Electrostatic Tailoring of Freestanding Polymeric Films for Multifunctional Thermoelectrics, Hydrogels, and Actuators.

Organic conducting polymer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) has garnered enormous attention in organic electronics due to its low-cost solution processability, highly tunable conductivity, superior mechanical flexibility, and good biocompatibility together with excellent atmospheric stability. Nevertheless, limited electrical properties and unfavorable water instability of pristine PEDOT:PSS film impede its further implementation in a broad spectrum of practical applications. In this work, the successful tailoring of the intrinsic electrostatic interaction within PEDOT:PSS and consequent optimized electrical properties are enabled by a simple yet effective ionic salt post-treatment strategy.

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).

Hydride-Induced Reconstruction of Pd Electrode Surfaces: A Combined Computational and Experimental Study.

Designing electrocatalysts with optimal activity and selectivity relies on a thorough understanding of the surface structure under reaction conditions. In this study, experimental and computational approaches are combined to elucidate reconstruction processes on low-index Pd surfaces during H-insertion following proton electroreduction. While electrochemical scanning tunneling microscopy clearly reveals pronounced surface roughening and morphological changes on Pd(111), Pd(110), and Pd(100) surfaces during cyclic voltammetry, a complementary analysis using inductively coupled plasma mass spectrometry excludes Pd dissolution as the primary cause of the observed restructuring.

Rim-brominated pillarplexes and their assembly self-sorting.

We report rim-brominated pillarplexes, new examples of functionalised supramolecular organometallic complexes (SOCs). The bromide atoms can be introduced to the established pristine ligand precursor, demonstrating late-stage diversification of our ligand platform. SC-XRD/ED-derived crystal structures of precursor and pillarplex salts are reported along with competitive assembly experiments of the Ag(I) pillarplex, showing narcissistic self-sorting behavior.

Hydrothermal Stability of Active Sites in Cu-Exchanged Small-Pore Zeolites for the Selective Catalytic Reduction of NO.

Combining operando X-ray absorption spectroscopy (XAS) and computational modelling shows unequivocally the distribution of active species in fresh and hydrothermally aged Cu-CHA and Cu-AEI zeolites during NH-assisted selective catalytic reduction of NO. Four principal species co-exist: (i) Cu cations coordinated to NH, (ii) Cu cations coordinated to the zeolite framework, (iii) solvated Cu cations, and (iv) framework-coordinated Cu species (Cu ) formed upon hydrothermal ageing of the zeolite sample. The Cu species were only observed in the hydrothermally aged zeolite samples and are formed upon the interaction of hydrated Cu cations with extra-framework Al (EFAl) generated during the hydrothermal treatment.

Trace Adsorptive Removal of PFAS from Water by Optimizing the UiO-66 MOF Interface.

The confluence of pervasiveness, bioaccumulation, and toxicity in freshwater contaminants presents an environmental threat second to none. Exemplifying this trifecta, per- and polyfluoroalkyl substances (PFAS) present an alarming hazard among the emerging contaminants. State-of-the-art PFAS adsorbents used in drinking water treatment, namely, activated carbons and ion-exchange resins, are handicapped by low adsorption capacity, competitive adsorption, and/or slow kinetics.

How to Assess and Predict Electrical Double Layer Properties. Implications for Electrocatalysis.

The electrical double layer (EDL) plays a central role in electrochemical energy systems, impacting charge transfer mechanisms and reaction rates. The fundamental importance of the EDL in interfacial electrochemistry has motivated researchers to develop theoretical and experimental approaches to assess EDL properties. In this contribution, we review recent progress in evaluating EDL characteristics such as the double-layer capacitance, highlighting some discrepancies between theory and experiment and discussing strategies for their reconciliation.

Co-Feeding CO for Methylfuran Aromatization over Bifunctional Zeolite-Supported ZnMoO.

Aromatization of biofuran offers promising approaches for sustainable biochemical production. However, this process is often hampered by low yields and severe coking on traditional zeolite catalysts. Herein, we report co-feeding CO for 2-methylfuran (MF) aromatization (CCMA) over bifunctional ZSM-5 supported ZnMoO.

Total Synthesis and Configuration Assignment of (+)-Myxoquaterine-450.

Myxoquaterines represent a recently discovered class of natural products with intriguing biological properties. They were isolated from Pendulasporacea albinea MSr 11954 and display a unique structure combining heterocyclic (pyrrole, oxazoline), hexaene, and 2-amino-1,3-diol subunits. We have now synthesized the first example of a myxoquaterine natural product, myxoquaterine-450, in a highly convergent fashion, in which the sensitive hexaene unit was established in the final stages of the synthesis (16 linear steps starting from l-serine).

London dispersion driven compaction of coordination cages in the gas-phase - a combined ion mobility and theoretical study.

Large self-assembled systems (such as metallosupramolecular rings and cages) can be difficult to structurally characterize, in particular when they show a highly dynamic behavior. In the gas-phase, Ion Mobility Spectrometry (IMS), in tandem with Electrospray Ionization Mass Spectrometry (ESI MS), can yield valuable insights into the size, shape and dynamics of such supramolecular assemblies. However, the detailed relationship between experimental IMS data and the actual gas-phase structure is still poorly understood for soft and flexible self-assemblies.

A Fast and Highly Stable Aqueous Calcium-Ion Battery for Sustainable Energy Storage.

Aqueous alkali-ion batteries are gaining traction as a low-cost, sustainable alternative to conventional organic lithium-ion batteries. However, the rapid degradation of commonly used electrode materials, such as Prussian Blue Analogs and carbonyl-based organic compounds, continues to challenge the economic viability of these devices. While stability issues can be addressed by employing highly concentrated water-in-salt electrolytes, this approach often requires expensive and, in many cases, fluorinated salts.

Silicon-aryl cooperative activation of ammonia.

Herein, we report the reactivity of N-heterocyclic carbene stabilized silylene-phosphinidene IDippPSi(TMS)SiTol (IDipp = 1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) with ammonia, which results in an intermolecular 1,5-hydroamination and dearomatization of the NHC wingtip. DFT calculations reveal an unprecedented mechanism involving ammonia coordination to the silicon center, Meisenheimer-type complex formation, and a proton abstraction by the dearomatized aryl moiety.

Photochemical Deracemization of N-Carboxyanhydrides En Route to Chiral α-Amino Acid Derivatives.

Readily accessible, racemic N-carboxyanhydrides (NCAs) of α-amino acids underwent a deracemization reaction upon irradiation at λ=366 nm in the presence of a chiral benzophenone catalyst. The enantioenriched NCAs (up to 98 % ee) serve as activated α-amino acid surrogates and, due to their instability, they were directly converted into consecutive products. N-Protected α-amino acid esters were obtained after reaction with MeOH and N-benzoylation (14 examples, 70 %-quant.

Design of an FPGA-Based Controller for Fast Scanning Probe Microscopy.

Atomic-scale imaging using scanning probe microscopy is a pivotal method for investigating the morphology and physico-chemical properties of nanostructured surfaces. Time resolution represents a significant limitation of this technique, as typical image acquisition times are on the order of several seconds or even a few minutes, while dynamic processes-such as surface restructuring or particle sintering, to be observed upon external stimuli such as changes in gas atmosphere or electrochemical potential-often occur within timescales shorter than a second. In this article, we present a fully redesigned field programmable gate array (FPGA)-based instrument that can be integrated into most commercially available standard scanning probe microscopes.

Impact of Ligand Design on an Iron NHC Epoxidation Catalyst.

An open-chain iron pyridine-NHC framework is expanded utilizing a benzimidazole moiety to deepen the understanding of the impact of electronic variations on iron NHC epoxidation catalysts, especially regarding the stability. The thereby newly obtained iron(II) NHC complex is characterized and employed in olefin epoxidation. It is remarkably temperature tolerant and achieves a TOF of ca.

Flavin-Catalyzed, Photochemical Conversion of Dehydroalanine into 4,5-Dihydroxynorvaline.

The chemical synthesis of unnatural amino acids (UAA) is a key strategy for preparing designed peptides, including pharmaceutically active compounds. Alterations of existing amino acid residues such as dehydroalanine (Dha) are particularly important since selected positions can be addressed without the necessity of a complete de novo synthesis. The intriguing UAA 4,5-dihydroxynorvaline (Dnv) is found in a variety of naturally occurring peptides and biologically active compounds.

Copper Imidazolin-imine Coordination Compounds as Precursors for a Cu/Al Complex.

The reactions of [(CFSOCu)(CH)] with the sterically hindered imidazolin-2-imine ligands DippImTMS (1,3-Bis(2,6-diisopropylphenyl)-2-(trimethylsilylimino)imidazoline) or DippImH (1,3-bis(2,6-diisopropylphenyl) imidazolin-2-imine) lead to the formation of the linear copper(I) complexes [Cu(DippImTMS)(OTf)] () and [Cu(DippImH)][OTf] (), respectively. The triflate counteranion in can be easily exchanged to the weakly coordinating [BAr] giving [Cu(DippImH)][BAr] () (BAr = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate). Substitution of the N-heterocyclic imine (NHI) ligand in by AlCp* (Cp* = pentamethylcyclopentadienyl) gives the tetrahedral [Cu(AlCp*)][BAr] ().

Isolation of a NHC-stabilized heavier nitrile and its conversion into an isonitrile analogue.

Nitriles (R-C≡N) have been investigated since the late eighteenth century and are ubiquitous encounters in organic and inorganic syntheses. In contrast, heavier nitriles, which contain the heavier analogues of carbon and nitrogen, are sparsely investigated species. Here we report the synthesis and isolation of a phosphino-silylene featuring an N-heterocyclic carbene-phosphinidene and a highly sterically demanding silyl group as substituents.

The influence of bulk stoichiometry on near-ambient pressure reactivity of bare and Pt-loaded rutile TiO(110).

The interaction of catalyst particles with reducible support materials can drastically change their reactivity. On rutile TiO, processes like particle encapsulation (caused by the "strong metal-support interaction", SMSI) have long been known to depend on the initial reduction state of the oxide. Despite this knowledge, sample stoichiometry has rarely been controlled in a reproducible manner in the surface science literature.