Acid Chloride Research Articles

Affinity Constants of Bovine Serum Albumin for 5 nm Gold Nanoparticles (AuNPs) with ω-Functionalized Thiol Monolayers Determined by Fluorescence Spectroscopy.

A detailed understanding of the binding of serum proteins to small (dcore <10 nm) nanoparticles (NPs) is essential for the mediation of protein corona formation in next generation nanotherapeutics. While a number of studies have investigated the details of protein adsorption on large functionalized NPs, small NPs (with a particle surface area comparable in size to the protein) have not received extensive study. This study determined the affinity constant (Ka) of BSA when binding to three different functionalized 5 nm gold nanoparticles (AuNPs). AuNPs were synthesized using three ω-functionalized thiols (mercaptoethoxy-ethoxy-ethanol (MEEE), mercaptohexanoic acid (MHA), and mercaptopentyltrimethylammonium chloride (MPTMA)), giving rise to particles with three different surface charges. The binding affinity of bovine serum albumin (BSA) to the different AuNP surfaces was investigated using UV-visible absorbance spectroscopy, dynamic light scattering (DLS), and fluorescence quenching titrations. Fluorescence titrations indicated that the affinity of BSA was actually highest for small AuNPs with a negative surface charge (MHA-AuNPs). Interestingly, the positively charged MPTMA-AuNPs showed the lowest Ka for BSA, indicating that electrostatic interactions are likely not the primary driving force in binding of BSA to these small AuNPs. Ka values at 25 °C for MHA, MEEE, and MPTMA-AuNPs were 5.2 ± 0.2 × 107, 3.7 ± 0.2 × 107, and 3.3 ± 0.16 × 107 M-1 in water, respectively. Fluorescence quenching titrations performed in 100 mM NaCl resulted in lower Ka values for the charged AuNPs, while the Ka value for the MEEE-AuNPs remained unchanged. Measurement of the hydrodynamic diameter (Dh) by dynamic light scattering (DLS) suggests that adsorption of 1-2 BSA molecules is sufficient to saturate the AuNP surface. DLS and negative-stain TEM images indicate that, despite the lower observed Ka values, the binding of MPTMA-AuNPs to BSA likely induces significant protein misfolding and may lead to extensive BSA aggregation at specific BSA:AuNP molar ratios.

Obtention of Suitable Pregnant Leach Solution (PLS) for Copper Solvent Extraction Plants from Copper Concentrate Using Hydrogen Peroxide and Iodine in a Sulfuric Acid–Chloride Medium

Copper leaching presents an environmentally friendly alternative to traditional sulfide ore processing methods. This study investigates an efficient leaching process for copper concentrate, utilizing a solution of sulfuric acid (H2SO4) and potassium iodide (KI) in a chloride medium (NaCl), enhanced by hydrogen peroxide (H2O2) at room temperature. A significant aspect of this research was optimizing the KI concentration to minimize iodide sublimation into iodine gas (I2). Through the experimental design, the optimal dosages of reagents were determined, leading to maximized copper extraction of approximately 27% in 45 min of testing at room temperature. The results showed that it is possible to obtain a suitable pregnant leach solution (PLS) (i.e., in the range of 3 to 8 g/L of Cu) for treatment in available copper solvent extraction (SX) plants with a cost of less than 4.5 USD/t Cu, according to the economic analysis carried out. The results of this study determine the most effective operational conditions for leaching and ensure a suitable PLS for SX plants in a cost-effective and environmentally friendly manner. This approach could significantly contribute to more sustainable practices in the mining and processing of copper ores.

Synthesis of Trisubstituted Furans from Activated Alkenes by P(III)/P(V) Redox Cycling Catalysis.

The organocatalytic formation of an underrepresented family of trisubstituted and tetrasubstituted furans from activated alkenes and acyl chlorides is reported. In a reaction sequence based on P(III)/P(V) redox cycling catalysis, the cyclic phosphine catalysts react with diacylethenes or acyl acrylates in Michael addition, followed by acylation and either an intramolecular Wittig reaction or a ring closure reaction, liberating the furans. The formed phosphine oxides are reduced in situ by phenylsilane as a terminal reductant. In the first step, 12 diacylethenes were converted to the respective trisubstituted furans. The reaction of acyl acrylates showed a surprising, catalyst-dependent alternate reaction forming tetrasubstituted furans. Two additional methods were developed, giving 14 trisubstituted furans using a phospholene catalyst and an additional 6 tetrasubstituted furans using a phosphetane catalyst. This encompassed 19 newly described compounds.

Corrosion Behavior of Ferritic 12Cr ODS and Martensitic X46Cr13 Steels in Nitric Acid and Sodium Chloride Solutions

Corrosion Behavior of Ferritic 12Cr ODS and Martensitic X46Cr13 Steels in Nitric Acid and Sodium Chloride Solutions

One-Step Phase Separation and Mineralization Fabrication of Membranes for Oily Wastewater Treatment.

Oily wastewater threatens the environment and the human health. Membrane technology offers a simple and efficient alternative to separating oil and water. However, complex membrane modifications are usually employed to optimize the separation performance. In this research, we develop an extremely simple one-step method to in situ calcium carbonate (CaCO3) nanoparticles onto a porous polyketone (PK) membrane via a nonsolvent induced phase separation (NIPS)-mineralization strategy. We utilized the unique chemical property of PK, which allows it to dissolve in a resorcinol aqueous solution. PK was mixed with tannic acid (TA) and calcium chloride (CaCl2) in a resorcinol aqueous solution to fabricate a casting solution. The activated membrane was cast and immersed into a sodium carbonate (Na2CO3) aqueous solution for taking the one-step NIPS-mineralization process. This proposed NIPS-mineralization mechanism comes to two conclusions: (i) the resulting membrane with comprehensive oleophobic properties and enhanced permeation flux for applications of oil/water separation with ultralow fouling and (ii) simplified the procedure to optimize the membrane performance using regular NIPS steps. The current work explores a one-step NIPS-mineralization technique that offers a novel approach to preparing membranes with highly efficient oil/water separation performance.

The use of amines as steel corrosion inhibitors in butanol-gasoline blends

Butanol is an interesting component used for blending gasoline fuels. However, the polar nature of butanol allows the solubility of water and ionic compounds in butanol-gasoline blends (BGBs) making them aggressive to mild steel. Amines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, morpholine, piperazine, and hexamethylenediamine, were tested as corrosion inhibitors for mild steel in BGBs. Additionally, the influence of the acetic acid and sodium chloride concentrations on the inhibition efficiency was examined. Electrochemical impedance spectroscopy andpotentiodynamic polarization were employed for the measurements, complemented by static immersion testing and an XPS surface analysis. The highest inhibition efficiency was demonstrated for diethylenetriamine, triethylenetetramine, andhexamethylenediamine, achieving a value of 95 % or more at aconcentration of 100 mg/L. The formation of ionic pairs involving protonated amines andchlorides was also confirmed. The XPS analysis revealed a very thin passive layer of iron oxides, which may form in the presence of amines, protecting mild steel in BGBs.

Iron-Catalyzed Friedel-Crafts-type 3,5-Diacylation of Indoles.

The exploration of remote functionalization of indoles is impeded by the inherently dominant reactivity intrinsic to the pyrrole moiety. Herein, we delineate a novel strategy facilitated by Lewis acid mediation, enabling the remote C-H functionalization, which culminates in the synthesis of an array of selectively functionalized indole derivatives, encompassing 3-trifluoroacetyl and 5-benzoyl motifs, utilizing trifluoroacetic anhydride and various acyl chlorides. Notably, the protocol exhibits versatility, as epitomized by the extension of C5-acylation to alkylation and sulfonation reactions. This methodology is distinguished by its exemplary regio- and chemo-selectivity, extensive substrate scope, commendable tolerance to a diverse array of functional groups, and the employment of comparatively mild reaction conditions.

Optimization of chemical treatments on the mechanical properties of banana leaves

Plant leaves, especially from bananas, have been used in food packing for a long time, and it has been proven that banana leaves possess the best attributes in developing bio-degradable packaging materials. The current study aims to determine the effects of four types of chemical treatments on the mechanical properties of banana leaves and to optimize the treatment conditions. Mature banana leaves were immersed in chemicals, namely glycerin (25%, 33%), citric acid (0.5%, 1%), calcium hydroxide (3%, 5%), and sodium chloride (5%, 10%) for seven days while drawing samples daily for testing. The treated samples were tested for mechanical properties such as hardness, tear resistance, and load-bearing capacity, using recommended protocols with slight modifications. The multi-response optimization was done using the statistical method named Grey Relational Analysis to select the best treatment setting. The results revealed that the treatments of citric acid solution (0.5%) for one day and two days, Glycerin (33.3%) for one day and two days, and NaCl solution (10%) for one day were among the first five in the Grey Relational Grades obtained for multi-response optimization and demonstrated a significant (p&lt;0.05) increment for all the three mechanical properties. Hence, the selected chemical treatments positively affect the mechanical properties of banana leaves at their optimum treatment conditions.

Study on the Reactivity of Mixed Carboxylic Palmitic Anhydrides via the Esterification Reaction Using Heterogeneous Catalyst

Abstract: of Organic Chemistry LR17ES08: Faculty of Sciences in Sfax, Route de Soukra Km 3,5 – BP 1171-3000, Sfax, Tunisia : The anhydrides were prepared in the presence of triethylamine in the organic solvent by a reaction between fatty acid and acid chloride. Mixed aromatic palmitic were more reactive and selective than the aliphatic anhydrides. The palmitic group was the most involved in acylation. Good yields of fatty esters were obtained with total conversion of mixed anhydrides.

Interactions between deep eutectic solvents and bovine serum albumin studied by spectroscopic and electrochemical methods

Deep eutectic solvent (DES) has become a potential protein extractant as its good biocompatibility, environmental friendliness and accessibility. In this study, two types of DESs, ferric chloride hexahydrate: oxalic acid (FeCl3·6H2O: H2C2O4) and choline chloride: zinc chloride (ChCl: ZnCl2), were prepared. The interactions between these two types of DESs and bovine serum albumin (BSA) were investigated by utilizing spectroscopic and electrochemical methods. It was found that both FeCl3·6H2O: H2C2O4 and ChCl: ZnCl2 are able to form complexes with BSA by a relatively high affinity. During the process, no significant change in BSA conformation was observed. The binding ratios of BSA in the FeCl3·6H2O: H2C2O4 and ChCl: ZnCl2 systems are up to 98.59 % and 98.14 %, respectively, indicating that the two DESs are both promising extractants for BSA. The interactions between the DESs and BSA are mainly hydrogen bond and van der Waals force, which are strong enough to extract BSA but not too strong for regeneration, making the DESs more applicable in the industry. Moreover, it was found that the binding ratio of BSA in the FeCl3·6H2O: H2C2O4-BSA system remains above 91.7 % in the temperature range of 298–313 K, illustrating the potential of FeCl3·6H2O: H2C2O4 to be used in BSA extraction under a wider range of temperature. In contrast, ChCl: ZnCl2 will be better used under lower temperatures.

Copper leaching from complex chalcopyrite-rich ores: Utilizing mechanical activation and wastewater-based sulfuric acid system

Complex chalcopyrite-rich ore is crucial in global copper resources, but is highly refractory in conventional sulfate leaching system. In this paper, we explore the leaching of complex chalcopyrite-rich ores employing a mechanically activated pretreatment combined with wastewater with high concentrations of chloride. The investigation delves into various parameters, including reaction temperature (60 to 90 °C), sulfuric acid concentration (0.005 to 2.0 M), chloride concentration (0 to 1.5 M), liquid/solid ratio (0 to 200), stirring speed (100 to 580 rpm), leaching time (0 to 4 h) and grinding time (0 to 7 h), to evaluate their impact on copper recovery from complex chalcopyrite-rich ores. Furthermore, a comprehensive kinetic analysis of copper leaching behavior was studied, encompassing specific surface area, amorphization degree, grain size, and microstrain. In the sulfuric acid system utilizing wastewater, the presence of mechanical activation and chloride content enhances copper leaching while mitigating the passivating effect of elemental sulfur. Notably, following a leaching period of 4 h at 80 °C, the copper leaching efficiency remarkably reached 89.46 %. In addition, kinetic analysis of copper leaching at temperatures ranging from 60 to 90 °C via a shrinking core model with R2 > 97 %, indicates that the leaching process of copper is primarily governed by solid product layer diffusion, with an activation energy of 54.32 kJ/mol. These findings highlight the efficacy of the proposed approach in optimizing copper recovery from complex chalcopyrite-rich ores, offering insights into the underlying mechanisms driving the leaching process.

Terminal conversion of polyamide membranes by homologous monomer vapors for chlorine-resistant desalination

Water scarcity is a global challenge and severely threatens human development. Membrane desalination shows great potential for producing freshwater from saltwater to alleviate this crisis. However, the dominating polyamide membranes suffer from the issue of poor chlorine resistance, which cause performance deterioration and shortens membrane lifespan. In this study, we report a concept of terminal conversion to design high-performance, antifouling, and especially chlorine-resistant polyamide desalination membranes. This amino-to-carboxyl conversion of commercial membranes can be simply performed by controllable and scalable chemical vapor deposition through exposure in homologous monomer vapor and hydrolysis of unreacted acyl chloride groups. We demonstrate that this conversion not only adjust the electronegativity and hydrophilicity of membranes to boost fouling resistance and reverse osmosis performance, but also tune the reactivity and electron cloud distribution of polyamide networks to restrain chlorine accessibility and substantially improve anti-chlorination property. After extreme chlorination for 240000 ppm h, the resultant membranes show limited rejection decline of only 7.2%. For high-salinity (35000 ppm) and high-pressure (38 bar) desalination, the modified membranes before and after chlorination for 144000 ppm h still exhibit rejection of 94.5% and 90.0% and flux of 75.2 and 71.4 L m-2 h-1, respectively, which are much better than those of the pristine membranes (89.6% and 63.5%, and 64.2 and 57.5 L m-2 h-1). Our findings pave an alternative mechanism and strategy to reconstruct polyamide membranes for efficient water desalination.

Foliar Application of Chitosan (CTS), γ-Aminobutyric Acid (GABA), or Sodium Chloride (NaCl) Mitigates Summer Bentgrass Decline in the Subtropical Zone.

Creeping bentgrass (Agrostis stolonifera) is an excellent cool-season turfgrass that is widely used in urban gardening, landscaping, and golf turf. Triennial field experiments from 2017 to 2019 were conducted to investigate effects of the foliar application of chitosan (CTS), γ-aminobutyric acid (GABA), or sodium chloride (NaCl) on mitigating summer bentgrass decline (SBD) and exploring the CTS, GABA, or NaCl regulatory mechanism of tolerance to summer heat stress associated with changes in chlorophyll (Chl) loss and photosynthetic capacity, osmotic adjustment (OA), oxidative damage, and cell membrane stability. The findings demonstrated that persistent ambient high temperatures above 30 °C during the summer months of 2017, 2018, and 2019 significantly reduced the turf quality (TQ), Chl content, photochemical efficiency of PSII (Fv/Fm and PIABS), leaf relative water content, and osmotic potential (OP) but significantly increased electrolyte leakage (EL) and the accumulations of free proline, water-soluble carbohydrate (WSC), hydrogen peroxide (H2O2), and malondialdehyde (MDA). The foliar application of CTS, GABA, or NaCl could significantly alleviate SBD, as reflected by improved TQ and delayed Chl loss during hot summer months. Heat-induced declines in Fv/Fm, PIABS, the net photosynthetic rate (Pn), the transpiration rate (Tr), and water use efficiency (WUE) could be significantly mitigated by the exogenous application of CTS, GABA, or NaCl. In addition, the foliar application of CTS, GABA, or NaCl also significantly improved the accumulations of free proline and WSC but reduced the EL, OP, and H2O2 content and the MDA content in leaves of creeping bentgrass in favor of water and redox homeostasis in summer. Based on the comprehensive evaluation of the subordinate function value analysis (SFVA), the CTS had the best effect on the mitigation of SBD, followed by GABA and NaCl in 2017, 2018, and 2019. The current study indicates that the foliar application of an appropriate dose of GABA, CTS, or NaCl provides a cost-effective strategy for mitigating SBD.

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.

Direct Synthesis of Monofluoromethylthioesters from Acyl Chlorides with Elemental Sulfur and Fluoroiodomethane

AbstractWe report an unprecedented Ni‐catalyzed direct monofluoromethylthiolation of acyl chlorides, in situ generated from carboxylic acids, with elemental sulfur (S8) as the S source and fluoroiodomethane (ICH2F) as the CH2F radical source to produce a series of monofluoromethylthioesters in moderate to good yields. This approach features excellent functional group tolerance and broad substrate scope. Additionally, the late‐stage monofluoromethylthiolation of complex bioactive molecules can also be accomplished using this method.

Synthesis, Characterization, Molecular docking, Antibacterial Activity, Antioxidant and Anticancer of New 1,2,4-Triazole Derivative

A novel 1,2,4-triazole-5-thiol derivative was designed through a series of reactions. Firstly, Azo derivative 1 was synthesized by a general method with two steps, a diazotization reaction in an acidic medium, and a coupling reaction in basic conditions. Secondly, Azo-carboxylic acid 1 reacted with SOCl2 to produce acid chloride derivative 2. Then carbothiamide derivative 3 was synthesized through substitution reaction by reacting 2 with 4-phenyl thiosemicarbazide in pyridine. In the next step, carbothiamide 3 was reacted with sodium hydroxide solution to afford target triazole derivative 4. The structures of all synthesized derivatives were confirmed by techniques (1H, 13C NMR, IR). Moreover, the triazole derivative 4 was evaluated for its biological activity as an anticancer, antioxidant, and antibacterial. The results presented that compound 4 has moderate antibacterial activity and a high free radical scavenging effect (IC50 30.2 μg/mL) compared to vitamin C (IC50 21 μg/mL). The anticancer activity results presented that compound 4 has a toxic effect on a colon cancer cell line CaCo-2. The potential effect of compound 4 on the 5lqf protein was examined in silico studies.

Multi-omic integration reveals alterations in nasal mucosal biology that mediate air pollutant effects on allergic rhinitis.

Allergic rhinitis is a common inflammatory condition of the nasal mucosa that imposes a considerable health burden. Air pollution has been observed to increase the risk of developing allergic rhinitis. We addressed the hypotheses that early life exposure to air toxics is associated with developing allergic rhinitis, and that these effects are mediated by DNA methylation and gene expression in the nasal mucosa. In a case-control cohort of 505 participants, we geocoded participants' early life exposure to air toxics using data from the US Environmental Protection Agency, assessed physician diagnosis of allergic rhinitis by questionnaire, and collected nasal brushings for whole-genome DNA methylation and transcriptome profiling. We then performed a series of analyses including differential expression, Mendelian randomization, and causal mediation analyses to characterize relationships between early life air toxics, nasal DNA methylation, nasal gene expression, and allergic rhinitis. Among the 505 participants, 275 had allergic rhinitis. The mean age of the participants was 16.4 years (standard deviation = 9.5 years). Early life exposure to air toxics such as acrylic acid, phosphine, antimony compounds, and benzyl chloride was associated with developing allergic rhinitis. These air toxics exerted their effects by altering the nasal DNA methylation and nasal gene expression levels of genes involved in respiratory ciliary function, mast cell activation, pro-inflammatory TGF-β1 signaling, and the regulation of myeloid immune cell function. Our results expand the range of air pollutants implicated in allergic rhinitis and shed light on their underlying biological mechanisms in nasal mucosa.

Simple One-Pot Preparation of Some Highly Electrophilic Haloacetylenes

Preparation of some bis(trialkylstannyl)acetylenes from the corresponding trialkylstannyl chlorides was improved. The tin reagents interact with reactive acid chlorides and bromides to afford intermediate 1-acyl-2-trialkylstannylacetylenes in quantitative yields. The subsequent halogenation performed as a one-pot procedure gives the target 1-acyl-2-haloacetylenes in high yields and provides an effective recycling of the expensive starting trialkylstannyl chlorides.

17β-estradiol induces hyperresponsiveness in guinea pig airway smooth muscle by inhibiting the plasma membrane Ca2+-ATPase

High serum estrogen concentrations are associated with asthma development and severity, suggesting a link between estradiol and airway hyperresponsiveness (AHR). 17β-estradiol (E2) has non-genomic effects via Ca2+ regulatory mechanisms; however, its effect on the plasma membrane Ca2+-ATPases (PMCA1 and 4) and sarcoplasmic reticulum Ca2+-ATPase (SERCA) is unknown. Hence, in the present study, we aim to demonstrate if E2 favors AHR by increasing intracellular Ca2+ concentrations in guinea pig airway smooth muscle (ASM) through a mechanism involving Ca2+-ATPases.In guinea pig ASM, Ca2+ microfluorometry, muscle contraction, and Western blot were evaluated. Then, we performed molecular docking analysis between the estrogens and Ca2+ ATPases.In tracheal rings, E2 produced AHR to carbachol. In guinea pig myocytes, acute exposure to physiological levels of E2 modified the transient Ca2+ peak induced by caffeine to a Ca2+ plateau. The incubation with PMCA inhibitors (lanthanum and carboxyeosin, CE) partially reversed the E2-induced sustained plateau in the caffeine response. In contrast, cyclopiazonic acid (SERCA inhibitor), U-0126 (an inhibitor of ERK 1/2), and choline chloride did not modify the Ca2+ plateau produced by E2. The mitochondrial uniporter activity and the capacitative Ca2+ entry were unaffected by E2. In guinea pig ASM, Western blot analysis demonstrated PMCA1 and PMCA4 expression. The results from the docking modeling demonstrate that E2 binds to both plasma membrane ATPases. In guinea pig tracheal smooth muscle, inhibiting the PMCA with CE, induced hyperresponsiveness to carbachol. 17β-estradiol produces hyperresponsiveness by inhibiting the PMCA in the ASM and could be one of the mechanisms responsible for the increase in asthmatic crisis in women.

Selective cross-metathesis of cellobiose derivatives with amido-functionalized olefinic structures: A model study for synthesis of cellulosic diblock copolymers

This work describes a model study for synthesis of cellulose-based block copolymers, investigating selective coupling of peracetyl β-d-cellobiose and perethyl β-d-cellobiose at their reducing-ends by olefin cross-metathesis (CM). Herein we explore suitable pairs of ω-alkenamides that permit selective, quantitative coupling by CM. Condensation reactions of hepta-O-acetyl-β-d-cellobiosylamine or hepta-O-ethyl-β-d-cellobiosylamine with acyl chlorides afforded the corresponding N-(β-d-cellobiosyl)-ω-alkenamide derivatives with an aromatic olefin or linear olefinic structures. Among the introduced olefinic structures, CM of the undec-10-enamide (Type I olefin) and the acrylamide (Type II olefin) gave the hetero-block tetramers, N-(hepta-O-ethyl-β-d-cellobiosyl)-N′-(hepta-O-acetyl-β-d-cellobiosyl)-alkene-α,ω-diamides, with >98 % selectivity. Moreover, selectivity was not influenced by the cellobiose substituents when a Type I olefin with a long alkyl tether was used. Although the amide carbonyl group could chelate the ruthenium atom and reduce CM selectivity, the results indicated that such chelation is suppressed by sterically hindered pyranose rings or the long alkyl chain between the amido group and the double bond. Based on this model study, selective end-to-end coupling of tri-O-ethyl cellulose and acetylated cellobiose was accomplished, proving the concept that this model study with cellobiose derivatives is a useful signpost for selective synthesis of polysaccharide-based block copolymers.