. The two-chromophore hypoxia probes encounter unfavorable energy transfer processes and different stabilities of the chromophores. Reported herein is a pure organic ratiometric hypoxia nanoprobe, assembled by a monochromophore, naphthalimide ureidopyrimidinone (BrNpA-UPy), bridged by a bis-UPy-functionalized benzyl skeleton. The joint factors of quadruple hydrogen bonding, the rigid backbone of UPy, and bromine substitution of the naphthalimide derivative facilitate bright phosphorescence (Φ_P=7.7 %, τ_P=3.2 ms) and fluorescence of the resultant nanoparticles (SNPs) at room temperature, which enable accurate, ratiometric, sensitive oxygen detection (K_sv=189.6 kPa⁻¹) in aqueous solution as well as in living HeLa cells.     

Natural Soft/Rigid Superlattices as Anodes for High-Performance Lithium-Ion Batteries

Volume expansion and poor conductivity are two major obstacles that hinder the pursuit of the lithium-ion batteries with long cycling life and high power density. Herein, we highlight a misfit compound PbNbS₃ with a soft/rigid superlattice structure, confirmed by scanning tunneling microscopy and electrochemical characterization, as a promising anode material for high performance lithium-ion batteries with optimized capacity, stability, and conductivity. The soft PbS sublayers primarily react with lithium, endowing capacity and preventing decomposition of the superlattice structure, while the rigid NbS₂ sublayers support the skeleton and enhance the migration of electrons and lithium ions, as a result leading to a specific capacity of 710 mAh g⁻¹ at 100 mA g⁻¹, which is 1.6 times of NbS₂ and 3.9 times of PbS. Our finding reveals the competitive strategy of soft/rigid structure in lithium-ion batteries and broadens the horizons of single-phase anode material design.     

Accelerating Crystallization of Open Organic Materials by Poly(ionic liquid)s

The capability to significantly shorten the synthetic period of a broad spectrum of open organic materials presents an enticing prospect for materials processing and applications. Herein we discovered 1,2,4-triazolium poly(ionic liquid)s (PILs) could serve as a universal additive to accelerate by at least one order of magnitude the growth rate of representative imine-linked crystalline open organics, including organic cages, covalent organic frameworks (COFs), and macrocycles. This phenomenon results from the active C5-protons in poly(1,2,4-triazolium)s that catalyze the formation of imine bonds, and the simultaneous salting-out effect (induced precipitation by decreasing solubility) that PILs exert on these crystallizing species.     

Metal–Organic Framework Membrane Nanopores as Biomimetic Photoresponsive Ion Channels and Photodriven Ion Pumps

Biological ion channels and ion pumps with sub-nanometer sizes modulate ion transport in response to external stimuli. Realizing such functions with sub-nanometer solid-state nanopores has been an important topic with wide practical applications. Herein, we demonstrate a biomimetic photoresponsive ion channel and photodriven ion pump using a porphyrin-based metal–organic framework membrane with pore sizes comparable to hydrated ions. We show that the molecular-size pores enable precise and robust optoelectronic ion transport modulation in a broad range of concentrations, unparalleled with conventional solid-state nanopores. Upon decoration with platinum nanoparticles to form a Schottky barrier photodiode, photovoltage across the membrane is generated with “uphill” ion transport from low concentration to high concentration. These results may spark applications in energy conversion, ion sieving, and artificial photosynthesis.