Hybrid Rhodamine Fluorophores in the Visible/NIR Region for Biological Imaging

Fluorophores and probes are invaluable for the visualization of the location and dynamics of gene expression, protein expression, and molecular interactions in complex living systems. Rhodamine dyes are often used as scaffolds in biological labeling and turn‐on fluorescence imaging. To date, their absorption and emission spectra have been expanded to cover the entire near‐infrared region (650–950 nm), which provides a more suitable optical window for monitoring biomolecular production, trafficking, and localization in real time. This review summarizes the development of rhodamine fluorophores since their discovery and provides strategies for modulating their absorption and emission spectra to generate specific bathochromic‐shifts. We also explain how larger Stokes shifts and dual‐emissions can be obtained from hybrid rhodamine dyes. These hybrid fluorophores can be classified into various categories based on structural features including the alkylation of amidogens, the substitution of the O atom of xanthene, and hybridization with other fluorophores.     

[(NHC)NiIIH]‐Catalyzed Cross‐Hydroalkenylation of Cyclopropenes with Alkynes: Cyclopentadiene Synthesis by [(NHC)NiII]‐Assisted C−C Rearrangement

A cross‐hydroalkenylation/rearrangement cascade (HARC), using a cyclopropene and alkyne as substrate pairs, was achieved for the first time by using new [(NHC)Ni(allyl)]BAr^F catalysts (NHC=N‐heterocyclic carbenes). By controlling the (NHC)Ni^IIH relative insertion reactivity with cyclopropene and alkyne, a broad scope of cyclopentadienes was obtained with highly selectively. The structural features of the new (NHC)Ni^II catalyst were important for the success of the reaction. The mild reaction conditions employed may serve as an entry for exploring (NHC)Ni^II‐assisted vinylcyclopropane rearrangement reactivity.     

Chemistry Design Towards a Stable Sulfide‐Based Superionic Conductor Li4Cu8Ge3S12

Sulfide‐based superionic conductors with high ionic conductivity have been explored as candidates for solid‐state Li batteries. However, moisture hypersensitivity has made their manufacture complicated and costly and also impeded applications in batteries. Now, a sulfide‐based superionic conductor Li₄Cu₈Ge₃S₁₂ with superior stability was developed based on the hard/soft acid–base theory. The compound is stable in both moist air and aqueous LiOH aqueous solution. The electrochemical stability window was up to 1.5 V. An ionic conductivity of 0.9×10^?4 S cm with low activation energy of 0.33 eV was achieved without any optimization. The material features a rigid Cu‐Ge‐S open framework that increases its stability. Meanwhile, the weak bonding between Li⁺ and the framework promotes ionic conductivity. This work provides a structural configuration in which weak Li bonding in the rigid framework promotes an environment for highly conductive and stable solid‐state electrolytes.     

Ultra‐Tough Inverse Artificial Nacre Based on Epoxy‐Graphene by Freeze‐Casting

Epoxy nanocomposites combining high toughness with advantageous functional properties are needed in many fields. However, fabricating high‐performance homogeneous epoxy nanocomposites with traditional methods remains a great challenge. Nacre with outstanding fracture toughness presents an ideal blueprint for the development of future epoxy nanocomposites. Now, high‐performance epoxy‐graphene layered nanocomposites were demonstrated with ultrahigh toughness and temperature‐sensing properties. These nanocomposites are composed of ca. 99 wt % organic epoxy, which is in contrast to the composition of natural nacre (ca. 96 wt % inorganic aragonite). These nanocomposites are named an inverse artificial nacre. The fracture toughness reaches about 4.2 times higher than that of pure epoxy. The electrical resistance is temperature‐sensitive and stable under various humidity conditions. This strategy opens an avenue for fabricating high‐performance epoxy nanocomposites with functional properties.     

Nanopore Sequencing Accurately Identifies the Mutagenic DNA Lesion O6‐Carboxymethyl Guanine and Reveals Its Behavior in Replication

O⁶‐carboxymethylguanine (O⁶‐CMG) is a highly mutagenic alkylation product of DNA, triggering transition mutations relevant to gastrointestinal cancer. However, precise localization of a single O⁶‐CMG with conventional sequencing platforms is challenging. Here nanopore sequencing (NPS), which directly senses single DNA bases according to their physiochemical properties, was employed to detect O⁶‐CMG. A unique O⁶‐CMG signal was observed during NPS and a single‐event call accuracy of >95 % was achieved. Moreover, O⁶‐CMG was found to be a replication obstacle for Phi29 DNA polymerase (Phi29 DNAP), suggesting this lesion could cause DNA sequencing biases in next generation sequencing (NGS) approaches.     

Electrochemical Monitoring of ROS/RNS Homeostasis Within Individual Phagolysosomes Inside Single Macrophages

The existence of a homeostatic mechanism regulating reactive oxygen/nitrogen species (ROS/RNS) amounts inside phagolysosomes has been invoked to account for the efficiency of this process but could not be unambiguously documented. Now, intracellular electrochemical analysis with platinized nanowire electrodes (Pt‐NWEs) allowed monitoring ROS/RNS effluxes with sub‐millisecond resolution from individual phagolysosomes impacting onto the electrode inserted inside a living macrophage. This shows for the first time that the consumption of ROS/RNS by their oxidation at the nanoelectrode surface stimulates the production of significant ROS/RNS amounts inside phagolysosomes. These results establish the existence of the long‐postulated ROS/RNS homeostasis and allows its kinetics and efficiency to be quantified. ROS/RNS concentrations may then be maintained at sufficiently high levels for sustaining proper pathogen digestion rates without endangering the macrophage internal structures.     

Atomic‐Scale Observation of the Metal–Promoter Interaction in Rh‐Based Syngas‐Upgrading Catalysts

The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO₂ utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic‐scale study of metal–promoter interactions in silica‐supported Rh, Rh–Mn, and Rh–Mn–Fe catalysts by aberration‐corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh–Mn/SiO₂ catalyst, the addition of Fe results in the formation of bimetallic Rh–Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided.     

Synergy between Plasmonic and Electrocatalytic Activation of Methanol Oxidation on Palladium–Silver Alloy Nanotubes

Localized surface plasmon resonance (LSPR) excitation of noble metal nanoparticles has been shown to accelerate and drive photochemical reactions. Here, LSPR excitation is shown to enhance the electrocatalysis of a fuel‐cell‐relevant reaction. The electrocatalyst consists of Pd_xAg alloy nanotubes (NTs), which combine the catalytic activity of Pd toward the methanol oxidation reaction (MOR) and the visible‐light plasmonic response of Ag. The alloy electrocatalyst exhibits enhanced MOR activity under LSPR excitation with significantly higher current densities and a shift to more positive potentials. The modulation of MOR activity is ascribed primarily to hot holes generated by LSPR excitation of the Pd_xAg NTs.     

顶空气相色谱法测定聚氯乙烯固体药用硬片中氯乙烯单体含量的测量不确定度评定

依据CNAS-GL06,对顶空气相色谱法测定聚氯乙烯固体药用硬片中氯乙烯单体含量的测量不确定度进行系统分析,找出影响测量结果不确定度的主要因素。对各不确定度分量进行了评定和量化,计算了合成标准不确定度和扩展不确定度,聚氯乙烯固体药用硬片中氯乙烯单体含量的测定结果表示为(4.17±0.18)×10-7,k=2。     

气相色谱质谱法测定植物油中脂肪酸

建立了气相色谱质谱法测定食用植物性油中脂肪酸检测的方法。植物油中的脂肪酸甘油酯在碱性条件下被水解为游离脂肪酸,随后采用三氟化硼将其转化为脂肪酸甲酯。采用同位素标记脂肪酸进行加标回收试验,回收率在94%以上。通过质谱的选择离子检测模式对硬脂酸、油酸、亚油酸等10种目标脂肪酸进行了检测,结果显示,该方法可用于油品的质量检测和日常分析。