High-Purity Ethylene Production from Ethane/Ethylene Mixtures at Ambient Conditions by Ethane-Selective Fluorine-Doped Activated Carbon Adsorbents.

Energy-efficient separation of light alkanes from alkenes is considered as one of the most important separations of the chemical industry today due to the high energy penalty associated with the applied conventional cryogenic technologies. This study introduces fluorine-doped activated carbon adsorbents, where elemental fluorine incorporation into the carbon matrix plays a unique role in achieving high ethane selectivity. This enhanced selectivity arises from specific interactions between surface-doped fluorine atoms and ethane molecules, coupled with porosity modulation.

Stabilizing Contorted Doubly-Reduced Tetraphenylene with Heavy Alkali Metal Complexation: Crystallographic and Theoretical Evidence.

The two-fold reduction of tetrabenzo[a,c,e,g]cyclooctatetraene (TBCOT, or tetraphenylene, 1) with K, Rb, and Cs metals reveals a distinctive core transformation pathway: a newly formed C-C bond converts the central eight-membered ring into a twisted core with two fused five-membered rings. This C-C bond of 1.589(3)-1.

Aminoalkylation of Alkenes Enabled by Triple Radical Sorting.

The direct synthesis of C(sp)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there is a strong impetus to develop new methods by which to access sp-rich molecules from commercial feedstocks, such as alkenes.

ICT-based fluorescent nanoparticles for selective cyanide ion detection and quantification in apple seeds.

In this report, we successfully engineered a novel probe based on an acceptor-donor-acceptor (A-D-A) architecture featuring dicyanovinyl-substituted thieno[3,2-]thiophene, termed DCVTT. The designed probe self-assembles into luminous nanoparticles (DCVTT NPs) upon introducing mixed aqueous solutions. These fluorescent nanostructures served as a ratiometric probe for detecting cyanide (CN) ions in aqueous-based environments, owing to the robust Intramolecular Charge Transfer (ICT) characteristics of DCVTT.

Parallel Proteomic and Transcriptomic Microenvironment Mapping (μMap) of Nuclear Condensates in Living Cells.

Cellular activity is spatially organized across different organelles. While several structures are well-characterized, many organelles have unknown roles. Profiling biomolecular composition is key to understanding function but is difficult to achieve in the context of small, dynamic structures.

Ultrasonic treatment-assisted reductive deposition of Cu and Pd nanoparticles on ultrathin 2D BiS nanosheets for selective electrochemical reduction of CO into C compounds.

In this work, we have ultrasonically deposited Cu and Pd nanoparticles on BiS nanoparticles, prepared using an ultrasonication assisted hydrothermal method. We implemented intense ultrasonic waves bearing frequency of 20 kHz and power of 750 W at the acoustic wavelength of 100 mm to reduce Cu and Pd nanoparticles on the BiS surface. The XRD confirmed the formation of highly crystalline BiS nanoparticles with a pure orthorhombic phase and the deposition of copper (Cu) and palladium (Pd) nanoparticles was indicated by the strengthening and broadening of the peaks.

Recent advances in heterogeneous porous Metal-Organic Framework catalysis for Suzuki-Miyaura cross-couplings.

Suzuki-Miyaura coupling (SMC), a crucial C-C cross-coupling reaction, is still associated with challenges such as high synthetic costs, intricate work-ups, and contamination with homogeneous metal catalysts. Research intensely focuses on strategies to convert homogeneous soluble metal catalysts into insoluble powder solids, promoting heterogeneous catalysis for easy recovery and reuse as well as for exploring greener reaction protocols. Metal-Organic Frameworks (MOFs), recognized for their high surface area, porosity, and presence of transition metals, are increasingly studied for developing heterogeneous SMC.

Solvent Effects and Internal Functions Control Molecular Recognition of Neutral Substrates in Functionalized Self-Assembled Cages.

suite of internally functionalized FeL cage complexes has been synthesized with lipophilic end groups to allow dissolution in varied solvent mixtures, and the scope of their molecular recognition of a series of neutral, nonpolar guests has been analyzed. The lipophilic end groups confer cage solubility in solvents with a wide range of polarities, from hexafluoroisopropanol (HFIP) to tetrahydrofuran, and the hosts show micromolar affinities for neutral guests, despite having no flat panels enclosing the cavity. These hosts allow interrogation of the effects of an internal functional group on guest binding properties, as well as solvent-based driving forces for recognition.

Electronic Desymmetrization of Cu(μ-E) Clusters (E = S, Se) Induced by Edge-to-Face π-Stacking Interactions in the Second Coordination Sphere.

A pair of cyclophane-encapsulated [Cu(μ-E)] complexes (E = S and Se) were characterized by resonant X-ray diffraction anomalous fine structure (DAFS), revealing unexpected polarization among the three Cu sites attributed to long-range effects of π-stacking interactions with cocrystallized benzene molecules. The resonant K-edge energies of individual Cu sites within the cluster molecules were found to vary as a function of distance from the cocrystallized benzene. This pattern was interpreted in the context of T-shaped, edge-to-face π-stacking with the assistance of theoretical charge density difference calculations.

Heteroatom-Based Ligand Engineering of Metal Organic Frameworks for Efficient and Robust Electrochemical Water Oxidation.

Metal-organic frameworks (MOFs) are promising catalysts for the electrochemical oxygen evolution reaction (OER) due to their high surface area, tunable pore structures, and abundant active sites. Ligand engineering is an important strategy to optimize their performance. Here, we report the synthesis of NiFe-MOFs based on three different ligands: 1,4-terephthalic acid (BDC), 2,4-thiophene dicarboxylic acid (TDC), and 2,5-furandicarboxylic acid (FDC), to investigate the effects of heteroatom-based aromatic rings on OER performance.

Ammonia electro-oxidation on nickel hydroxide: phases, pH and poisoning.

Nickel hydroxide is a leading alternative to platinum group metals for electrocatalysis of the ammonia oxidation reaction (AOR), an important process for energy conversion and environmental remediation. Nevertheless, the dependence of AOR electrocatalysis on the different crystalline phases at the electrode surface (α-Ni(OH)/γ-NiOOH β-Ni(OH)/β-NiOOH) has never been investigated. Herein, the crystalline β-Ni(OH) and the disordered α-Ni(OH) were synthesized and characterized by XRD, HRSEM, and Raman and FTIR spectroscopies.

Sensitive electrochemical sensor of levofloxacin using boron-doped diamond (BDD) electrode modified with TiCT (MXene) material.

Overuse of levofloxacin (LEV) is often associated with bacterial resistance and serious health problems, underscoring the need for reliable sensing and monitoring of LEV molecules. Therefore, this study aimed to investigate LEV using boron-doped diamond (BDD) and boron-doped diamond modified with MXene (TiCT) (BDD-MXene) electrode. The successful deposition of MXene on the BDD surface was confirmed using scanning electron microscope (SEM).

Electrochemical immunosensor for the predictive cancer biomarker SLFN11 using reduced graphene oxide/MIL-101(Cr)-NH composite.

SLFN11 is a predictive cancer biomarker essential for identifying tumors that are sensitive to DNA-damaging agents, facilitating more personalized and effective treatment approaches. Detecting this biomarker can guide therapeutic decisions and improve outcomes for cancer patients. However, existing detection methods for SLFN11 are complex and require advanced techniques.

Ga-doped ZnO nanoparticles for enhanced CO gas sensing applications.

Gallium-doped zinc oxide (GZO) has demonstrated significant potential in gas-sensing applications due to its enhanced electrical and chemical properties. This study focuses on the synthesis, characterization, and gas-sensing performance of GZO nanoparticles (NPs), specifically targeting CO₂ detection, which is crucial for environmental monitoring and industrial safety. The GZO samples were synthesized using a sol-gel method, and their crystal structure was determined through X-ray diffraction (XRD), confirming the successful incorporation of gallium into the ZnO lattice.

N Dissociation vs Reversible 1,2-Methyl Migration in PCP Cobalt(I) Complexes in the Stereoselective Isomerization () of Allyl Ethers.

With growing efforts pushing toward sustainable catalysis, using earth-abundant metals has become increasingly important. Here, we present the first examples of cobalt PCP pincer complexes that demonstrate dual stereoselectivity for allyl ether isomerization. While the cationic cobalt complex [((PCP)Co)-μ-N][BAr ] () mainly favors the -isomer of the enol ether, the corresponding methyl complex [(PCP)CoMe] () mostly gives the -isomer.

Iron-Catalyzed Cross-Electrophile Coupling for the Formation of All-Carbon Quaternary Centers.

Quaternary carbon centers are desirable targets for drug discovery and complex molecule synthesis, yet the synthesis of these motifs within traditional cross-coupling paradigms remains a significant challenge due to competing β-hydride elimination pathways. In contrast, the bimolecular homolytic substitution (S2) mechanism offers a unique and attractive alternative pathway. Metal porphyrin complexes have emerged as privileged catalysts owing to their ability to selectively form primary metal-alkyl complexes, thereby eliminating the challenges associated with tertiary alkyl complexation with a metal center.

Stereoselective Synthesis of 1,n-Dicarbonyl Compounds Through Palladium-Catalyzed Ring Opening/Isomerization of Densely Substituted Cyclopropanols.

We report a highly diastereoselective protocol for the synthesis of 1,4- and 1,5-dicarbonyl compounds from densely substituted cyclopropanols. The methodology involves a palladium-catalyzed ring opening reaction followed by a "metal-walk" and oxidation of a remote hydroxyl group. The methodology represents a new application of cyclopropanols as initiation sites for chain walking remote functionalization.

μMap-Interface: Temporal Photoproximity Labeling Identifies F11R as a Functional Member of the Transient Phagocytic Surfaceome.

Phagocytosis is usually carried out by professional phagocytic cells in the context of pathogen response or wound healing. The transient surface proteins that regulate phagocytosis pose a challenging proteomics target; knowledge thereof could lead to new therapeutic insights. Herein, we describe a novel photocatalytic proximity labeling method: "μMap-Interface", allowing for spatiotemporal mapping of phagocytosis.

Modulating Core Polarity in Metal-free Covalent Organic Frameworks for Selective Electrocatalytic Hydrogen Peroxide Production.

Tuning the charge density at the active site to balance the adsorption ability and reactivity of oxygen is extremely significant for driving a two-electron oxygen reduction reaction (ORR) to produce hydrogen peroxide (HO). Herein, we have highlighted the influence of intermolecular polarity in covalent organic frameworks (COFs) on the efficiency and selectivity of electrochemical HO production. Different C3 symmetric building blocks have been utilized to regulate the charge density at the active sites.

Stereochemical Impacts on Acyclic Mechanochemical Carbon-Carbon Bond Activation.

The influence of stereochemistry on the mechanochemistry rate is studied using a new mechanophore based on a benzopinacol (BP) skeleton. Two sets of BP diastereomers, the meso R,S and the R,R/S,S were isolated, incorporated into the center of a poly(methyl acrylate), and their mechanical activation rate was measured in solution. Under mechanical stress, the central C-C bond in BP is cleaved, providing two independent benzophenone molecules with higher UV-absorption coefficient at 254 nm.

Exploring nanoparticle dynamics in binary chemical reactions within magnetized porous media: a computational analysis.

Artificial Neural Networks are incredibly efficient at handling complicated and nonlinear mathematical problems, making them very useful for tackling these challenges. Artificial neural networks offer a special computational architecture that is extremely valuable in disciplines like biotechnology, biological computing, and computational fluid dynamics. The present work investigates the applicability of back-propagation artificial neural networks in conjunction with the Levenberg-Marquardt algorithm for evaluating heat transmission in hybrid nanofluids.

Triboelectric nanogenerator based on silane-coupled LTA/PDMS for physiological monitoring and biomechanical energy harvesting.

Energy harvesting from ambient sources present in the environment is essential to replace traditional energy sources. These strategies can diversify the energy sources, reduce maintenance, lower costs, and provide near-perpetual operation of the devices. In this work, a triboelectric nanogenerator (TENG) based on silane-coupled Linde type A/polydimethylsiloxane (LTA/PDMS) is developed for harsh environmental conditions.

Isocyanide Substituent Influences Reductive Elimination versus Migratory Insertion in Reaction with an [Fe(μ-H)] Complex.

Iron hydrides are proposed reactive intermediates for N and CO conversion in industrial and biological processes. Here, we report a reactivity study of a low-coordinate di(μ-hydrido)diiron(II) complex, Fe(μ-H), where is a bis(β-diketiminate) cyclophane, with isocyanides, which have electronic structures related to N and CO. The reaction outcome is influenced by the isocyanide substituent, with 2,6-xylyl isocyanide leading to H loss, to form a bis(μ-1,1-isocyanide)diiron(I) complex, whereas all of the other tested isocyanides insert into the Fe-H bond to give (μ-1,2-iminoformyl) complexes.