Chemistry methods : new approaches to solving problems in chemistry最新文献

Herein, the use of solvatochromic fluorescent probes for detecting polarity in cellular microenvironments, a complex physicochemical parameter that influences various biological processes, is reviewed. The nature of polarity itself is related to the physicochemical properties of the environment that affect the spectroscopic properties of luminophores. The mechanisms of solute–solvent interactions and photophysical processes, such as intramolecular charge transfer and photoinduced electron transfer, which are fundamental to understanding the response of the probes to polarity changes are discussed. In the intracellular context, solvatochromic probes have been used to determine polarity in different organelles and subcellular structures. The review puts emphasis on the various targeting strategies and the most commonly utilized photophysical parameters for estimating polarity are focused here. A special attention is paid to those approaches capable of providing absolute quantification of intracellular polarity, for instance, through ratiometric measurements or the use of fluorescence lifetime imaging to improve the accuracy of measurements. Reliable intracellular polarity measurements may provide invaluable information to understand physiological and pathological processes, including neurodegenerative diseases or cancer.

Atomically precise metal clusters have demonstrated significant advantages in homogeneous catalysis, heterogeneous catalysis, electronic catalysis, and photocatalysis. As much, electrocatalytic reduction of nitrate pollution into valuable compounds is a low-energy consumption and environmentally friendly route, which combines environmental and economic advantages by efficiently eliminating pollutant and recycling waste. This review systematically summarizes the current researches on atomically precise metal clusters in the electroreduction of nitrate to produce high-valued chemicals such as ammonia, urea, cyclohexanone oxime, and amino acids. The emphasis on the complexed reaction pathways and key intermediates involved in the conversion of nitrate into different target products is studied. The relationship between the structure of metal clusters and catalytic properties is delved into. This review aims to provide valuable insights for the design of high-performance metal cluster catalysts to achieve efficient conversion from nitrate to high-value-added chemicals.

Vapor phase metalation (VPM) via atomic layer deposition is emerging as a sustainable, solvent-free method for precise material functionalization. This study demonstrates selective zinc metalation of multilayered (NH₄)₂V₇O1₁₆ nanostructured squares using diethylzinc (DEZ) as a volatile precursor. A sequence of samples—(HDA)V₇O₁₆·nH₂O (S-1), (NH₄)₂V₇O₁₆·nH₂O (S-2), iodine-functionalized (S-3), and Zn-metalated (S-4)—was characterised via XRD, HRTEM/SAED, FIB-SEM, ESEM, ATR-FTIR, Raman microscopy, and XPS. The V7₇O₁₆ bilayer framework revealed a triclinic crystal structure (P-1 space group) for the first time. VPM enabled the transformation into Zn₃V3₃O₈ and wurtzite ZnO nanoparticles with structural precision and minimal waste. Metalation was achieved from a single half-cycle (210 seconds total), allowing fine control over deposition dynamics. This process also induced a magnetic transition from spin-frustrated semiconducting behavior to ferrimagnetism. The results underscore VPM's potential for low-impact, high-precision synthesis of multifunctional oxides, aligning with circular economy principles by reducing waste and enhancing recyclability. Applications span spintronics, neuromorphic computing, and sustainable catalysis.

Lipidation, such as S-palmitoylation, is an important, reversible post-translational modification of proteins determining not only their stability and folding but also their interactions with other proteins or membranes. However, in contrast to other post-translational modifications, lipidation is less explored, and lipidated proteins are underrepresented in large-scale studies. To advance the analysis of S-palmitoylation by mass spectrometry (MS), a model peptide containing four potential modification sites is selected. By selectively introducing S-palmitoylation, a set of multiply modified peptides is generated, differing in the sites as well as the degree of modification. Importantly, the solubility of the peptides decreased tremendously with increasing degree of modification, requiring the use of alternative solvents. Nonetheless, using direct-infusion MS, the ionization and fragmentation behavior of the differently modified peptides is characterized. Lipidation is found to be stable during tandem MS, and the sites of modification can be unambiguously identified. The use of dimethyl sulfoxide during electrospray ionization further improves the signal intensity of multiply modified peptides. In summary, the identification of S-palmitoylation even in multiply modified peptides is possible; however, further improvements are required for large-scale analyses.

Knowledge-based catalyst design requires the identification of the active structure during reaction, i.e., by operando spectroscopy, and at different conversion levels. However, for reactions that run at elevated pressure, such as methanol, Fischer–Tropsch, or ammonia synthesis, obtaining spectroscopic data at realistic conditions remains a major challenge. In particular, standard operando setups often fail to replicate the high-pressure, high-conversion regimes relevant to industrial processes. This requires specially designed reactors, and here, how additive manufacturing enables the development of spectroscopic reactors for operando studies of catalysts under high-pressure conditions at different conversion levels up to equilibrium is reported. The reactor has two consecutive zones with independent temperature control and individual catalyst loading. An X-ray-transparent window in the latter zone allows for spatially resolved spectroscopic monitoring of the catalyst structure. A mobile setup is constructed for operation at a synchrotron source, and the functionality of the reactor is demonstrated in an operando X-ray absorption spectroscopy study using a Cu/ZnO/ZrO₂ catalyst during CO₂ hydrogenation to methanol. The dual-zone design enabled simulation of an end-of-catalyst-bed environment, including condensation, which is highly critical for industrial relevance yet difficult to realize in conventional operando experiments.

A chemo-divergent Friedel–Crafts alkylation and Friedel–Crafts acylation of arenes with α-diazo ketones has been developed. In this reaction, Cu(OTf)₂ catalyzed the Friedel–Crafts alkylation via Cu-carbene intermediate, while hexafluoroisopropanol (HFIP) promoted the Friedel–Crafts acylation via the ketene intermediate. This protocol provides a controllable aromatic C(sp2)H bond functionalization of arenes by tuning the reaction conditions.

Herein, the design and validation of high-throughput experimentation reactor and modular environment for synthesis (HERMES), a 3D-printed photoreactor capable of running 24 reactions simultaneously, employing a standard reaction block and a single Kessil lamp are reported. The reactor features stirring and temperature control modules, making it an efficient tool for photochemical research in academic environments. It provides an accessible and reproducible platform for accelerating reaction discovery and optimization, while also serving as a valuable training tool in high-throughput experimentation (HTE).

Reducing atmospheric CO₂ is crucial for mitigating climate change and ensuring a sustainable future. The building sector is a major contributor, consuming 40% of global raw materials and accounting for 35% of global energy consumption. As a result, there is a growing demand for more sustainable building materials. Herein, a scalable, energy-efficient, and low-emission approach is presented to convert various waste streams into building materials via carbon mineralization and 3D printing. Calcium ions are extracted from recycled concrete using ammonium salt leaching methods and then reacted with CO₂ gas to form high-purity calcium carbonate through mineralization. This calcium carbonate is formulated into a bio-based mineral binder by incorporating kraft lignin as a rheological modifier. The binder is further combined with sawdust to produce printable inks for additive manufacturing. The resulting 3D-printed structures demonstrate robust mechanical properties and modular design potential, making them suitable for non-load-bearing building applications. By integrating CO₂ sequestration and renewable materials, this work demonstrates a closed-loop strategy for carbon capture, waste valorization, and digital fabrication, providing a new avenue for decarbonizing the built environment.

The catalytic hydrogenation of oxalic acid to glycolic acid (GA) and/or ethylene glycol (EG) has been identified as a promising route for producing value-added chemicals and potential hydrogen carriers. GA serves as a precursor for plastics and cosmetics, while EG can function as a liquid organic hydrogen carrier. In this work, an eco-friendly and scalable bottom-up approach to fabricate a Ru-based hydrogenation catalyst on θ-alumina-coated SiC foam is presented. Nitrogen doping of the MOF(Al)-based template enhances the mechanochemical stability of the resulting alumina coating by significantly modifying its surface texture and morphology. This phase-stabilization method enables higher OA conversion compared to γ-alumina and yields nearly equimolar amounts of GA and EG under continuous-flow conditions (120 °C, 50 bar). These findings demonstrate the potential of this synthesis approach for producing stabilized metal oxide phases with tailored morphologies that improve catalyst performance.

The production and widespread use of synthetic pigments and dyes have significant environmental and health impacts. Despite this, synthetic colorants remain dominant due to their wide color range, high stability, strong tinting power, and lower cost compared to natural alternatives. Therefore, to offer sustainable and competitive substitutes, eco-friendly methods for producing bio-based pigments with similar performance are essential. Herein, a methodology has been developed to extract the entire colored organic fraction occluded within seashell biomineral waste, which comprises pigments and pigment-macromolecule complexes. This process involves an optimized cleaning procedure of the biomineral soft tissues, a tailored biochemical extraction, and detailed characterization of the extracted fraction. Applied to sea urchin skeletons, this method successfully isolates polyhydroxylated naphthoquinone (PHNQ)-macromolecule complexes. These complexes show superior pH stability in purple hues compared to free PHNQ, which shifts from red to purple in basic conditions. Notably, the approach enhances colorant yield by up to five times. These results, together with mineral pigment synthesis and fabric dyeing assays performed with the extracted colored organic fraction, contribute to a better understanding of the origin of color in biominerals and reveal the versatility of these natural pigments for environmentally friendly coloring of both organic and inorganic materials.