Acryloyl Research Articles

Revisiting the Synthesis of Cellulose Acrylate and Its Modification via Michael Addition Reactions.

The synthesis of cellulose acrylate from cellulose with acryloyl chloride has been problematic due to unexpected gelation of the reaction mixture, but we discovered that the use of bulky amines was crucial for the reproducibility of the synthesis of cellulose acrylate. The solubility of the obtained cellulose acrylate depended on the reaction conditions due to the possible cross-linking oxa-Michael reaction between a remaining hydroxy group and the introduced acrylate group. The synthesized cellulose acrylate worked as a useful precursor of chemically modified cellulose materials because it reacted with various functionalized nucleophiles such as secondary amines and thiols as a Michael donor. This method was applied to the synthesis of N-methyl-d-glucamine-modified cellulose that works as an adsorbent for the removal of B(OH)3 in water.

A simple indanone-based red emission fluorescent probe for the rapid detection of cysteine in vitro and in vivo

Cysteine is a vital biothiols that plays an important role in numerous physiological and pathological processes. The development of simple molecule tools for detection and analysis Cys in subcellar environment is significant for further exploring their pathophysiological. In this work, a simple but activated fluorescent probe AMIA was constructed with a donor-π-accepter (D- π -A) structure, which using an indanone as the electron-withdrawing unit acting as the fluorophore, dimethylamino group attached to the position 4 of the benzene ring as the electron-donating, two double bonds as the linker group, and the acryloyl ester group as the trigger and response unit. This probe AMIA was exhibited highly selective and sensitive response to Cys over other amino acids and ions under physiological conditions. It was found that AMIA showed a red turn-on fluorescence response at 630 nm towards Cys with a large stroke shift of 170 nm and a very low detection limit of 26.3 nM. HRMS, 1H NMR and TD-DFT calculation further confirmed that the response mechanism is the Cys triggered the addition-cyclization reaction between AMIA’ acryloyl group and Cys’ sulfhydryl and amino unit, leading to the release of a red fluorescent dye AMIA-OH, which can be identified by naked eyes. Furthermore, AMIA was successfully applied for simultaneous determination of Cys in living cells and zebrafish with lower cytotoxicity and good cell permeability. We hope that this novel indanone-based probe AMIA will provide a new reference for visualized Cys in other complex biological system.

Self-strengthening and conductive cellulose composite hydrogel for high sensitivity strain sensor and flexible triboelectric nanogenerator

Triboelectric nanogenerators (TENGs) as promising energy harvesting devices have gained increasing attention. However, the fabrication of TENG simultaneously meets the requirements of green start feedstock, flexible, stretchable, and environmentally friendly remains challenging. Herein, the hydroxyethyl cellulose macromonomer (HECM) simultaneously bearing acrylate and hydroxyl groups was first synthesized and used as a crosslinker to prepare the chemically and physically dual-crosslinked cellulose composite hydrogel for an electrode material of stretchable TENG. Meanwhile, the in-situ polymerization of pyrrole endowed the hydrogel with satisfactory conductivity of 0.40 S/m. More impressively, the synergies of the cellulose rigid skeleton and the construction of the dual-crosslinking network significantly improved the mechanical toughness, and the hydrogel exhibited excellent self-strengthening through cyclic compression mechanical training, the self-strengthening efficiency reached 124.7 % after 10 compression cycles. Given these features, the hydrogel was used as wearable strain sensors with extremely high sensitivity (GF = 3.95) for real-time monitoring human motions. Additionally, the hydrogel showed practical applications in stretchable H-TENG for converting mechanical energy into electric energy to light LEDs and power a digital watch, and in self-powered wearable sensors to distinguish human motions and English letters. This work provided a promising strategy for fabricating sustainable, eco-friendly energy harvesting and self-powered electronic devices.

Strategy of eudragit coated curcumin nanoparticles delivery system: Release and cell imaging studies in simulated gastrointestinal microenvironments

Curcumin has a broad-spectrum anti-tumor effect and has no toxic side effects. However, the unique diketone structure of curcumin will undergo diketo-enol tautomerism under different acid-base conditions, resulting in its instability under physiological conditions. In addition, the low biocompatibility and absorption rate of curcumin also limit the use of curcumin drugs. In this paper, curcumin was modified by substitution of acryloyl and acrylsulfonyl groups, and four kinds of nanoparticles with regular morphology were prepared using non-toxic and non-irritating acrylic resin as coating material to improve the stability and bioavailability of the compounds. Zeta potential testing shows that the composites surface carries positive charges and have good stability. In the release experiment, four complexes have the potential for slow and controlled release. Imaging of Hela cells with different channels was performed, and the imaging results showed that the complexes could enter the cells and be absorbed by them, demonstrating good imaging performance. MTT experiments have shown that the complexes have certain anti-tumor activity and low cytotoxicity. In general, the complexes synthesized in this paper have potential in the field of drug fluorescence imaging detection. At the same time, this experiment provides a new idea for the design of slow and controlled release of drugs.

Benzothiazole-Based Fluorescent Probe as a Simple and Effective Platform for Functional Mitochondria Imaging.

Mitochondrial imaging is crucial for studying disease pathogenesis and diagnosis. However, commercially available mitochondria-specific fluorescent probes are limited due to the difficulty in modifying cationic probes for functional bioimaging of mitochondria. To address this, we prepared a hydroxythiophene-conjugated benzothiazole (BzT-OH) as a platform for the design of functional fluorescent probes. Two probes, BzT-OAc and BzT-OAcryl, were synthesized by substituting the hydroxy group in BzT-OH with acetate and acrylate groups, respectively. BzT-OAc demonstrated blue fluorescence that shifted to green emission after enzymatic cleavage of the acetate group, allowing for monitoring of endogenous esterase activity. BzT-OAcryl showed high selectivity for cysteine at pH > 8.0, owing to its pH-responsive property, and could detect pH perturbations caused by mitochondrial dysfunction. Both probes exhibited high biocompatibility, quantum yield, and large Stokes shifts in mitochondria. BzT-OH can be easily conjugated with other functional groups and substrates of various enzymes for designing fluorescent probes for functional mitochondrial imaging. The photofunctional property of the probe can be changed due to the involvement of the hydroxyl group in the excited state intermolecular proton transfer.

Microstructure and anti-corrosion properties of acrylic bone cement-based with MOF nanostructured hybrid coatings on AZ31 Mg alloy

Surface modification of biomedical AZ31 magnesium (Mg) alloy substrates with biocompatible and applicable polymer coatings is an effective and simple method to improve corrosion resistance. Herein, the biodegradable acrylic bone cement incorporation with different content of metal organic frameworks (Ce-MOFs or Zn-MOFs) coated on biodegradable Mg alloy (AZ31) substrates was fabricated by using a dip-coating method. Then, various characterizations like X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) and the water contact angle (WCA) tests were performed to determine the composition, morphology, structure, and wettability of the coatings. The compact acrylic bone cement coatings improve the hydrophilic effect due to the micro/nanostructure of acrylic and hydrophilic groups, but the addition of a small amount of Ce-MOF and Zn-MOFs structures reduces the hydrophilic effect of the coating surface. According to the electro-chemical analysis, prepared acrylic coating has better corrosion behavior compared to AZ31 sample. The PM sample demonstrates the lowest corrosion current density (icorr = 0.095 mA cm−2) compared to other samples. The dense acrylic compact coatings with higher amount of Ce-MOF content blocks the pores in the coating and lead to an inhibitory effect and improved the corrosion behaviors. The dense acrylic bone cement containing MOF coatings with improved electrochemical activity inhibits diffusion of the aggressive ions to the alloy surface.

Photocrosslinkable carboxylated polyvinyl alcohol nanocomposite hydrogels with enhanced compressive strength and cell adhesion

Polyvinyl alcohol (PVA) hydrogel is a kind of biomaterial with broad application prospects in the biomedical fields, but its poor mechanical properties and weak cell adhesion hinder its development. Herein, carboxylated PVA with acrylate groups (PVAGMACOOH) is synthesized, and consequently carboxylated PVA nanocomposite hydrogels are fabricated by UV-irradiating the mixture of PVAGMACOOH solution and nano-scale hydroxyapatite (HAP). The nanocomposite hydrogel can gel within several seconds under the UV light irradiation. Notably, it exhibits excellent compressive strength without fracture in the strain of more than 90%, while its tensile strength is 14.6 times of the pure PVA hydrogel without HAP, indicating energy dissipation mechanism by macromolecular chain creep and good load transferring from macromolecules to nanoparticles. Furthermore, the introduction of HAP significantly enhances cytocompatibility and cell adhesion of the hydrogel. The hydrogel would be a potential candidate for various biomedical applications.

Understanding the thermodynamic phase equilibria for the allyl acetate, allyl acrylate and allyl methacrylate under CO2 as supercritical solvent

Acrylic acid allyl ester groups show the non-ideal phase equilibria and have slightly or strong polarity. Phase equilibria for the allyl acetate, allyl acrylate and allyl methacrylate in conformity with chain-length play a crucial role as organic monomers in a number of chemical industries. The curves of the solution mixture for allyl acetate, allyl methacrylate, and allyl acrylate under high-pressure supercritical CO2 (super CO2) are examined with the help of a fabricated method at various temperatures within the boundary of (313.2 −393.2) K and pressures within (1.75–16.27) MPa. The three system for super CO2 + allyl acetate, super CO2 + allyl methacrylate and super CO2 + allyl acrylate solutions have critical mixed curves which show largest in p-T space between Tc (- critical temperatures) of super CO2 and allyl acetate or allyl acrylate or allyl methacrylate. The liquid + vapor data of super CO2 of three systems at a fixed pressure decreases with rise in temperature. The super CO2 + allyl acetate, super CO2 + allyl acrylate and super CO2 + allyl methacrylate systems display phase behavior of type-I. For the application at Peng-Robinson equation in theoretical investigation, solubility curves between the predicted and test results of the super CO2 + allyl acetate, super CO2 + allyl acrylate and super CO2 + allyl methacrylate binary systems were obtained the satisfactory agreement. The properties (pc, Tc and ω) and vapor pressure of allyl acetate, allyl acrylate and allyl methacrylate were estimated with group contribution and useful method.

Computationally developed acrylated epoxidized methyl ester based pressure-sensitive adhesives

Healthcare sector is increasingly demanding pressure-sensitive adhesives (PSAs) to be bio-sourced and biodegradable to replace petro-based PSAs, which are neither renewable nor sustainable. This investigation employs MD simulations to develop bio-based PSAs by replacing low Tg monomers such as 2-ethylhexyl acrylate partially and fully with acrylated epoxidized methyl ester (AEME). The simulation procedures used in this study were verified by comparing specific properties with published literature. The glass transition temperatures of all developed systems show insignificant differences and are well below application as desirable for developing PSA products. Also, these values closely match Fox equation estimates and are in good accord with experimental values. Surface characteristics like surface energy and interfacial adhesion with Al substrate have been predicted. A ∼79 % increment in surface energy with AEME content ensures good substrate wettability and thermodynamic work of adhesion. The interaction energy with Al substrate has been increased by ∼365 % with addition of AEME reflecting improved adhesion strength and enhanced tackiness of the PSA copolymer. AEME provides polar groups like acrylate and hydroxyl groups, which helps improve adhesion strength. The polar groups associated with AEME and increased crosslinking density enhanced mechanical properties of developed PSA systems. This computational research lays the path for developing innovative bio-based PSAs used in adhesive bandages and transdermal patches.

Retention of titanium copings to implant-supported fixed dental prostheses.

The aim of this in vitro study was to assess the effects of using different cements and titanium copings designs on the retention of implant-supported fixed dental prostheses (IFDPs) using a pull-out test. Fifty zirconia (ZirCAD; Ivoclar Vivadent) and 20 prepolymerized denture acrylic resin (AvaDent) rectangular (36mm × 12mm × 8mm) specimens were milled to mimic the lower left segmental portion of the All-on-Four IFDPs. Cylindrical titanium copings (Variobase; Straumann) (V) were used in 2 prepolymerized denture acrylic resin groups (n = 10) while conical titanium copings (Straumann) (C) were used as a control group for zirconia with 4 groups using cylindrical titanium copings. Before cementation, the outer surfaces of all titanium copings and the intaglio bonding surface of prosthetic specimens were airborne-particle abraded. All specimens were cemented following the manufacturer's recommendations and instructions according to the experimental design. After artificial aging (5000 cycles of 5°C 55°C, dwelling time 20s; 150 N, 1.5Hz in a 37°C water bath), all specimens were subjected to retention force testing using a pull-out test using a universal testing machine and a custom fixture with a crosshead speed 5mm/min. Modes of failure were classified as Type 1, 2, or 3. Retention force values were analyzed by the t-test for the prepolymerized denture acrylic resin specimen groups, and 1-way ANOVA and the Tukey test for the zirconia groups at α = 0.05. Mean and standard deviation retention force values varied from 101.1±67.1 to 509.0±65.2 N for the prepolymerized denture acrylic resin specimen groups. The zirconia groups ranged from 572.8±274.7 to 1416.1 ±258.0 N. There is no statistically significant difference in retention force values between V and C specimens cementing to zirconia with Panavia SA cement (Kuraray Noritake) (p = 0.587). The retention forces and failure modes were influenced by the cement used (p < 0.05). Modes of failure were predominantly Type 2 (mixed failure) and Type 1 (adhesive fracture from prosthetic materials) except for the quick-set resin group (Type 3, adhesive failure from coping). When bonding IFDPs onto titanium copings, quick-set resin provided significantly higher retention force for prepolymerized denture acrylic resin prostheses. Conical and cylindrical titanium copings performed similarly when cemented to zirconia with Panavia SA cement under the same protocol. The stability of the bonded interface and retention forces between zirconia prostheses and titanium copings varied from the cement used.

An AIE-active fluorescent probe with near-infrared (NIR) emission for selectively monitoring and bioimaging Cys in living cells

Cysteine (Cys), as a kind of essential bio-thiols, plays a pivotal role in modulating cell metabolism, maintaining intracellular redox balance and facilitating protein synthesis. In order to investigate its role in these physiological processes, fluorescent probe was selected as an important method for selectively detecting Cys. However, most of the probes possess ACQ effect, which limits their applications in the field of biosensing and bioimaging. Herein, an AIE-active fluorescent probe TCF-TPA was synthesized for specifically detecting Cys in HeLa cells. TCF-TPA, consisted of a tricyanofuran (TCF) fluorophore, was modified with an acrylate group for distinguish Cys from other bio-thiols, and the incorporation of electron-donating triphenylamine endowed the probe with AIE property and strong intramolecular charge transfer effect, thereby enabling the probe to have near-infrared (NIR) emission length (666 nm). Meanwhile, TCF-TPA possessed low detection limit for Cys (73.0 nM) and was successfully performed bioimaging of Cys in HeLa cells.

Enhancing the Activity of Surface Immobilized Antimicrobial Peptides Using Thiol-Mediated Tethering to Poly(ethylene glycol).

Considering the need for versatile surface coatings that can display multiple bioactive signals and chemistries, the use of more novel surface modification methods is starting to emerge. Thiol-mediated conjugation of biomolecules is shown to be quite advantageous for such purposes due to the reactivity and chemoselectivity of thiol functional groups. Herein, the immobilization of poly(ethylene glycol) (PEG) and antimicrobial peptides (AMPs) to silica colloidal particles based on thiol-mediated conjugation techniques, along with an assessment of the antimicrobial potential of the functionalized particles against Pseudomonas aeruginosa and Staphylococcus aureus is investigated. Immobilization of PEG to thiolated Si particles is performed by either a two-step thiol-ene "photo-click" reaction or a "one-pot" thiol-maleimide type conjugation using terminal acrylate or maleimide functional groups, respectively. It is demonstrated that both immobilization methods result in a significant reduction in the number of viable bacterial cells compared to unmodified samples after the designated incubation periods with the PEG-AMP-modified colloidal suspensions. These findings provide a promising outlook for the fabrication of multifunctional surfaces based upon the tethering of PEG and AMPs to colloidal particles through thiol-mediated biocompatible chemistry, which has potential for use as implant coatings or as antibacterial formulations that can be incorporated into wound dressings to prevent or control bacterial infections.

Catalytic Cracking of Polylactic Acid to Acrylic Acid

Comprehensive SummaryAs a typical type of sustainable plastic, polyesters can be recycled or upcycled into value‐added chemicals in a variety of methods. However, excess reagents are required for most of the depolymerization and upcycling processes, causing the emission of environmental pollutants and the waste of chemical resources. Here we demonstrate a one‐pot catalytic process to directly crack polylactic acid into acrylic acid by acid catalyst with the assistance of an ionic liquid, Bu4PBr. Polylactic acid is attacked by the Br– from Bu4PBr and the H+ from acid to form oligomers containing Br or acryloyl group, and these oligomers serve as intermediates to produce acrylic acid during their mutual transformation. The acrylic acid is vaporized directly from the reactor and obtained in a collector with a selectivity around 90 % when polylactic acid is fully converted. This green process shows great advantages in atom economy compared to the conventional recycling/upcycling methods for polyesters, in addition, a better efficiency in converting the polymer than the corresponding monomer could inspire new upcycle strategies for different plastic wastes.

Synthesis and Energetic Properties of N-Substituted 3,4- and 3,5-Dinitropyrazoles.

3,4- and 3,5-Dinitropyrazoles (DNPs) were substituted with acryl and allyl groups on the N1 nitrogen atom, resulting in three novel energetic materials. These compounds are all liquids at room temperature with melting points ranging from -60.2 to -38.6 °C and were fully characterized by high-resolution mass spectrometry, elemental analysis, proton and carbon nuclear magnetic resonance spectroscopy, and Fourier transform infrared spectroscopy. These materials were also tested for electrostatic discharge, friction, and impact sensitivities and then compared to DNP starting materials and to the explosive nitroglycerin (NG). These results indicate that the synthesized compounds are less sensitive to impact compared to NG and have higher thermal stabilities to decomposition.

Effect of charge on the stabilization of water-in-water emulsions by thermosensitive bis-hydrophilic microgels

HypothesisMolecular surfactants are not able to stabilize water-in-water (W/W) emulsions, unlike nano or micro-particles, which can achieve this in some cases. However, the effect of electrostatic interactions between particles on the emulsion stability has rarely been investigated. We hypothesize that introducing charges modifies the stabilization capacity of particles and renders it both pH- and ionic strength-dependent. ExperimentsCharge was introduced into bis-hydrophilic and thermoresponsive dextran/polyN-isopropylacrylamide microgels by replacing a small fraction of polyN-isopropylacrylamide with acrylic acid groups. The size of the microgels was obtained by dynamic light scattering. The stability and microstructure of dextran/poly(ethyleneoxide)-based W/W emulsions, was studied as a function of pH, NaCl concentration and temperature using confocal microscopy and by analytical centrifugation. FindingsThe swelling degree of charged microgels depends on the pH, ionic strength and the temperature. In the absence of salt, charged microgels do not adsorb at the interface and have little stabilizing effect even after neutralization. However, the interfacial coverage and the stability increase with rising concentration of NaCl. Saltinduced stabilization of these emulsions was also observed at 50 °C. Increasing the temperature strongly influences the emulsion stability at low pH.

Naturally Derived Maleic Chitosan/Thiolated Sodium Hyaluronate Hydrogels as Potential 3D Printing Tissue Engineering Materials

Abstract3D printing is an attractive method to accurately construct artificial organs or alternative materials with complicated structures and functional performance. Naturally derived hydrogels have emerged as promising materials for the preparation of biomimetic 3D organization or scaffolds by 3D printing due to their good biocompatibility, high water content, and fascinating 3D network. However, the poor printing properties and weak structural stability of naturally derived hydrogels limit their applications. In this study, photopolymerizable hydrogels are designed based on maleic chitosan (MCS) and thiolated sodium hyaluronate (SHHA). The Michael addition between MCS and SHHA improves the viscosity of the mixed solution. Moreover, it benefits the 3D printing process, followed by photopolymerization (acrylate‐thiol step‐chain polymerization and acrylate–acrylate chain polymerization) to form a stable covalent network rapidly. The rheological property, swelling behaviors, microstructure, and in vitro degradation are tuned by adjusting the molar ratio of the thiol group and acrylate group. In addition, MCS/SHHA hydrogel scaffolds with good accuracy and enhanced structural stability are prepared using extrusion‐based 3D printing and photopolymerization technology. The hydrogels display excellent cytocompatibility and can support adherence of L929 cells, which can be used as prospective materials for tissue engineering applications.

Synthesis, characterization and application of MP@ p (EGDMA-co-HPMA) in adsorption and release of cefpodoxime

A responsive polymer was synthesized from polymeric chain coatings with N-(2-hydroxypropyl) methacrylamide (HPMA) and Ethylene glycol dimethyl acrylate (EGDMA) groups (MP@ p (EGDMA-co-HPMA)) and was used to adsorption/release of Cefpodoxime (CPD) from its liquid dispersions. The results revealed that magnetic polymer could effectively adsorb CPD at pH =8 at about 30 °C. Also, the adsorption of CPD on magnetic polymer was best fitted to the Langmuir model. The drug release results indicated the thermo and pH sensitivity behavior of magnetic polymer with 35% of CPD release at acidic (pH = 1.2) and 62% at alkaline (pH = 7.4) solutions.

Preparation and Properties of Shape Memory PEG/IEM Resin and Its Composite Designed for Ureter Stent.

In this paper, isocyanoethyl methacrylate (IEM) is used to functionalize the two ends of poly(ethylene glycol)(PEG) diol with acrylic acid groups through an urethanisation reaction. The synthesized PEG/IEM resin is then photo-cured with a 405nm ultraviolet lamp. Ttrans of the PEG/IEM resin can be regulated by the different molecular weights of PEG and the use of plasticizer Triacetin to reach 44°C, which is closer to the human body temperature. Cytotoxicity assay and DMA shape memory cycling testing show that the PEG/IEM resin has excellent biocompatibility and shape memory properties. The flower structure is prepared and its shape recovery process is demonstrated. The performance of 10wt% nano Fe3 O4 /PEG4000/IEM resin and its composite spring stent structure satisfy the requirement of the stent properties in vivo, and can quickly recover to the original shape under magneticallydriven. This work provides a material option for developing new biological application devices such as ureter stents. This article is protected by copyright. All rights reserved.

Polybutadiene Dielectric Elastomers with High Dielectric Constant and Ultralow Dielectric Loss via Tuning Grafted Polar Groups.

This work describes an easy and effective process for preparing a homogeneous polybutadiene (PB) dielectric elastomer with improved actuated strain by utilizing a photochemical thiol-ene click reaction. The carboxyl groups and various ester groups are used for grafting on the PB. Since the length of the alkyl chains of the ester groups will significantly influence the polarities of the carbonyl groups and hydrogen bonding effect, the influence of polarity and hydrogen bonding effect on the dielectric properties and mechanical properties of the modified polybutadienes is carefully discussed. Very interestingly, it is found that the increment of dielectric constant of PB modified by carboxyl groups is the lowest one compared to other modified PBs with the ester groups. Meanwhile, the modified PBs with the ester groups could achieve pretty low dielectric loss factor, and finally, a high dielectric constant (3.6), low dielectric loss factor (0.0005), and large actuated strain (≈25%) of the modified polybutadienes could be achieved by the modified PBs with butyl acrylate groups. This work provides a simple and effective method for the designing and synthesizing of a homogeneous high electromechanical performance dielectric elastomer with high dielectric constant and low dielectric loss.

Flexible dual-functionalized hyaluronic acid hydrogel adhesives formed in situ for rapid hemostasis

Hydrogel adhesives integrating both rapid and strong adhesion to blooding tissues and biocompatibility are highly desired for fast hemostasis. Herein, a flexible hyaluronic acid hydrogel adhesive is fabricated via photocrosslinking of the solution originating from dopamine-conjugated maleic hyaluronic acid (DMHA) in situ. The introduction of acrylate groups with high substitutions into the hydrogel matrix endows the adhesive with rapid gelation and strong tissue adhesion properties through photopolymerization. Moreover, the high substitution of catechol groups with unoxidized state can not only induce red blood cell aggregation and platelets adhesion but also adhere to wound tissue to further enhance hemostasis. Based on its bio-adhesion and procoagulant activity, the DMHA hydrogel formed in situ reveals superior hemostatic performance in the rat liver injury model and noncompressible hemorrhage model, and rabbit femoral artery puncture model, compared to commercial products (gauze, absorbable gelatin sponge) and oxidized DMHA (SMHA) hydrogel. Besides, the hydrogel exhibited good adaptability, biodegradability, and superior cytocompatibility as well as negligible inflammation. This hydrogel adhesive is a promising biological adhesive for hemorrhage control.