Acryloyl Moiety Research Articles

TDDFT elucidating the PET-Inhibition Mediated fluorescence enhancement in a Cysteine probe

TDDFT has been used to confirm the cysteine-sensing mechanism of a reported fluorescent probe (Talanta, 2020, 220, 12136). Frontier molecular orbital analysis showed that the probe underwent a PET process from quinazolinone to acryloyl, which made the fluorescence quenched together with nonplanar structure. Cysteine removed the acryloyl moiety and inhibited the PET process. The planar geometry of the probe-cysteine product enlarged the conjugated system and enhanced the green fluorescence of the fluorophore. Moreover, the charge redistribution also led to the excited-state proton transfer process, ultimately enhanced the fluorescence intensity and a notable Stocks shift.

Novel quinolin-4-ylcarbonylhydrazine having N-(3-arylacryloyl) moiety: Design, synthesis and biological evaluation as potential cytotoxic agents against MDA-MB-231 via tubulin assembly inhibition

A new set of quinolin-4-ylcarbonylhydrazine derivatives 7a-i and 9a,b bearing 3-arylacryloyl moiety has been synthesized and investigated for their potential anticancer activity. The synthetic protocol involves the following step: the target quinoline derivatives 7a-i and 9a,b appended to the acryloyl moiety were synthesized from quinolin-4-carbohydrazide intermediate with respective ethyl 2-arylamido-3-arylacrylate compounds. The cytotoxic activity study was evaluated using the functional MTT method. The most of target compounds displayed potent cytotoxic activity against MDA-MB-231 cell line. Among them, compounds 7d and 7 h were found to be promising antiproliferative agents with IC50 values of 4.04 and 1.78 μM, respectively, relative to the effective anticancer drug, Dox (IC50 = 5.33 μM). Compound 7 h exhibited cytotoxic activity by causing cell cycle to block at G2/M phase in addition to pro-apoptotic effect, as shown by flow cytometric measurement. In addition, the inhibitory action against β-tubulin polymerization was investigated. Finally, compound 7 h diminished the level of mitochondrial potential by almost 2.8-fold compared to control, indicating that the cellular death proceeds through the provoke of the intrinsic mitochondrial pathway of apoptosis.

Akriloil Grup İçeren Schiff Bazlarının Potansiyometrik İyon-Seçici Sensörlerde İyonofor Olarak Kullanımının Araştırılması

Bu çalışmada, yeni sentezlenen iyonoforlar kullanılarak tümüyle katı-hal krom (III)-seçici potansiyometrik polivinil klorür (PVC) membran sensör geliştirildi. Bu amaçla yeni sentezlenen akriloil grup içeren (E)-4-(4-Nitro fenilimino) metil fenil akrilat (A1), (E)-4-(4-kloro fenilimino) metil fenil akrilat (A2) ve (E)-4-(4-hidroksibenzil dimino) benzoik asit akrilat (A3) schiff bazları iyonofor olarak kullanıldı. En uygun potansiyometrik özelliklere sahip membran bileşimi farklı oranlarda iyonoforlar (A1, A2 ve A3), plastikleştiriciler (o-nitrofeniloktil eter (o-NPOE)), bis (2-etilheksil) sebekat (DOS), dibutil ftalat (DBP) dioktil ftalat (DOP) ve PVC kullanılarak belirlendi. Ayrıca, potasyum tetrakisparaklorofenil borat (KTpClPB) ve sodyum tetrafenil borat (NaTPB) elektrotlarının doğrusal çalışma aralığına ve eğimine her onkat’lık iyon aktivitesi değişimine karşı etkisi de araştırıldı. Geliştirilen krom (III)-seçici sensör için % 1,0 A2 bileşiği, % 67,0 (a/a) o-NPOE ve % 32,0 (a/a) PVC oranları en uygun membran bileşimi olarak belirlendi. Geliştirilen krom (III)-seçici sensör pH 3,50’de 1,3×10-7−1,0×10-1 M konsantrasyon aralığında standart krom (III) iyon çözeltisine karşı doğrusal cevap sergiledi (R2= 0,9938). Sensör ile doğrusal çalışma aralığındaki her onkat’lık standart krom (III) konsantrasyon değişiminin ortalaması 27,12±0,81 mV’luk eğim değeri, tekrarlanabilir potansiyeller elde edildi. Geliştirilen tümüyle katı-hal krom (III)-seçici potansiyometrik PVC membran sensörün tayin limiti 6,3×10-8 M ve cevap süresi ≤10 s olarak belirlendi. Yaygın bazı katyon türlerinin geliştirilen sensör üzerindeki girişim etkileri incelendi. Önerilen sensörün analitik olarak kullanılıp kullanılamayacağını araştırmak için, gerçek numunelerde krom (III) iyonunun potansiyometrik tayini gerçekleştirildi. Elde edilen sonuçlar indüktif olarak eşleştirilmiş kütle spektrometresi (ICP-MS) metodu ile elde edilen verilerle istatiksel olarak karşılaştırıldı.

Efficient exfoliation of UV-curable, high-quality graphene from graphite in common low-boiling-point organic solvents with a designer hyperbranched polyethylene copolymer and their applications in electrothermal heaters

The use of stabilizer with designer structures can effectively promote graphite exfoliation in common solvents to render functionalized graphene desirable for their various applications. Herein, a hyperbranched polyethylene copolymer, HBPE@Py@Acryl, simultaneously bearing multiple pyrene terminal groups and pendant acryloyl moieties has been successfully synthesized from ethylene with a Pd-diimine catalyst based on unique chain walking mechanism. The unique structural design of the HBPE@Py@Acryl makes it capable of effectively promote graphite exfoliation in a series of common, low-boiling-point organic solvents, e.g. CHCl3, to render stable graphene dispersions with concentrations effectively adjustable by changing feed concentrations of graphite and polymer or sonication time. Meanwhile, it can be irreversibly adsorbed on the exfoliated graphene surface based on the π-π interactions between them to concurrently render acryloyl-functionalized graphene free of structural defects, with majority (92.7%) of them having a thickness of 2–3 layers. This allows us to obtain graphene electrothermal films simply by filtration and UV irradiation, which exhibit outstanding stability in use. The action mechanism of the HBPE@Py@Acryl as stabilizer for promoting graphite exfoliation and the role of UV irradiation on improving the stability in use of resulting graphene films have been elucidated.

A novel xanthylene-based effective mitochondria-targeting ratiometric cysteine probe and its bioimaging in living cells

In this study, a mitochondria-specific fluorescent probe for efficient ratiometric detection of Cys was designed and investigated. Probe 1 is composed of a xanthylene skeleton and a benzyl group containing an acryloyl moiety. The probe showed excellent water solubility, good selectivity and sensitivity toward Cys over other analytes, and afforded an extremely low detection limit of 33.7 nM. The possible detection mechanism was ascertained by HRMS analysis. Moreover, probe 1 had excellent mitochondrial-targeting ability (the Pearson's correlation coefficient was 0.96), and was capable of monitoring endogenous Cys in living HeLa cells by dual channel ratiometric bioimaging, demonstrating its significant potential in biological applications.

Computational Insight into Conformational Rearrangement and Intramolecular-H Bond Analysis of Some Calix[4]Arenes Including Acryloyl Moiety

Computational Insight into Conformational Rearrangement and Intramolecular-H Bond Analysis of Some Calix[4]Arenes Including Acryloyl Moiety

Synthesis, characterization, conformational equilibrium and intramolecular hydrogen bond analysis of Novel Azocalix[4]arenes including acryloyl moiety using DFT studies

Azocalix[4]arenes were synthesized via diazo-coupling reaction with aniline in 1:1, 1:2, 1:3 and 1:4 molar ratio. Novel Azocalix[4]arenes having Acryloyl moiety were prepared esterification reaction with metallic sodium and Acryloyl chloride with the same molar ratio of Azocalix[4]arene derivatives. The spectroscopic characterizations of the compounds were made by using IR, UV–Vis, 1H NMR and 13C NMR spectroscopies. In our study, the validation of the exact conformation of Azocalix[4]arene existing in a Cone, Partial Cone, 1,2-Alternate and 1,3-Alternate was realized by spectroscopic and DFT analyses. These results reveal that the compounds exist in the Cone conformation because of the existence of Intramolecular Hydrogen Bonds (IHBs) in the calixarene core. According to the conformational analysis, Cone conformation corresponds to the minimum energy for compounds 6, 7 and 8, as well. Both DFT and NMR results confirmed that a conformational rearrangement of compound 9 is 1,3-Alternate conformer. The experimental results were correlated with the theoretical calculations. In addition, Natural Bond Orbital (NBO) calculations were used to examine the electronic characteristics of the intramolecular hydrogen bonds. NBO energies show that the main contributions to energy stabilization correspond to LP → σ* interactions for IHBs, O⋅⋅⋅OH and the delocalisation LP → π* for OCO.

Lipase-catalyzed asymmetric synthesis of naphtho[2,3-c]furan-1(3H)-one derivatives by a one-pot dynamic kinetic resolution/intramolecular Diels–Alder reaction: Total synthesis of (−)-himbacine

One-pot sequential reactions using the acyl moieties installed by enzymatic dynamic kinetic resolution of alcohols have been little investigated. In this work, the acryloyl moiety installed via the lipase/oxovanadium combo-catalyzed dynamic kinetic resolution of a racemic dienol [4-(cyclohex-1-en-1-yl)but-3-en-2-ol or 1-(cyclohex-1-en-1-yl)but-2-en-1-ol] with a (Z)-3-(phenylsulfonyl)acrylate underwent an intramolecular Diels–Alder reaction in a one-pot procedure to produce an optically active naphtho[2,3-c]furan-1(3H)-one derivative (98% ee). This method was successfully applied to the asymmetric total synthesis of (−)-himbacine.

Fluorescent coumarin-based probe for cysteine and homocysteine with live cell application

Cysteine (Cys) and homocysteine (Hcy) are two of important biological thiols and function as important roles in several biological processes. The development of Cys and Hcy probes will help to explore the functions of biothiols in biological systems. In this work, a new coumarin-based probe AC, containing an acryloyl moiety, was developed for Cys and Hcy detection in cells. Cys and Hcy undergo a nucleophilic addition and subsequent cyclization reaction to remove to the acryloyl group and yield a fluorescent product, 7-hydroxylcomuarin. The probe AC showed good selectivity for cysteine and homocysteine over glutathione and other amino acids and had low detection limits of 65nM for Cys and 79nM for Hcy, respectively. Additionally, confocal imaging experiments demonstrated that the probe AC can be applied to visualize Cys and Hcy in living cells.

Tough polyion-complex hydrogels from soft to stiff controlled by monomer structure

Tough hydrogels with adjustable stiffness are expected for adapting application as various biomaterials. Oppositely charged polyelectrolytes form tough and self-healing physical polyion-complex (PIC) hydrogels via formation of inter-chain ionic bonds with a wide distribution in bond strength. The strong bonds serve as permanent crosslinking to impart elasticity and the weak bonds as reversible sacrificial bonds to dissipate energy and to self-heal. In this work, we fabricate four PIC hydrogels using four positively charged trimethyl-ammonium monomers with slightly different chemical moieties and a same negatively charged polymer. The obtained PIC hydrogels all show high toughness but large difference in stiffness, extensibility, and self-recovery kinetics. With slight difference in the monomer structure of the polycations, the modulus of the hydrogels varies over two orders in magnitude, from 0.36 to 56 MPa, and the difference in elongation at break is up to five times. The presence of acryloyl moiety and methyl moiety increase the stiffness of the hydrogels. In the temperature range studied, all the four PIC hydrogels exhibit the rheological simple behaviours, following the time-temperature superposition principle. The four samples show quite different dynamic relaxation spectra over wide frequency range, revealing large difference in the strength distribution of dynamic ionic bonds. SEM observation reveals quite different phase separation structure for the four samples, in which the polymer chain stiffness should play an important role. This understanding of structure-properties of the PIC hydrogels will merit the designing of various supramolecular tough hydrogels and therefore broaden the scope of hydrogels for the applications as biomaterials.

A near-infrared fluorescent probe for rapid and selective detection of hydrosulfide and imaging in live cells

A heptamethine cyanine-based near-infrared (NIR) fluorescent probe Cy-1 for hydrosulfide detection was developed, with the response mechanism based on nucleophilic substitution of acryloyl moiety by HS−. Upon addition of NaHS, Cy-1 displayed a rapid fluorescence quenching (excited at 700 nm) and a quick fluorescence enhancement (excited at 544 nm) as well as obvious changes in absorption spectra and color. The response was fast within tens of seconds and could be observed by naked eyes. By contrasting Cy-1 with the reported probe CyAC, the superiority of Cy-1 in selectivity over Cys was demonstrated. Besides, it also exhibited excellent selectivity and sensitivity to HS− over various anions (0.33-μM detection limit). Additionally, this probe was successfully applied in fetal bovine serum samples and imaging of hydrosulfide in living cells.

Synthesis of novel Schiff Bases containing acryloyl moiety and the investigation of spectroscopic and electrochemical properties

A novel Schiff bases and their acryloyl derivatives were synthesized through the reaction of p-hydroxybenzaldehyde in order of with aniline, p-chloroaniline, p-nitroaniline, p-methylaniline and p-aminobenzoic acid. The structures of these compounds were characterised spectroscopic techniques such of IR, 1H NMR, 13C NMR and Mass spectroscopy. π→π* and n→π* transitions were determined via UV–vis spectroscopy studies performed in EtOH, CHCl3, and DMF. Furthermore, the inhibition efficiencies of these new compounds were investigated on the surface of steel within the solution of 0.1 M NaCl, 0.1 M NaOH and 0.10 M H2SO4 solution via cyclic voltammetry and Tafel extrapolation methods.

Synthesis and cytotoxicity of novel chromenone derivatives bearing 4-nitrophenoxy phenyl acryloyl moiety

This work describes synthesis of novel chromenone derivatives bearing 4-nitrophenoxy phenyl acryloyl moiety through the reaction of 4-(4-nitrophenoxy)benzaldehydes and 3-acetyl-2H-chromen-2-ones in refluxing toluene. Cytotoxicity of all compounds was evaluated using a tetrazolium (MTT) colorimetric assay against human breast cancer cell line, MDA-MB-231.

Polymerisation of a T Cell Epitope with an Immunostimulatory C3d Peptide Sequence Enhances Antigen Specific T Cell Responses

The complement protein C3d and C3d derived peptides that bind CD21 are known to enhance immunity to co-immunised antigens. In this study we have synthesised the minimal CD21 binding sequence of C3d (1227LYNVEA1232) as mono, di and tri tandem repeats and derivatised the N-terminus with an acryloyl moiety. These acryloyl-(C3d) n peptides were co-polymerised with a acryloyl-T cell epitope (PAS1K) from the Porphyromonas gingivalis antigen the RgpA–Kgp proteinase–adhesin complex. The ability of C3d containing polymers to enhance T cell immunity in vitro and in vivo was evaluated. When used to stimulate in vitro PAS1K-primed or RgpA–Kgp complex-primed T cells the C3d containing PAS1K polymers induced a mixed and significantly (p < 0.05) higher IL-4 and IFNγ T cell response compared to that induced by the PAS1K peptide or polymer. PAS1K polymers containing tandem repeats of C3d induced a significantly (p < 0.05) stronger maximal proliferative response, at the same antigenic dose, compared to that induced by the PAS1K peptide or polymer. When used as immunogens to prime T cells all of the C3d containing PAS1K polymers induced a dominant IFNγ T cell response and reduced the antigen dose required for maximal proliferation 150-fold compared to that required for the PAS1K-peptide or polymer primed T cells. In conclusion, the 6 residue sequence LYNVEA from C3d is sufficient to enhance immunity to an antigen and that the effect is more pronounced when C3d is part of the immunising antigen rather than an in vitro stimulating antigen.

Formation of a Liquid-Crystalline Interpenetrating Poly(ionic liquid) Network Hydrogel

Preparation of a liquid-crystalline ionic-liquid (IL)-based interpenetrating polymer network (IPN) is described. The IPN is prepared sequentially by first photopolymerizing a self-assembled aqueous mixture of an IL monomer (1-(10-(acryloyloxy)decyl)-3-methylimidazolium chloride) that possesses an acryloyl moiety at the terminus of a C10 alkyl chain of the IL cation. In the second step, an acrylate counteranion is introduced and then photopolymerized to yield a durable self-supporting network polymer. Thermal analysis indicates the formation of a homogeneous (well-blended constituent polymers) IPN. The IPN adopts a lamellar structure possessing some residual in-plane tetragonal perforations, as evidenced by small-angle X-ray scattering (SAXS). The IPN can absorb large quantities of water, swelling to nearly 60 times its original volume, but retains mechanical integrity making it a durable hydrogel.

The stability and reactivity of activated acryloylcarbamates as reagents for the synthesis of N‐1 substituted thymine and uracil – an NMR and DFT study

AbstractThe mechanism of the decomposition of acryloylcarbamates 7a–b yielding highly reactive isocyanates 3a–b was proposed based on NMR measurements and quantum chemical calculations. A good agreement between the experimental kinetic data and DFT calculations allowed us to demonstrate that the stability of 7a–d depends on the presence of methyl in the acryloyl moiety and the position of the nitro group in the nitrophenolic part of the molecule. Furthermore, the reactivity of 7a–d with weakly nucleophilic and sterically hindered 2,4,6‐tri‐tert‐butylaniline was explored by 1H NMR demonstrating the usefulness of reagents 7a–d offering access to a variety of 1‐N‐substituted uracils and thymines with potentially interesting biological properties. Copyright © 2010 John Wiley &amp; Sons, Ltd.

Cysteine‐reactive covalent capture tags for enrichment of cysteine‐containing peptides

Considering the tremendous complexity and the wide dynamic range of protein samples from biological origin and their proteolytic peptide mixtures, proteomics largely requires simplification strategies. One common approach to reduce sample complexity is to target a particular amino acid in proteins or peptides, such as cysteine (Cys), with chemical tags in order to reduce the analysis to a subset of the whole proteome. The present work describes the synthesis and the use of two new cysteinyl tags, so-called cysteine-reactive covalent capture tags (C3T), for the isolation of Cys-containing peptides. These bifunctional molecules were specifically designed to react with cysteines through iodoacetyl and acryloyl moieties and permit efficient selection of the tagged peptides. To do so, a thioproline was chosen as the isolating group to form, after a deprotection/activation step, a thiazolidine with an aldehyde resin by the covalent capture (CC) method. The applicability of the enrichment strategy was demonstrated on small synthetic peptides as well as on peptides derived from digested proteins. Mass spectrometric (MS) analysis and tandem mass spectrometric (MS/MS) sequencing confirmed the efficient and straightforward selection of the cysteine-containing peptides. The combination of C3T and CC methods provides an effective alternative to reduce sample complexity and access low abundance proteins.

Formation of a Biomimetic, Liquid-Crystalline Hydrogel by Self-Assembly and Polymerization of an Ionic Liquid

Preparation and polymerization of a methylimidazolium-based ionic liquid (IL) that incorporates an acryloyl moiety at the terminus of a C8 alkyl chain is described. The IL monomer weakly self-assembles upon addition of water and oligomerizes on mild heating. Initiator-free polymerization (as evidenced by FT-IR spectroscopy) can be achieved by UV irradiation, forming an elastic, self-supporting hydrogel. Small-angle X-ray scattering (SAXS) studies on the unsupported polymer demonstrate that the hydrogel adopts an ordered lamellar structure. The polymer can absorb large quantities of water, swelling to nearly 200 times its original volume and, in the process, becoming a highly disordered lamellar structure. Swelling studies conducted using a range of organic solvents demonstrate that the polymer can also be swollen (albeit to a lesser extent) by polar, hydrogen-bonding solvents such as ethanol.

Acryloylated Glucose 3-Nitropropanoates from Indigofera kirilowii

Two unique glucose esters of 3-nitropropanoic acid with acryloyl moieties, kirilowin A and kirilowin B, were isolated from the roots of Indigofera kirilowii. Their structures were elucidated by detailed spectroscopic analysis. The two acrylates constitute new additions to the toxic glucose conjugates of 3-nitropropanoic acid in angiosperms.

Covalently grafted phospholipid monolayer on silicone catheter surface for reduction in platelet adhesion

We report a novel method of surface grafting a polymeric phospholipid system containing an acryloyl end group (1stearoyl-2-[12-(acryloyloxy)-dodecanoyl]- sn-glycero-3-phosphocholine) onto medical grade silicone catheters. The surface of silicone catheters was functionalized in a sequence of steps: plasma polymerization of allyl alcohol on the catheter surface, grafting acryloyl moieties and in situ polymerization of the pre-assembled acryloyl terminated phospholipids on the acryloyl functionalized catheter surface. The surface morphological changes analyzed by scanning electron microscopy (SEM) and atomic force microscopy (AFM), a sharp decrease in water contact angle, and appearance of N1s peak in XPS analysis indicated a successful monolayer grafting of the phospholipid. In platelet adhesion tests performed using platelets isolated from rabbit plasma, the phospholipid grafted surface showed fewer adhered platelets, without emerging pseudopodes or aggregation. However, ungrafted catheter surface showed large number of platelets in extensively spread and aggregated states. Thus, this modified phospholipid system and its simple grafting technique was very effective with regard to suppressing in vitro platelet adhesion on the silicon catheter surface.