Carboxylate Salts Research Articles

Ring Expansion from 16‐Membered Macrocyclic Lactones Using Yamaguchi and Photoinduced Decarboxylative Radical Macrolactonization

This study describes a new strategy for synthesizing 31‐, 33‐, 46‐, and 48‐membered macrocyclic lactones from commercially available 16‐membered macrocyclic lactones using the Yamaguchi reaction and photoinduced decarboxylative radical macrolactonization. Despite challenges with the low solubility of substrates and the slow rate of photochemical radical cyclization, the preparation of enlarged macrocyclic lactones from 16‐membered macrocyclic lactones was successfully accomplished. Additionally, the effect of the Lewis acidity of the counter cation in the carboxylate salt provided mechanistic insights into the photoinduced decarboxylative radical macrolactonization.

Antimicrobial Efficacy of GS-2 on Reusable Food Packaging Materials for Specialty Crops.

The European Union (EU) regulations mandate 10% of all food packaging to be reusable by 2030. United States (U.S.) exporters of specialty crops face new challenges in ensuring microbiological food safety using reusable packaging. A novel antimicrobial formulation consisting of ammonium carboxylate salt of capric acid and L-arginine (GS-2) was recently developed as a spray coating chemical for food packaging materials. In this study, we evaluated the antimicrobial efficacy of GS-2 against microbial strains representing three foodborne bacterial pathogens (Escherichia coli O157:H7, Listeria monocytogenes, Salmonella enterica), one fungal spoilage organism (Aspergillus niger), and one surrogate viral pathogen (murine norovirus) on three reusable plastic materials (acrylonitrile butadiene styrene, high-density polyethylene, and polypropylene) and one cardboard packaging material, respectively. Different chemical concentrations, exposure times, and storage conditions were individually evaluated for the relative antimicrobial efficacies of GS-2 against these microorganisms. Our results showed that GS-2 was highly effective for inactivating bacterial pathogens on both plastic and cardboard surfaces. For instance, 3% GS-2 achieved a >5 log CFU/in2 reduction in E. coli O157:H7, L. monocytogenes, and S. enterica on tested plastic surfaces at an exposure time of 60 min. However, its efficacy against A. niger and murine norovirus was less optimal, resulting in a ≤1 log CFU/in2 reduction on all tested surfaces. Based on our study, GS-2 demonstrated a strong potential as an antibacterial coating reagent for reusable food packaging materials to minimize pathogen contamination and ensure the safety of the specialty crops.

Hydrogen-bonding interactions in the salts 2,4,6-triaminopyrimidin-1-ium sorbate dihydrate, 2,4,6-triaminopyrimidin-1-ium N-phenylantharanilate and 2,4,6-triaminopyrimidin-1-ium p-toluenesulfonate.

Three salts, namely, 2,4,6-triaminopyrimidin-1-ium sorbate dihydrate, C4H8N5+·C6H7O2-·2H2O, (I), 2,4,6-triaminopyrimidin-1-ium N-phenylanthranilate, C4H8N5+·C13H10NO2-, (II), and 2,4,6-triaminopyrimidin-1-ium p-toluenesulfonate, C4H8N5+·C7H7O3S-, (III), were synthesized, characterized by X-ray diffraction techniques and their supramolecular interactions investigated. In all three crystal structures, protonation of the pyrimidine moiety occurs at the N1 position and is reflected in a widening of the C-N-C bond angle. In salts (I)-(III), the primary acid-base interaction occurs through a pair of N-H...O hydrogen bonds to give a heterodimeric R22(8) synthon. Salts (II) and (III) form a discrete centrosymmetric base pair that produces a homodimeric R22(8) synthon and salt (I) forms a water-mediated base pair resulting in a tetrameric R44(12) synthon. The supramolecular patterns exhibited by sulfonate salt (III) mimic the patterns of carboxylate salt (II) and both exhibit a DADA array (D = donor and A = acceptor) quadruple hydrogen-bonded pattern. The crystal structures of salts (I) and (III) are stabilized by offset and face-to-face aromatic π-π stacking interactions, respectively. The resulting architectures in salts (I)-(III) are a supramolecular sheet with a rosette-like architecture in (I), a supramolecular sheet-like architecture in (II) and a three-dimensional supramolecular network in (III).

Physical and Chemical Evolution of PTFE-α-Al2O3 Composites Versus 304 SS Tribofilms During Dry Sliding

Polytetrafluoroethylene (PTFE) is renowned for its remarkably low friction coefficient (µ ~ 0.1) yet exhibits notably high wear rates (K ~ 104) in dry sliding applications. To mitigate this, various metallic and non-metallic fillers have been explored, consistently demonstrating a reduction in wear rates of unfilled PTFE between 10 and 104 times. Among these fillers, α-Al2O3 is one of the most extensively studied materials. 5 wt% of α-Al2O3 filler into PTFE yields a composite material, PTFE- α-Al2O3, characterized by a wear rate a staggering 104 times lower than unfilled PTFE. This reduction in wear has been attributed to the formation of tribofilms on the PTFE composite and metal counterbody material. These tribofilms emerge due to the interaction between broken fluropolymer chains and environmental water and oxygen. This interaction results in the creation of carboxylate salt groups, which subsequently react with metal/metal oxide particles (both from the counterbody and the metal filler) to form tribofilms. Despite numerous studies scrutinizing the chemical composition of the tribofilms pre- and post-test, the chemical development of these films has remained largely unexplored. In this study, the authors utilize attenuated total reflection infrared spectroscopy (ATR-IR), transmission infrared (IR) spectroscopy, optical microscopy, and stylus profilometry to observe tribofilm development. A thorough topographical and chemical description of the tribofilm is provided via these techniques. The ratio of carboxylate salt groups directly corresponds with improved wear performance and these changes are very local to the worn polymer surface. This discovery contributes to a deeper understanding of the tribological behavior of PTFE-α-Al2O3 composites.Graphical

Avoidance of crystallization of hydrophobic drugs in an amorphous solid dispersion during spray-drying and storage

The study examined the efficacy of additives in preventing the crystallization of functional ingredients during the spray-drying process. Spray-drying of a hydrophobic drug from alcohol in the presence of a hydrophilic carrier-forming agent was utilized as a representative scenario, which frequently leads to the crystallization of the main drug component induced by the drying process. Ibuprofen (IBP) and its four congeners were employed as representatives of readily crystallizable hydrophobic pharmaceutical compounds. Disaccharides were intentionally employed as components of the drug carrier to create conditions conducive to crystallization. Ten materials, including the IBP congeners, were investigated for their anti-crystallization properties. The findings indicated that additives with a hydrophobic moiety similar to that of IBP and a carboxylic acid salt moiety effectively prevented IBP and its congeners from crystallizing when the additive content was ≥0.2 g/g-drug during spray-drying and storage at 30 °C over silica gel.

Study on the behavior of AAEMs removal and the evolution of microscopic characteristics in high alkali coal under different acids

ABSTRACT In this paper, the removal behavior of alkali and alkaline earth metals (AAEMs) and the evolution of microscopic characteristics in high alkali coal under the leaching of inorganic and organic acids are studied. The results show inorganic acids have better effect on the removal of AAEMs because of their stronger ability to convert carboxylate and phenol salts into covalent carboxylic acids and phenols. Citric acid has a slightly weaker effect than inorganic acids, and oxalic acid has the least effect. The improvement of slagging characteristics is consistent with the removal ability. Sulfuric acid, hydrochloric acid and citric acid are more effective in enhancing the calorific value of coal, with an enhancement of about 0.60 MJ/kg. After leaching, the pores and cracks in the coal are developed, and the mesopores have a tendency to shift to a lower pore size range. This trend is most pronounced in citric acid leached coal and hydrochloric acid leached coal. Sulfuric acid seriously damage the surface morphology, which results in a tendency of large pore transfer in S-form coal.

Light‐Activated Nanocatalyst for Precise In‐Situ Antimicrobial Synthesis via Photoredox‐Catalytic Click Reaction

AbstractThe excessive and prolonged use of antibiotics contributes to the emergence of drug‐resistant S. aureus strains and potential dysbacteriosis‐related diseases, necessitating the exploration of alternative therapeutic approaches. Herein, we present a light‐activated nanocatalyst for synthesizing in situ antimicrobials through photoredox‐catalytic click reaction, achieving precise, site‐directed elimination of S. aureus skin infections. Methylene blue (MB), a commercially available photosensitizer, was encapsulated within the CuII‐based metal–organic framework, MOF‐199, and further enveloped with Pluronic F‐127 to create the light‐responsive nanocatalyst MB@PMOF. Upon exposure to red light, MB participates in a photoredox‐catalytic cycle, driven by the 1,3,5‐benzenetricarboxylic carboxylate salts (BTC−) ligand presented in the structure of MOF‐199. This light‐activated MB then catalyzes the reduction of CuII to CuI through a single‐electron transfer (SET) process, efficiently initiating the click reaction to form active antimicrobial agents under physiological conditions. Both in vitro and in vivo results demonstrated the effectiveness of MB@PMOF‐catalyzed drug synthesis in inhibiting S. aureus, including their methicillin‐resistant strains, thereby accelerating skin healing in severe bacterial infections. This study introduces a novel design paradigm for controlled, on‐site drug synthesis, offering a promising alternative to realize precise treatment of bacterial infections without undesirable side effects.

Light-Activated Nanocatalyst for Precise In-Situ Antimicrobial Synthesis via Photoredox-Catalytic Click Reaction.

The excessive and prolonged use of antibiotics contributes to the emergence of drug-resistant S. aureus strains and potential dysbacteriosis-related diseases, necessitating the exploration of alternative therapeutic approaches. Herein, we present a light-activated nanocatalyst for synthesizing in situ antimicrobials through photoredox-catalytic click reaction, achieving precise, site-directed elimination of S. aureus skin infections. Methylene blue (MB), a commercially available photosensitizer, was encapsulated within the CuII-based metal-organic framework, MOF-199, and further enveloped with Pluronic F-127 to create the light-responsive nanocatalyst MB@PMOF. Upon exposure to red light, MB participates in a photoredox-catalytic cycle, driven by the 1,3,5-benzenetricarboxylic carboxylate salts (BTC-) ligand presented in the structure of MOF-199. This light-activated MB then catalyzes the reduction of CuII to CuI through a single-electron transfer (SET) process, efficiently initiating the click reaction to form active antimicrobial agents under physiological conditions. Both in vitro and in vivo results demonstrated the effectiveness of MB@PMOF-catalyzed drug synthesis in inhibiting S. aureus, including their methicillin-resistant strains, thereby accelerating skin healing in severe bacterial infections. This study introduces a novel design paradigm for controlled, on-site drug synthesis, offering a promising alternative to realize precise treatment of bacterial infections without undesirable side effects.

A comprehensive investigation of cholesteric liquid crystal interpenetrating polymer networks for metal ion sensor technology

This study outlines the fabrication process of a photonic polymer cholesteric liquid crystal (PCLC) engineered for dynamic response to external stimuli. The methodological framework includes the precise templating of PCLC onto an interpenetrating polymer network (IPN) following selective UV crosslinking and the careful removal of nonreactive mesogens. The sensor component of the PCLC film is composed of poly(acrylic acid) hydrogel. A key aspect of the process involves the formation of micro-holes through acetone treatment to enhance sensitivity. Additionally, functionalization with potassium hydroxide (KOH) improves the detection of calcium ions (Ca2+) by disrupting hydrogen bonds and facilitating the formation of potassium carboxylate salt. Combining the inherent properties of PCLC with the hydrogel’s responsiveness to metal ions results in a sophisticated sensor designed to detect Ca2+ ions through the modulation of PCLC pitch, creating distinct transmission bands. The manuscript provides a detailed quantitative analysis of stimulus-induced changes in PCLC wavelength, using measured spectra to refine and optimize process conditions. The resulting PCLC sensor demonstrates exceptional sensitivity (9.30 nm/mM) within the 1–15 mM Ca2+ ion concentration range, along with excellent specificity. This cost-effective, user-friendly, and colorimetric sensing modality holds significant promise for various applications in analytical chemistry.

Therapeutic efficacy of Strobilanthes urticifolia-infused pectin/polyacrylic acid hydrogel for targeted hepatorenal fibrosis mitigation: A multifaceted biomaterial approach.

Pectin/polyacrylic acid (PPAA) hydrogel is a unique and versatile biomaterial with applications in drug delivery, wound healing, tissue engineering, and agriculture, owing to its tailored properties and multifunctional attributes. This study aims to harness the therapeutic potential of Strobilanthes urticifolia extract within a PPAA hydrogel matrix to attenuate liver and kidney fibrosis through targeted and sustained delivery of biologically active substances. PPAA hydrogel was prepared by free radical polymerization, followed by its porosity and swelling determination. The results depicted the porous nature of PPAA hydrogel and improved swelling properties at pH 7.4, confirming its drug delivery promise. The polyphenolic-enriched S. urticifolia extracts of leaf and flower were loaded onto PPAA hydrogel, and the loading efficiency was 87% (leaf) and 62.5% (flower). Moreover, slow-release studies showed controlled and prolonged release of polyphenols for 7 days. The polyphenolic-enriched hydrogel's microstructure was characterized using SEM, FTIR, and thermogravimetric analysis (TGA). SEM results revealed a highly porous structure of polyphenol enriched PPAA hydrogel, while FTIR analysis confirmed the presence of functional groups such as OH group of carboxylic acid, aliphatic CH2 stretching due to acrylic acid grafting with pectin, CO stretching due to acid linkage with pectin, CH of aromatic ring, and CH of carboxylate salt in PPAA hydrogel. TGA of PPAA hydrogel showed its stability up to 488°C. Additionally, the S. urticifolia extract loaded PPAA hydrogel displayed significant antibacterial properties and minimum inhibitory concentrations against both Gram-positive and Gram-negative bacteria. In vivo studies carried out on rats demonstrated that polyphenolic enriched PPAA hydrogel significantly attenuates liver and kidney fibrosis. Therefore, it is concluded from the present study that loading of polyphenolic enriched extract from leaves and flower of S. urticifolia enhanced the biomedical applications of PPAA hydrogel. RESEARCH HIGHLIGHTS: The PPAA hydrogel developed in this study exhibits a highly porous structure and improved swelling properties at physiological pH (7.4), making it an excellent candidate for drug delivery systems. S. urticifolia extracts, rich in polyphenols, were successfully incorporated into the PPAA hydrogel with high loading efficiencies of 87% for leaf and 62.5% for flower extracts. Loading of polyphenolic enriched extracts of S. urticifolia onto PPAA enhanced its biological activities such as antibacterial, hepatoprotective, and reno-protective activities as depicted by in vitro and in vivo studies.

Enantioselective Synthesis of β-l-5-[(E)-2-Bromovinyl)-1-((2S,4S)-2-(hydroxymethyl)-1,3-(dioxolane-4-yl) Uracil)] (l-BHDU) via Chiral Pure l-Dioxolane.

β-l-5-((E)-2-Bromovinyl)-1-((2S,4S)-2-(hydroxymethyl)-1,3-(dioxolane-4-yl) uracil (l-BHDU, 17) is a potent and selective inhibitor of the varicella-zoster virus (VZV). l-BHDU (17) has demonstrated excellent anti-VZV activity and is a preclinical candidate to treat chickenpox, shingles (herpes zoster), and herpes simplex virus 1 (HSV-1) infections. Its monophosphate prodrug (POM-l-BHDU-MP, 24) demonstrated an enhanced pharmacokinetic and antiviral profile. POM-l-BHDU-MP (24), in vivo, effectively reduced the VZV viral load and was effective for the topical treatment of VZV and HSV-1 infections. Therefore, a viable synthetic procedure for developing POM-l-BHDU-MP (24) is needed. In this article, an efficient approach for the synthesis of l-BHDU (17) from a readily available starting material is described in 7 steps. An efficient and practical methodology for both chiral pure l- & d-dioxolane 11 and 13 were developed via diastereomeric chiral amine salt formation. Neutralization of the amine carboxylate salt of l-dioxolane 10 provides enantiomerically pure l-dioxane 11 (ee ≥ 99%). Optically pure 11 was utilized to construct the final nucleoside l-BHDU (17) and its monophosphate ester prodrug (POM-l-BHDU-MP, 24). Notably, the reported process eliminates expensive chiral chromatography for the synthesis of chiral pure l- & d-dioxolane, which offers avenues for the development and structure-activity relationship studies of l- & d-dioxolane-derived nucleosides.

Room temperature self-healable ionic polymers by incorporating ammonium and carboxylate salt

In this study, we report the fabrication and characteristics of a self-healing polymer forming an ionically bonded network based on carboxylic acids and alkyl amines. The self-healing polymer forming an ionically bonded network is prepared from acrylic acid-containing carboxylic groups in the main chain and ammonium carboxylate salts derived from alkyl amines of varying lengths. The nature of the ion bonding between alkyl amines and carboxylic acids within the polymer matrix was analyzed using Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared Spectroscopy (FT-IR). The self-healing polymer, incorporating ionically bound entities like ammonium carboxylate salts, demonstrated 100% self-healing efficiency at room temperature overnight, in contrast to the reference polymer without ion bonding. Various lengths of alkyl amines used to form ammonium carboxylate salts exhibited remarkable properties such as over 500% elongation at break, adhesive strength exceeding 300 gf, and light transmittance of over 90%, all dependent on the length of the alkyl chain.

Characterization of the hypergolic ignition of green fuels with hydrogen peroxide by drop test and jet impingement

This work presents an experimental study on the hypergolic behavior of variants of N,N,N’,N’-tetramethylethylenediamine (TMEDA)/N,N-dimethylethanolamine (DMEA) system, named PAHyp 0, with 93 wt% hydrogen peroxide. Two different copper-based catalyst and one cobalt-based catalytic agent were dissolved in the fuels to trigger the pre-ignition reactions. When employing copper chloride dihydrate, the resultant fuel requires methanol (ternary system) as a stabilizing agent, whereas both carboxylic salts of copper and cobalt dissolved in TMEDA/DMEA deliver a stable formulation (binary system) without the need for any organic solvent. Shadowgraph high-speed imaging was used to capture the ignition process and pressure wave development of over 30 fuel samples in a modified drop test. An ignition/stability envelope was proposed to map the safe and unstable formulations. It was demonstrated that the concentration of TMEDA should be no more than 50% in the binary system, while the amount of methanol should fall within a concentration window of 33 to 50% in the ternary system. Lower loadings of catalyst, ranging from 0.5 to 1.0 wt%, are required to deliver stable fast-igniting fuels. Three promising formulations catalyzed with 1 wt% copper salts were selected to perform impinging jet fire experiments. Impinging jets yielded significantly lower ignition delay times than drop tests due to the better mixing conditions. However, it was verified that ignition may fail for low values of jet velocities, below 0.8 m/s, and for high jet velocities, exceeding 14 m/s. An attempt to explain the ignition and non-ignition events was made by using the fundamentals of explosion limits of the hydrogen/oxygen system and oxidation reactions at low temperature. Remarkably, ultra-fast ignitions of about 10 ms were measured by the impinging jet setup within near-optimal operational conditions. Therefore, TMEDA/DMEA-based fuels with reduced catalyst loadings (0.5–1.0 wt%) offer new opportunities in aerospace propulsion and should be further studied.

Sustainable Twist – Towards Highly Atom Efficient Grignard Processes

AbstractCopper salts, which are widely applied in chemical processes, are highly toxic for aquatic life with devastating and long‐lasting effects. The most sustainable measure to prevent negative impact on surface water bodies is the elimination of copper from chemical processes. In Grignard reactions, acyl chlorides are widely used in combination with copper(I) chloride to introduce acyl substituents to aromatic compounds. We demonstrate that carboxylic acid anhydrides are a competent and highly selective alternative to acyl chlorides when used in the absence of copper(I) catalysts. An integrated value stream cycle allows for recycling of the carboxylate salt byproducts by reaction with ketene, thereby reducing the waste output to almost zero. This proposed process can therefore contribute to minimizing both chemical waste and heavy metal input into water bodies.

Laboratory study on the transformation of oil-water interface properties under direct current electric field

Interface tension is one of the important mechanisms that affect crude oil recovery and plays an important role in the development of tight oil reservoirs. Electrical-enhanced oil recovery can be used as a technology to reduce interfacial tension and improve crude oil recovery. In the previous research process of Electrical-enhanced oil recovery, the focus was more on the influence of electric field on wettability, and the understanding of the changes in interfacial tension under electric field action is not yet comprehensive. This article designs an orthogonal experiment to study the effect of electric field on oil-water properties. The degree of influence of three factors, namely sodium chloride solution concentration (C), direct current voltage (V), and voltage action time (t), on interfacial tension is studied. Gas chromatography, four component analysis, and Fourier transform infrared spectroscopy are combined to discuss the mechanism of the influence of changes in solution pH, crude oil components, and oil phase functional groups on interfacial tension. The results show that an external electric field can effectively reduce the interfacial tension between oil and water, and the maximum change in interfacial tension after the experiment can be reduced from 23.21 mN/m to 0.37 mN/m; Through range analysis, it can be concluded that the concentration of sodium chloride solution has the greatest impact on interfacial tension, followed by DC voltage and voltage action time. The optimal experimental conditions are 0.5 mol/L sodium chloride solution, 10 V DC voltage, and a voltage action time of 18 h, and the change in interfacial tension is related to the increase in pH value. The change in crude oil composition is also an important reason for the decrease in interfacial tension under external electric fields. Finally, Fourier transform infrared spectroscopy was used to determine that under the action of an electric field, the increase in pH of the sodium chloride solution resulted in the formation of carboxylate salts through chemical reactions between alkaline substances of solution and acidic substances of the oil, which were the key factors in reducing interfacial tension. This study helps to understand and explore the principles and mechanisms of Electrical-enhanced oil recovery in improving oil recovery, with the aim of contributing to the development and promotion of Electrical-enhanced oil recovery technology.

Self-assembly mechanism and application performance in aqueous solutions mediated by ethylene oxide chains in alcohol ether carboxylates and cocamidopropyl betaine

Zwitterionic Cocoamidopropyl Betaine (CAB) and anionic alcohol ether carboxylates have garnered significant attention within the realms of green and colloid chemistry owing to their inherent biocompatibility, multi-responsiveness, and diverse applications. Systematic inquiry into the physicochemical properties, self-assembly mechanisms, and application efficacy of complex systems comprising alcohol ether carboxylate salts with varying ethylene oxide (EO) units (AECnH, n = 5, 7, 9) and CAB-35 in aqueous solutions was undertaken. It was discerned that the optimum physicochemical attributes of the complex system are attained at a molar ratio of AEC of 0.5 (αAEC = 0.5). Incremental augmentation in the number of EO units facilitated the formation of rod-like micelles, exhibiting relatively unstable characteristics, while a reduction in the number of EO units led to the generation of comparatively stable spherical micelles. The self-assembly of micelles in these hybrid systems predominantly hinges upon hydrogen bonding, electrostatic interactions, and hydrophobic forces. Furthermore, kinetic analysis validated that the genesis of micelles in all three hybrid systems is propelled by enthalpy, with the adsorption process entailing a mechanism characterized by mixed diffusion-kinetic adsorption. The optimal wetting performance of the complex system was observed at αAEC = 0.5, while the foam performance demonstrated a diminishing trend with escalating αAEC. This comprehensive discourse delineates the synergistic mechanisms and application efficacy of two distinct classes of green surfactants with disparate charges in aqueous solutions, while contemplating the influence of varying numbers of ethylene oxide chains. Not only does it furnish fundamental insights into their properties, but it also proffers a novel standpoint for the exploration of green surfactants.

Peculiarities of Calcite Interaction with Carboxylic Acids

This research examined the interaction of calcite with carboxylic acids (formic, citric, malic, and oxalic acids) at temperatures ranging from 22 to 80 °C. Experiments were carried out using an open batch reactor to prevent the impact of aggressive CO2 byproducts. The dissolution rate was determined to be a combination of the chemical interaction of calcite with acid and the promotion of dissolution by calcium carboxylate salt. When acid concentrations are low, the surface chemical reaction acts as a limiting step with an activation energy of 42 kJ∙mol-1. Conversely, at higher acid concentrations, the formation of calcium carboxylate with reduced solubility hinders its dissolution, thereby restricting the overall calcite dissolution process. Both stages are significantly influenced by temperature. The specific functional groups present in the acids aid in the formation of surface species with Ca2+ cations. The properties of these functional groups impact the stability of the species and the dissolution of calcite.

Highly Anti-Markovnikov Selective Oxidative Arene Alkenylation Using Ir(I) Catalyst Precursors and Cu(II) Carboxylates.

The Ir(I) complex [Ir(μ-Cl)(coe)2]2 (coe = cis-cyclooctene) is a catalyst precursor for benzene alkenylation using Cu(II) carboxylate salts. Using [Ir(μ-Cl)(coe)2]2, propenylbenzenes are formed from the reaction of benzene, propylene, and CuX2 (X = acetate, pivalate, or 2-ethylhexanoate). The Ir-catalyzed reactions selectively produce anti-Markovnikov products, trans-β-methylstyrene, cis-β-methylstyrene, and allylbenzene, along with minor amounts of the Markovnikov product, α-methylstyrene. The selectivity for the anti-Markovnikov products changed as the reaction progressed. For example, in a reaction that uses 240 equiv of Cu(OHex)2 (related to Ir), the selectivity for the anti-Markovnikov products increases from 18:1 at 3 h to 42:1 at 42 h with 30 psig of propylene at 150 °C. Studies of product stability have revealed that the increase in the selectivity for anti-Markovnikov products is not the result of an isomerization process or the selective decomposition of specific products. Rather, the change in selectivity correlates with the ratio of Cu(II) to Cu(I) in the solution, which decreases as the reaction progresses. We propose that the identity of the active catalyst changes as Cu(I) is accumulated, resulting in the formation of an active catalyst that is more selective for anti-Markovnikov products. Using a 4:1 Cu(I)/Cu(II) ratio at the start of the reaction, a 65(3):1 anti-Markovnikov/Markovnikov ratio is observed.

Analysis of aromatic carboxylic acid and calcium salt couples with gas chromatography-mass spectrometry: Implications and comparison with in situ measurements at Mars' surface

Aromatic organic salts such as benzoates or phthalates may be widespread degradation products of organic molecules at the surface of Mars. The low volatility of these aromatic carboxylic salts could have compromised their detection through thermal extraction in situ analyses such as those performed by the Viking landers. However, over the years, analytical chemistry laboratories on board current and future Martian surface missions, such as the Sample Analysis at Mars (SAM) instrument suite on board the Curiosity rover and the Mars Organic Molecule Analyzer (MOMA) instrument of the Rosalind Franklin ExoMars rover, respectively, have evolved. These instruments have improved in efficiency to detect refractory and polar organic compounds, which could influence the detection of aromatic organic salts. To evaluate the capability of detecting aromatic organic salts on Mars with in situ instruments, we performed laboratory experiments under Viking, SAM, and MOMA-like Gas Chromatography-Mass Spectrometry (GC–MS) conditions with two carboxylic acid/salt couples: phthalic acid/calcium phthalate and benzoic acid/calcium benzoate. We studied the behavior and signatures of both molecular forms when using pyrolysis and derivatization experiments and the implications of these results in the search for organic molecules on Mars. This study showed that the Viking experiments could not have detected the presence of aromatic carboxylic salts in Martian samples because its maximum pyrolysis temperature was too low (500 °C). However, we showed that calcium benzoate and calcium phthalate, despite their refractory nature, could be identified indirectly through the detection of thermal and derivatized degradation products, both with SAM and MOMA. No conclusive proof of the presence of these aromatic organic salt species have been found in the SAM in situ data but given the right instrumental set-up they could be detected if present. The conclusions of this work raise essential questions on the detectability of refractory molecules, the analytical efficiency of flight instruments, and the interpretation of in situ data.

Transport of carboxylate salts of varying chain lengths in crosslinked polyether membranes

Carboxylate anions of various chain lengths are important molecules for many applications such as CO2 reduction, membrane-based bioreactors, etc. Also, carboxylate anions are ubiquitous in biological molecules such as amino acids, fatty acids, etc. Therefore, understanding the transport behavior of carboxylates of different chain lengths in polymer materials is important both as a fundamental phenomenon but also for designing materials for applications. Here, we characterized transport behavior by measuring the permeability (P), and total partition coefficient (K) for a series of polymer membranes for four model carboxylate salts—sodium salts of formate (NaOFm), acetate (NaOAc), propionate (NaOPr), and butanoate (NaOBu)—at varied upstream salt concentrations (0.1–1 M) or a series of polyethylene glycol diacrylate (PEGDA)-based membranes with 1) varying pre-polymerization water content; 2) varying uncharged side chain comonomer (polyethylene glycol methacrylate, PEGMA), and 3) varying charged comonomer)2-acrylamido-2-methyl-1-propanesulfonic acid, AMPS). Also, diffusivity values of the four salts through the membranes have been calculated based on the solution diffusion model equation (PK × D), experimentally obtained permeability, and total partition coefficients. For a majority of these membranes, NaOFm's permeability is much higher than the other three carboxylate salts (NaOAc, NaOPr, and NaOBu) seemingly due to the lower chain length and thereby smaller hydrated diameter. In terms of total partition coefficient, a size-based trend is not observed. For example, NaOBu's total partition coefficient (K) is generally the largest among the four, and at higher upstream salt concentrations (1 M), the values of the total partition coefficients of the four salts converge. From this we conclude that the carboxylate salt transport through these PEGDA-based non-porous dense membranes to be primarily driven by kinetics and not sorption.