Acrylic Acid Derivatives Research Articles

(E)‑phenethyl 3‑(3,5‑dihydroxy‑4‑isopropylphenyl) acrylate gel improves DNFB-induced allergic contact hypersensitivity via regulating the balance of Th1/Th2/Th17/Treg cell subsets

(E)‑phenethyl 3‑(3,5‑dihydroxy‑4‑isopropylphenyl) acrylate gels (THCA354) is a novel polyphenols acrylic acid derivative. To investigate the immunoregulatory mechanisms of THCA354, we established a mouse model of 2,4‑dinitrofluorobenzene (DNFB)-induced allergic contact dermatitis (ACD). Responses of Th1, Th2, Th17 and regulatory T cells (Tregs) were determined by flow cytometry, reverse-transcriptase polymerase chain reaction (RT-PCR) and enzyme linked immunosorbent assay (ELISA). Our study found that topical application of THCA354 gel could inhibit ear swelling, reduce inflammatory cell infiltration, down-regulate Th1/Th17 responses and enhance Th2/Treg responses. These findings indicated that THCA354 gel exerted its immunotherapeutic effects by modulating the balance of Th1/Th2/Th17/Treg cell subsets, suggesting that THCA354 gel could be used as a promising drug candidate for intervention of ACD.

Platinum-Catalyzed Deuteration of Acrylic and Methacrylic Acid Derivatives

Key words deuteration - platinum on carbon - acrylic acid derivatives - methacrylic acid derivatives

Terminal Alkenes from Acrylic Acid Derivatives via Non-Oxidative Enzymatic Decarboxylation by Ferulic Acid Decarboxylases.

Fungal ferulic acid decarboxylases (FDCs) belong to the UbiD‐family of enzymes and catalyse the reversible (de)carboxylation of cinnamic acid derivatives through the use of a prenylated flavin cofactor. The latter is synthesised by the flavin prenyltransferase UbiX. Herein, we demonstrate the applicability of FDC/UbiX expressing cells for both isolated enzyme and whole‐cell biocatalysis. FDCs exhibit high activity with total turnover numbers (TTN) of up to 55000 and turnover frequency (TOF) of up to 370 min−1. Co‐solvent compatibility studies revealed FDC's tolerance to some organic solvents up 20 % v/v. Using the in‐vitro (de)carboxylase activity of holo‐FDC as well as whole‐cell biocatalysts, we performed a substrate profiling study of three FDCs, providing insights into structural determinants of activity. FDCs display broad substrate tolerance towards a wide range of acrylic acid derivatives bearing (hetero)cyclic or olefinic substituents at C3 affording conversions of up to >99 %. The synthetic utility of FDCs was demonstrated by a preparative‐scale decarboxylation.

Topology Effect of AIEgen-Appended Poly(acrylic acid) with Biocompatible Segments on Ca2+-Sensing and Protein-Adsorption-Resistance Properties.

We recently reported that tetraphenylethene-appended poly(acrylic acid) derivatives (e.g., PAA-TPE0.02) can serve as fluorescent Ca2+ sensors in the presence of physiological concentrations of biologically relevant ions, amino acids, and sugars. However, in the presence of basic proteins such as albumins, the Ca2+-sensing property of the polymer is significantly impaired due to the nonspecific adsorption of protein molecules, which competes with binding to Ca2+. To solve this problem, we explored new designs by focusing on the polymer-chain topology of PAA-TPE0.02 with biocompatible segments. Here, we report the Ca2+-sensing and protein-adsorption-resistance properties of various types of PAA-TPE0.02 copolymers with a poly(oligoethylene glycol acrylate) (polyOEGA) segment, featuring a random, diblock, triblock, or 4-armed-star-block structure. Through this study, we show an interesting topology effect; i.e., a branch-shaped PAA-TPE0.02-co-polyOEGA with biocompatible segments at every terminal (i.e., 4-armed-star-block copolymer) exhibits both good Ca2+-sensing and protein-adsorption-resistance properties.

The synthesis of diethyl 2-(2,2 $$'$$ ′ -bipyridin-4-ylmethylene)malonate and diethyl 3,3 $$'$$ ′ -(2,2 $$'$$ ′ -bipyridine-4,4 $$'$$ ′ -diyl)diacrylate

The new acrylic acid derivatives diethyl 2-(2,2 $$'$$ -bipyridin-4-ylmethylene)malonate and diethyl 3,3 $$'$$ -(2,2 $$'$$ -bipyridine-4,4 $$'$$ -diyl)diacrylate which may be used for the introduction of metal coordination sites in polyacrylates were synthesized and characterized. Intermediates of the syntheses were prepared by improved synthetic protocols working under microwave conditions whenever it was advantageous for the resulting product in terms of reaction time and/or chemical yield. In addition, the crystal structure of one of the intermediates, 4,4 $$'$$ -dibromo-2,2 $$'$$ -bipyridine (6), is reported, in which molecules are arranged into infinite chains by C-H—Br interactions. SYNOPSIS Synthesis and characterization of new 2,2’-bipyridine ligands with substituents related to acrylic acid esters are reported. These compounds offer the possibility to incorporate 2,2’-bipyridine ligands or coordination compounds derived from them into polyacrylate materials.

Direct Deuteration of Acrylic and Methacrylic Acid Derivatives Catalyzed by Platinum on Carbon in Deuterium Oxide

AbstractThe platinum on carbon (Pt/C)‐catalyzed deuteration of acrylic and methacrylic acid derivatives in deuterium oxide (D2O) efficiently proceeded to give the corresponding acrylic acid‐d3 and methacrylic acid‐d5 derivatives. The olefinic functionality, as well as the methyl group on the unsaturated functionality of the substrate, were satisfactorily deuterated via the hydrogen (H)‐deuterium (D) exchange reaction. The obtained deuterated compounds are useful building blocks and efficiently converted to the corresponding desired products including a polymer without the degradation of the original deuterium contents.magnified image

Synthesis and characterization of metal ion-imprinted polymers

In this study, ion-imprinted polymeric materials from an aqueous solution were prepared to remove metal ions \((\hbox {M}^{2+})\) like \(\hbox {Ni}^{2+}\), \(\hbox {Co}^{2+}\), etc. To prepare ion-imprinted polymers (IIPs), acrylic acid derivatives (XA) like acrylamide (AAm), methacrylic acid and itaconic acid were chosen as monomers. Metal ions formed binary chelate complexes with the help of 8-hydroxyquinoline (8-HQ). The solution containing functional monomers and the binary complex were polymerized with the help of various cross-linkers [ethylene glycol dimethylacrylate (EGDMA) or trimethylpropane trimethacrylate (TMPTMA)] and the target ion was removed from this polymer through an applicable method to produce IIPs. Furthermore, the control polymers (CPs) were synthesized through the same method without using metal ion. Characterization of the polymeric materials was investigated through spectroscopic (FTIR/ATR), thermal (TGA, DSC) and surface (SEM and XRD) analyses. Functional monomers, cross-linkers and the target ion’s species were changed during preparation of IIPs to observe their effect on imprinting of the target ion. Adsorption of the target ion to the prepared IIPs and the factors affecting the adsorption like concentration, pH, temperature, mass, etc. were studied.

The Synthesis of (1,3,4-Oxadiazol-2-yl)Acrylic Acid Derivatives with Antibacterial and Protistocidal Activities

A series of new 1,3,4-oxadiazol-2-yl-acrylic acids was synthesized by cyclization of 4-(2-R-hydrazino)- 4-oxo-2-butenic acids, and their antibacterial and protistocidal activities were studied. The p-substituted benzyl derivatives in the Z-form were shown to exhibit a high protistocidal activity, which exceeded that of the reference drug Baycox (toltrazuril) by several times, whereas the 3-hydroxy-2-naphthyl derivative, in addition to a very high protistocidal activity, also exhibited a moderate antibacterial activity.

The trans/cis photoisomerization in hydrogen bonded complexes with stability controlled by substituent effects: 3-(6-aminopyridin-3-yl)acrylate case study.

The association of aminopyridine-based acrylic acid and its salt was studied by NMR titration experiments. The AA (acceptor, acceptor) hydrogen-bonding pattern present in the salt forms a complex readily with a DD (donor, donor) hydrogen-bonding pattern of the substituted ureas even in polar and competitive environment. The double carbon–carbon bond in the acrylic acid derivative is subjected to photoisomerization. This is dependent on the association with substituted urea derivatives. The substituent in ureas influences the trans/cis isomerization kinetics and position of the photostationary state. Two mechanisms that influence the photoisomerization were proposed. To the best of our knowledge, the trans/cis photoisomerization influenced by the substituent in such a hydrogen-bonding pattern has not observed previously. It was shown that interaction with urea derivatives causes lowering of the trans-to-cis photoreaction rates.

Synthesis of biocompatible amino acid-modified poly(acrylic acid) derivatives for intracellular gene delivery

ABSTRACTCationic polymers provide versatile traits that fit for nonviral gene delivery applications. However, cationic polymers could exhibit significant cytotoxicity. Poly(acrylic acid) by conjugating side chains with either primary amine or with different number of alpha mine of alanine (denoted as PAla polymers) was chemically modified and the impact of amine groups of poly(acrylic acid) regarding biocompatibility and intracellular gene delivery efficiency was investigated. Design of PAla polymers proved that the incorporation of alanine in cationic polymers may significantly decrease cytotoxicity of the resulting polymers while maintaining the efficiency of cellular uptake and the intracellular gene delivery of the DNA/cationic polymer complex.

Mesoscopic Structural Aspects of Ca2+-Triggered Polymer Chain Folding of a Tetraphenylethene-Appended Poly(acrylic acid) in Relation to Its Aggregation-Induced Emission Behavior

We recently reported that tetraphenylethene-appended poly(acrylic acid) derivatives [PAA-TPEx (x = 0.01–0.05)] provide a fluorescent Ca2+ sensor, where aggregation-induced emission (AIE) of the TPE pendants occurs in conjunction with Ca2+-triggered polymer-chain folding. On the basis of dynamic and static light-scattering data, here we discuss the hydrodynamic radius and molar mass of PAA-TPE0.01 in the presence of Ca2+, Mg2+, or Na+ at various concentrations and elucidate the origin of the Ca2+ selectivity. In contrast to Na+, which exclusively triggered nonfluorescent interpolymer aggregation of PAA-TPE0.01, Ca2+ and Mg2+ induced polymer-chain folding associated with AIE from the TPE pendants. Importantly, Ca2+ caused polymer-chain folding more effectively than Mg2+. Consequently, polymer aggregates formed in the presence of Ca2+ possessed a much higher inner density than those formed in the presence of Mg2+, leading to a more pronounced AIE behavior and, in turn, the Ca2+ ion selectivity over Mg2+.

Boranes in Organic Chemistry 1. α-Carbonylalkyl- and β-Oxyalkylboranes in Organic Synthesis

<p>This review is devoted to the synthesis of a-carbonylalkyl- and β-hydroxy-alkyl boranes and their use in organic synthesis. a-Carbonyl-alkylboranes include several heteroatomic compounds, in particular, [1.2.3]-diazaborinines, uracyl boronic acids, and [1.2.3.4]-diaza-diboretes. The latter type has been obtained by the ketene aminoborations. The reactions of halogenboranes with diazoesters and sulfur ylides resulting in formation of a-carbonyl alkylborates containing diazofunction or ylide structural fragment are described. Amino and halogen boration of acetylenic acid esters was also used for the synthesis of a-carbonyl alkyl boranes. Reactions involving Cr-carbene complexes and acetylenic borone esters were presented for the synthesis of naphthoquinone boronic acids. The formation of amidoboranes by boration of dichloroacetanilides was remined. Boration of 4,8-dimethoxy-2-quinolone with trimethylborates leading to 2-quinolone-3-boronic acid was described. The common synthetic method to a-carbonyl alkyl boranes based on the hydroboration of acrylic acid derivatives was discussed. The results of enhydrazones hydroboration, leading to stable cyclic complexes have been mentioned. The interaction of a-bromoketones with trialkyl or dialkylboranes represents as a general synthetic method to a-carbonyl alkyl boranes. Synthetic approaches to â-hydroxy alkyl boranes are performed. The wide spread hydroboration of vinyl and allyl esters received a well-described attention. The hydroboration of cyclanone enol acetates, 3-keto- and 17-keto-steroids and cyclic allyl alcohol acetates was discussed. The results of aliphatic and alicyclic vinyl esters (including dihydrofuran derivatives) boralylation leading to β-hydroxy alkyl boranes have been envisaged. The synthesis of optically active β-hydroxy alkyl boranes using chiral borane hydrides was discussed. The heterocyclic boran dihydrides are obtained by the hydroboration of dihydropyranes, chromenes and flavenes. Borosilylation of allyl allenylic esters was also been envisaged. The synthetic scheme to optically active boranes and further optically active alcohols were presented. The problems of selectivity regularities in hydroboration reaction by intermolecular complex formations have been discussed.</p>

Peptidyl-Prolyl Model Study: How Does the Electronic Effect Influence the Amide Bond Conformation?

The triple-helical structure of collagen, the most abundant protein in animal bodies, owes its stability to post-translationally installed hydroxyl groups at position 4 of prolyl residues. To shed light on the nature of this phenomenon, we have examined the influence of the 4-substituent on the amide isomerism in peptidyl-prolyl analogues. The rigid bicyclic skeleton of 2,4-methanoprolines allowed us to follow the through-bond impact of the substituent group (electronic effect) without the side-chain conformation being affected by a stereoelectronic effect. These proline analogues were prepared by [2 + 2] photocycloaddition of (2-allylamino)acrylic acid derivatives. Subsequent pKa studies demonstrated a remarkable electronic effect of the 4-fluorine substitution, while the effect of the 4-methyl group was negligible. The trans/cis amide ratio was measured in model compounds under low temperature conditions. The observed prevalence for a trans-amide is extraordinary, and in this regard, 2,4-methanoproline is closer to primary α-amino acids than to proline. At the same time the amide rotation velocities were 3-4 orders of magnitude higher when compared to N-acetylprolyl. Finally, our results indicate that the electronic effect of the 4-substituent only affects the kinetics of the amide isomerization but not the thermodynamic prevalence for the trans-rotamer.

Rheological and sensory properties of hydrophilic skin protection gels based on polyacrylates

Introduction. With the current increases in occupational skin diseases, literature data attesting the decreasing efficiency of barrier creams with respect to the manufacturer’s declarations and legal regulations granting skin protection gels for employees, research is required to analyse and evaluate the recipes used for hydrophilic skin protection gels based on polyacrylates. Methods. This study investigated the rheological properties, pH and sensory perception of hydrophilic barrier gels based on polyacrylates. Results. The acrylic acid derivatives used were good thickeners, and helped to form transparent gels of adequate durability. They could be used to create hydrophilic films on the surface of the skin to protect it against hydrophobic substances. A correlation was shown between the results of the rheological properties and the barrier properties of the gels. This confirms the possibility of monitoring the quality of the gels at the stage of recipe development. Conclusions. Polyacrylates are viable for use in industry to produce hydrophilic barrier creams suitable for skin protection.

An Unusual Diterpene-Enhygromic Acid and Deoxyenhygrolides from a Marine Myxobacterium, Enhygromyxa sp.

Three new compounds, enhygromic acid (1) and deoxyenhygrolides A (2) and B (3), were isolated from a marine myxobacterium, Enhygromyxa sp. Compound 1 was found to be an acrylic acid derivative with a rare polycyclic carbon skeleton, decahydroacenaphthylene, by spectroscopic analyses. Compounds 2 and 3 were deoxy analogs of the known γ-alkylidenebutenolides, enhygrolides. Compound 1 exhibited cytotoxicity against B16 melanoma cells and anti-bacterial activity against Bacillus subtilis, and enhanced the NGF-induced neurite outgrowth of PC12 cells.

Polymorphism and Isostructurality of the Series of 3-(4,5-Diaryl-4H-1,2,4-triazole-3-yl)propenoic Acid Derivatives

Polymorphism of four biologically active 3-(4,5-diaryl-4H-1,2,4-triazole-3-yl)propenoic acid derivatives has been investigated. Traditional solution-based solid-state forms screening revealed three anhydrous forms of 3-[4-phenyl-5-(2-pyridyl)-4H-1,2,4-triazole-3-yl]propenoic acid. Noteworthy, two pairs of concomitant polymorphs were detected for this system. Two other compounds were found to be dimorphic. The molecular and crystal structures of all obtained crystal forms were established by single-crystal X-ray diffraction. The resulting crystal structures were analyzed in terms of molecular conformation, intermolecular interaction patterns, and crystal packing motifs. The experimental studies were supported by extended lattice and interaction energy calculations. It was found that the carboxylic group adopts the anti conformation in all studied forms and is involved in the intramolecular O–H···Ntriazole hydrogen bonding. In consequence, the association modes are dominated by the weak C–H···O, C–H···N hyd...

Copper-Catalyzed Stereodefined Construction of Acrylic Acid Derivatives from Terminal Alkynes via CO2 Insertion.

IPrCuCl catalyzes the CO2 insertion reaction undergone by a dialkylvinylborane intermediate derived from alkynyltrialkylborate by a 1,2-alkyl group migration to afford α-alkyl acrylic acids with excellent regio- and stereoselectivities.

Radiation Induced Grafting of Viscose Rayon Fabrics with Some Acrylic Acid Derivatives and Styrene

Radiation induced grafting of viscose rayon fabrics, consisting mainly of cellulose fibers, with some acrylic acid derivatives, namely methyl acrylate, acrylamide and acrylonitrile, and also styrene, has been studied. The resultant graft yields have been determined as a function of the applied different experimental parameters. The impact of the graft yields on the physicochemical properties of viscose rayon fabrics such as swelling, moisture absorption, tensile strength, elongation at break, crease recovery angle and also dyeing ability of the grafted fabrics, has been also studied.

A deciduous directing group approach for the addition of aryl and vinyl nucleophiles to maleimides.

A Rh(iii)-catalyzed C-H activation followed by conjugate addition to maleimides, using carboxylic acid as a traceless/deciduous directing group, to formally furnish a Csp2-Csp3 bond is presented. For the first time, derivatives of acrylic acid have been shown as surrogates for the unstable and expensive alkenyl boronic acids.

Applications of polymers in intraocular drug delivery systems.

We are entering a new era of ophthalmic pharmacology where new drugs are rapidly being developed for the treatment of anterior and posterior segment of the eye disease. The pharmacokinetics of drug delivery to the eye remains a very active area of ophthalmic research. Intraocular drug delivery systems allow the release of the drug, bypassing the blood-ocular barrier. The main advantage of these preparations is that they can release the drug over a long time with one single administration. These pharmaceutical systems are of great important in the treatment of the posterior segment diseases, and they can be prepared from biodegradable or nonbiodegradable polymers. Biodegradable polymers have the advantage of disappearing from the site of action after releasing the drug. The majority of intraocular devices are prepared from nonbiodegradable polymers, and they can release controlled amounts of drugs for months. Nonbiodegradable polymers include silicone, polyvinyl alcohol, and ethylene-vinyl acetate. The polymers usually employed to prepare nanoparticles for the topical ophthalmic route are poly (acrylic acid) derivatives (polyalquilcyanocrylates), albumin, poly-ε-caprolactone, and chitosan. Dendrimers are a recent class of polymeric materials with unique nanostructure which has been studied to discover their role in the delivery of therapeutics and imaging agents. Hydrogels are polymers that can swell in aqueous solvent system, and they hold the solvents in a swollen cross-linked gel for delivery. This review exhibits the current literature regarding applications of polymers in ophthalmic drug delivery systems including pharmacokinetics, advantages, disadvantages, and indications aimed to obtain successful eye therapy.Method of Literature Search:A systematic literature review was performed using PubMed databases into two steps. The first step was oriented to classification of intraocular polymers implants focusing on their advantages and disadvantages. The second step was focused on the role of polymers therapy for intraocular pathology with clinical examples. The search strategy was not limited by year of publication.