Surface Hydration and Antifouling Activity of Coatings of Polymers and Their Zwitterionic Derivatives Prepared Using Initiated Chemical Vapor Deposition (iCVD).

Sum frequency generation vibrational spectroscopy was applied to study the surface hydration and protein adsorption behavior on several polymer coatings based on pyridine, imidazole, and amine side groups along with vinyl or methacrylate backbones and their corresponding zwitterionic forms with carboxybetaine or sulfobetaine side chains, prepared by initiated chemical vapor deposition (iCVD). iCVD also enables facile tuning of the cross-linking density of the polymer coatings by blending in a cross-linker during the deposition, namely, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetrasiloxane. Our results show that both the low- and high-cross-linking density zwitterionic polymers exhibit significantly better antifouling activities compared to those of the polymers without the zwitterionic side chains.

Photoredox-Catalyzed Decarboxylation of Oxetane-2-Carboxylic Acids Initiated by Oxidation of DIPEA.

Oxetanes are valuable motifs in medicinal chemistry applications, with demonstrated potential to serve as bioisosteres for an array of functional groups. Through the visible-light-mediated photoredox hydrodecarboxylation of 2-aryl oxetane 2-carboxylic acids this work enables access to the products of a [2+2]-photocycloaddition between alkenes and aryl aldehydes without the challenges associated with a traditional UV-light-mediated Paternò-Büchi reaction. Investigation into the hydrodecarboxylation mechanism reveals substrate-dependent modes of initiation under the conditions reported herein.

Enhancing Confidence in Microplastic Spectral Identification via Conformal Prediction.

Microplastics are an emerging pollutant of concern, with environmental observations recorded across the world. Identifying the type of microplastic is challenging due to spectral similarities among the most common polymers, necessitating methods that can confidently distinguish plastic identities. In practice, a researcher chooses the reference vibrational spectrum that is most like the unknown spectrum, where the likeness between the two spectra is expressed numerically as the hit quality index (HQI).

Surfactants can compete with microplastics for surfaces using adhesives as substrates for microplastic sequestration.

Experimental efforts supplemented by modeling gauged whether common additives found in soaps and laundry detergents interfered with polyacrylate adhesive-based capture of microplastics. On the experimental front, poly(2-ethylhexyl acrylate) (PEHA) samples were evaluated using gravimetric analysis, probe tack, and functional assessments of adhesive-coated glass slides immersed into DI water solutions containing both microparticles and additives (solvents, softeners, and non-ionic surfactants). Nylon-6 spheres and polyethylene terephthalate microplastics were chosen for adsorption using a count-based method by ImageJ imaging analysis.

Synthesis of heteroleptic bis-phosphine bis-NHC iron (0) complexes: a strategy to enhance small molecule activation.

We report the synthesis of heteroleptic iron complexes supported by both a bis-phosphine ligand (depe) and a bis-NHC ligand. The mixed ligand sets provide access to iron (0) adducts of N and CO that are highly activated, in comparison to homoleptic ( Fe(depe)L) variants. Computational and experimental studies revealed the mixed ligand set distorts the geometric and electronic structure to yield an unusually basic iron.

Machine Learning Predictions of Methane Storage in MOFs: Diverse Materials, Multiple Operating Conditions, and Reverse Models.

A machine learning (ML) model is developed for predicting useable methane (CH) capacities in metal-organic frameworks (MOFs). The model applies to a wide variety of MOFs, including those with and without open metal sites, and predicts capacities for multiple pressure swing conditions. Despite its wider applicability, the model requires only 5 measurable structural features as input, yet achieves accuracies that surpass less-general models.

Strategies in photochemical alcohol oxidation on noble-metal free nanomaterials as heterogeneous catalysts.

Using light absorbing semiconductors to harvest solar energy has long been considered as a promising approach for driving chemical reactions. Photochemical oxidation of alcohols catalyzed by noble-metal free nanomaterials is particularly attractive due to the bio-derivable nature of the substrate and the wide availability of such catalysts. Here, a number of strategies that could facilitate the progress are discussed, where it is concluded that the photochemical alcohol oxidation process can benefit from both mechanistic optimization of the electron-transfer steps and structural engineering of the light-absorbing nanomaterials.

Probing the Saltwater Immersion Effect on Buried Interfacial Structures between a Sealant and Adhesion Promoter at the Molecular Level.

In this research, we used sum frequency generation vibrational spectroscopy to investigate the buried interface of a thiol-epoxy model aerospace sealant in contact with a silane-based adhesion promoter (6111) following exposures to 3% saltwater at elevated temperatures and elevated temperatures alone. The results suggest that the saltwater caused a change at the interface between the adhesion promoter and sealant, while an elevated temperature of 60 °C itself did not affect the interfacial structure noticeably. Model hydrolyzed and nonhydrolyzed silanes were also used in the study to compare with the adhesion promoter 6111 to understand the interfacial behavior of main silane components in 6111 as well as their potential role in adhesion.

Designed additive suppresses interpenetration in IRMOF-10.

IRMOF-10, derived from biphenyl-4,4'-dicarboxylic acid and zinc, is a prototype for an open cubic structure prone to interpenetration. Interpenetration can compromise MOF pore volume and surface area which drives the need to develop strategies to synthesize non-interpenetrated MOFs. In this work, an additive design strategy was employed to suppress interpenetration of IRMOF-10.

Solvent Exchange Dynamics in M(dobdc): An Interplay among Binding Strength, Exchange Kinetics, and Cooperativity.

Solvent exchange is a crucial step in ensuring the complete activation of metal-organic frameworks (MOFs); however, the conditions for solvent exchange vary among MOFs, even within the isostructural variants. This study examines the factors contributing to solvent exchange by investigating the isostructural M(dobdc) (M═Mg, Co, Zn) series. Common solvents ,-dimethylformamide (DMF), ethanol (EtOH), and methanol (MeOH) are employed to assess the solvent exchange at coordinatively unsaturated sites (CUS) of M(dobdc).

Speciation and Reactivity of Mono- and Binuclear Ni Intermediates in Aminoquinoline-Directed C-H Arylation and Benzylation.

This paper describes detailed organometallic studies of the aminoquinoline-directed Ni-catalyzed C-H functionalization of 2,3,4,5-tetrafluoro--(quinolin-8-yl)benzamide with diaryliodonium reagents. A combination of F NMR spectroscopy and X-ray crystallography is used to track and characterize diamagnetic and paramagnetic intermediates throughout this transformation. These provide key insights into both the cyclometalation and oxidative functionalization steps of the catalytic cycle.

An evaluation of resolution, accuracy, and precision in FT-IR spectroscopy.

Infrared spectroscopy is a foundational technique for the elucidation of chemical structures. The advancements in interferometric spectroscopy, and specifically the development of Fourier transform infrared (FT-IR) spectroscopy, are responsible for the widespread usage of IR spectrometers ranging from teaching labs to pharmaceutical quality control. FT-IR affords an excellent signal-to-noise ratio that permits sensitive sampling with quantitative accuracy and high wavenumber precision based on well documented advantages (Jacquinot, Fellgett, Connes).

Visible-Light Photocatalytic C-H Amination of Arenes Utilizing Acridine-Lewis Acid Complexes.

This report describes the development of a visible-light photocatalytic system for C(sp)-H amination that leverages -generated photocatalysts. We demonstrate that the combination of acridine derivatives and Lewis acids forms potent photooxidants that promote the C-H amination of electronically diverse arenes upon irradiation with visible-light (440 nm). A first-generation photocatalyst composed of Sc(OTf) and acridine effects the C-H amination of substrates with oxidation potentials ≤ +2.

Synthesis of Biindene Derivatives via Pd-Catalyzed Alkene Difunctionalization Reactions.

The palladium-catalyzed cross-coupling of 2-allylphenyl triflate and related electrophiles with substituted indenes affords biindene derivatives in moderate to good yields with high selectivity for thermodynamically preferred alkene isomers. The transformations involve alkene nucleopalladation with indenyl anions, and we also demonstrate that 2-allylphenyl triflates can be transformed to indenes under similar conditions. The scope of this transformation, along with the mechanism of formation of both indene and biindene products, is described.

Revisiting the Reactivity of the Dismissed Hydrogen Atom Transfer Catalyst Succinimide--oxyl.

Phthalimide--oxyl (PINO) and related radicals are promising catalysts for C-H functionalization reactions. To date, only a small number of -oxyl derivatives have demonstrated improved activities over PINO. We postulate that the lack of success in identifying superior catalysts is associated not only with challenges in the design and synthesis of new structures, but also the way catalysts are evaluated and utilized.

Revisiting poly(vinyl chloride) reactivity in the context of chemical recycling.

Poly(vinyl chloride) (PVC) is one of the highest production volume polymers due to its many applications, and it is one of the least recycled due to its chemical structure and frequent formulation with additives. Developing efficient PVC recycling techniques would enable PVC waste to be reused or repurposed in other processes. Within this context, the literature on PVC modification offers considerable insight into versatile reaction pathways, potentially inspiring new approaches for repurposing PVC waste into value-added products.

Development of High-Throughput Experimentation Approaches for Rapid Radiochemical Exploration.

Positron emission tomography is a widely used imaging platform for studying physiological processes. Despite the proliferation of modern synthetic methodologies for radiolabeling, the optimization of these reactions still primarily relies on inefficient one-factor-at-a-time approaches. High-throughput experimentation (HTE) has proven to be a powerful approach for optimizing reactions in many areas of chemical synthesis.

Adsorption of Natural Gas in Metal-Organic Frameworks: Selectivity, Cyclability, and Comparison to Methane Adsorption.

Evaluation of metal-organic frameworks (MOFs) for adsorbed natural gas (ANG) technology employs pure methane as a surrogate for natural gas (NG). This approximation is problematic, as it ignores the impact of other heavier hydrocarbons present in NG, such as ethane and propane, which generally have more favorable adsorption interactions with MOFs compared to methane. Herein, using quantitative Raman spectroscopic analysis and Monte Carlo calculations, we demonstrate the adsorption selectivity of high-performing MOFs, such as MOF-5, MOF-177, and SNU-70, for a methane and ethane mixture (95:5) that mimics the composition of NG.

Salt-Bridged Peptide Anion Gaseous Structures Enable Efficient Negative Ion Electron Capture Dissociation.

We previously discovered that electron attachment to gaseous peptide anions can occur within a relatively narrow electron energy range. The resulting charge-increased radical ions undergo dissociation analogous to conventional cation electron capture/transfer dissociation (ECD/ETD), thus enabling a novel tandem mass spectrometry (MS/MS) technique that we termed negative ion electron capture dissociation (niECD). We proposed that gaseous zwitterionic structures are required for niECD with electron capture either occurring at or being directed by a positively charged site.

Rational Design of a Necklace-like ZIF-67/Poly(vinylidene fluoride) Electrospun Nanofiber Hybrid Membrane for Simultaneous Removal of PM and SO.

Growing concerns over poor air quality, especially in urban and industrial regions, have led to increased global demands for advanced air-purification technologies. However, the stability and airborne pollutant control abilities of the available air-purification materials under diverse environmental conditions are limited. Thus, the advanced development of filtration materials that can effectively control different types of pollutants, such as particulate matter (PM) and gaseous pollutants, simultaneously has attracted attention.

Sensitizing Explosives Through Molecular Doping.

Cocrystallization assembles multicomponent crystals in defined ratios that are held together by intermolecular interactions. While cocrystals have seen extensive use in the pharmaceutical industry for solving issues with stability and solubility, extension to the field of energetic materials for improved properties has proven difficult. Predicting successful coformers remains a challenge for systems lacking well-understood synthons that promote reliable intermolecular assembly.

Attenuating N-Oxyl Decomposition for Improved Hydrogen Atom Transfer Catalysts.

The design of N-oxyl hydrogen atom transfer catalysts has proven challenging to date. Previous efforts have focused on the functionalization of the archetype, phthalimide-N-oxyl. Driven in part by the limited options for modification of this structure, this strategy has provided only modest improvements in reactivity and/or solubility.

Selective (α)-l-Rhamnosylation and Neuroprotective Activity Exploration of Cardiotonic Steroids.

This work describes the studies on the direct C3-glycosylation of the C19-hydroxylated cardiotonic steroids strophanthidol, -ouabagenin, and ouabagenin using a strategy based on protection of the C5 and C19 hydroxyl groups with boronic acids. While this strategy resulted in a successful one-pot C3-selective glycosylation of strophanthidol and -ouabegenin, it failed to provide ouabain from ouabagenin. The neuroprotective activity of the synthetic and natural glycosides against LPS-induced neuroinflammation was explored in neonatal mouse primary glia cells.

Perchlorate-Free Energetic Oxidizers Enabled by Ionic Cocrystallization.

The search for a suitable replacement for the ubiquitous oxidizer ammonium perchlorate (AP) is a top priority to enable more sustainable solid rocket motors. The oxidizing salts ammonium nitrate (AN) and ammonium dinitramide (ADN) are regarded as potential green replacements for AP, but suffer from a plethora of handling and processing issues including poor stability and a needle-like crystal morphology which inhibits dense packing; these prevent their widespread use. In the present work, ionic cocrystallization is leveraged to produce the first cocrystals of these oxidizing salts with an energetic coformer and the first such cocrystals to maintain a positive oxygen balance.