Diacrylic Acid Research Articles

Preparation of a Porous Protein-Based Composite Material by In Situ Polymerization of Pickering High Internal Phase Emulsion for Adsorption of Lead Ions.

The preparation of complex porous materials using a small molecular surfactant as the stabilizer of a high internal phase emulsion can result in harm to the environment. In this study, porous composites based on soy protein isolate with poly(acrylic acid) were prepared by in situ polymerization of a high internal phase monomer emulsion with an internal phase volume fraction of 80%. The material was prepared from acrylic acid and an N,N-methyl diacrylic acid monomer solution as the continuous phase, peanut oil as the dispersed phase, and soy protein isolate as the composite stabilizer. Scanning electron microscopy showed that porous composites exhibited a concave/convex three-dimensional interpenetrating pore structure. Fourier-transform infrared spectra revealed the existence of many active groups such as carboxyl, amino, hydroxyl, and sulfhydryl. The composite had a high adsorption capacity for lead ions, even at low concentration, with a removal rate of up to 95.7%. The adsorption process conformed to a two-stage model involving internal diffusion and Langmuir isothermal adsorption. The maximum saturated adsorption capacity was 36.71 mg/g when the initial solution concentration was 150 mg/L, the adsorbent concentration was 7.0 g/L, and the adsorption mechanism involved chemical interactions between the lead ions and the composite groups -COOH, -OH, and -SH.

Efficient hydrocarboxylation of alkynes based on carbodiimide-regulated in situ CO generation from HCOOH: An alternative indirect utilization of CO2

The role of carbodiimide as dehydrant in the chemo-, regio- and stereoselective Pd (II/0)-catalyzed hydrocarboxylation of various alkynes with HCOOH releasing CO in situ is reported for the first time to obtain α , β -unsaturated carboxylic acids. Both symmetrical and unsymmetrical monoalkynes show good reactivity. Importantly, 2,2'-(1,4-phenylene)diacrylic acid can also be synthesized in high yield through the dihydrocarboxylation of 1,4-diethynylbenzene. Besides, an excellent result in gram scale experiment and TON up to 900 can be obtained, displaying the efficiency of this protocol. Notably, regulating the types and concentrations of dehydrant can control the CO generation, avoiding directly operating toxic CO and circumventing sensitivity issue to the CO amount. On the basis of the attractive features of formic acid including easy preparation through CO 2 hydrogenation and efficient liberation of CO, this protocol using formic acid as bridging reagent between CO 2 and CO can be perceived as an indirect utilization of CO 2 , offering an alternative method for preparing acrylic acid analogues. We provide a new strategy for using carbodiimide as dehydrant to realize highly chem-, regio- and stereoselective Pd-catalyzed hydrocarboxylation of alkynes with HCOOH as both CO source and hydrogen donor, as a protocal for indirect utilization of CO 2 .

Sensitive X-ray detection and imaging by a scintillating Lead(II)-based Metal-Organic framework

Scintillators that exhibit X-ray stimulated light response have attracted increasing attention for their wide application in medical diagnosis and treatment, security inspection, industrial flaw detection and other aspects. However, the broader application of traditional inorganic and organic scintillators has been limited by their high preparation cost or poor adaptability to changeable environments. Here, a scintillating 1D metal–organic framework (MOF) [Pb(adda)(DMF)]n1 (H2adda = (2E,2′E)-3,3′-(anthracene-9,10-diyl) diacrylic acid, DMF = N,N-dimethylformamide) was prepared by a low-cost and short-cycle solvothermal process. Benefiting from the intrinsic synergistic effect of functional motifs and robust architecture, sensitive and steady X-ray response signals of 1 are demonstrated with an excellent linearity to the X-ray dose rates and stable light output under 9 h per day continuous irradiation during five days. In addition, the flexible MOF-based scintillator film is firstly applied in X-ray imaging application, which achieves a relatively high spatial resolution of 5.5 lp mm−1. This work provides an effective visualization tool for X-ray radiography and verifies the potential application of flexible MOF-based scintillator film for X-ray imaging.

Covalently Linked, Two-Dimensional Quantum Dot Assemblies.

Using nanoscale building blocks to construct hierarchical materials is a radical new branch point in materials discovery that promises new structures and emergent functionality. Understanding the design principles that govern nanoparticle assembly is critical to moving this field forward. By exploiting mixed ligand environments to target patchy nanoparticle surfaces, we have demonstrated a novel method of colloidal quantum dot (QD) assembly that gives rise to 2D structures. The equilibration of solutions of spherical and quasispherical QDs, including CdS, CdSe, and InP, with 2,2'-bipyridine-5,5'-diacrylic acid resulted in the preferential formation of 2D assemblies over the course of days as determined by transmission electron microscopy analysis. Small-angle X-ray scattering confirms the existence of the QD assemblies in solution. The dependence of the assembly on linker properties (length and rigidity), linker concentration, and total concentration was investigated, together with the data point to a mechanism involving ligand redistribution to create a patchy surface that maximizes the steric repulsion of neighboring QDs. By operating in an underexchanged regime, the arising patchiness results in enthalpically preferred directions of cross-linking that can be accessed by thermal equilibration.

A New La(III)-MOF for Efficient Dye Photodegradation and Protective Effect on Exercise Pain After Total Knee Arthroplasty by Reducing Nicotinic Acetylcholine Receptors Expression

The creation of multifunctional metal-based coordination complexes has been a hot topic in the fields of material science and biomedicine for their great potential application, metal–organic frameworks (MOFs) process the features of both coordination complexes and semiconductor materials might fit the requirements of the targeted materials. In this study, the assembly of the light-harvesting linker with La(III) ion produced a three-dimensional MOF [La2(adda)3(H2O)2]n (1) (H2adda = (2E,2′E)-3,3′-(anthracene-9,10-diyl) diacrylic acid), which could be applied as an effective catalyst for the Rhodamine B’s degradation. The treatment effect of compound 1 on exercise pain after total knee arthroplasty (TKA) on rat model was evaluated. The times of rats licking the surgery tissues was counted in the analgesic animal model. The content of the nicotinic acetylcholine receptors on presynaptic membrane was determined by RT-PCR. The possible binding interaction of the drug-like La(III) complex to the DNA structure has been further reviewed by molecular docking simulation.

Fluorescence Modulation of an Aggregation-Induced Emission Active Ligand via Rigidification in a Coordination Polymer and Its Application in Singlet Oxygen Sensing

A new Zn(II)-based coordination polymer (CP) having the formula [Zn(L)(2,2'-bpy)] (1) was synthesized using ZnCl2, 3,3'-(anthracene-9,10-diyl)diacrylic acid ligand (H2L), and 2,2'-bipyridine (2,2'-bpy) in DMF under solvothermal conditions. Here, the anthracene-based dicarboxylic acid ligand shows aggregation-induced emission (AIE) activity in an ethanol/hexane medium. Single-crystal X-diffraction analysis reveals that the one-dimensional (1D) zigzag chainlike structure of 1 is assembled from tetrahedrally coordinated Zn2+ ions interconnected by 2,2'-bpy and ditopic anthracene-based ligand molecules. The crystal structure analysis reveals that the ditopic anthracene-based flexible ligand adopts a twisted conformation in the CP crystal compared to its free state. Because of the twisted conformation of the ATE active ligand in the CP crystal, a large (similar to 80 nm) hypsochromic shift was observed in the emission spectrum with a drastic color change compared to the free state of ligand. The origin of these rare fluorescence properties is ascribed to the twisted diacrylic acid ligand conformation and rigidity in the CP crystal. An unprecedented response was observed toward singlet oxygen (O-1(2)) by 1 via a fluorescence turn-off mechanism. The presence of the anthracene moiety is the main influential factor for O-1(2) sensing, which undergoes [4 + 2] cycloaddition reaction with O-1(2), producing a nonemissive 9,10-endoperoxide product. The unique photoluminescence properties along with tunable fluorescence responses indicate that incorporating an AIE active anthracene core into the CP crystal is a beneficial strategy to develop new fluorescent materials with significant sensing ability.

Four novel Co(II) metal-organic frameworks based on semi-rigid ligand and their secondary building units transformation

Four novel 3D Co(II)-containing metal–organic frameworks (MOFs), namely [Co(ADDA)] (1), [Co(ADDA)(bipy)]·1.5H2O (2), [Co0.5(HADDA)(bipy)0.5] (3) and [Co(ADDA)(bipy)0.5] (4) (H2ADDA = 3,3'-(anthracene-9,10-diyl)diacrylic acid, bipy = 4,4′-bipyridine), have been successfully obtained based on reasonable synthetic strategies. N-donor auxiliary ligand, reaction medium and reaction temperature jointly induce interesting transformation of secondary building unit (SBU), resulting in structure diversities and topology variations. Notably, by increasing the reaction temperature in the mother liquid, 4 with {Co2(COO)4} paddle-wheel SBU can be generated by the single-crystal to single-crystal transformation of 3 with mononuclear {CoO4} SBU. Furthermore, the magnetic properties and electrocatalytic activities of these four Co-MOFs are also investigated in detail.

A fluorinated Zr-based MOF of high porosity for high CH4 storage

An organic linker H2FBDA (H2FBDA = (2E, 2′E)-3,3'-(2-fluoro-1,4-phenylene) diacrylic acid) with the electron-withdrawing fluoro-group, has been applied to construct a Zr-based metal-organic framework, the ZJU-800 (ZJU = Zhejiang University). ZJU-800, derived from UiO-66 and isostructural with NU-801, is explored for high-pressure methane storage capacity of 10.0 mmol/g at 65 bar and room temperature, with good thermal and water stability. It is shown that the amount of methane uptake is 61.2% higher than that of UiO-66 at 35 bar.

A luminescent barium-based metal-organic framework: Synthesis, structure and efficient detection of 4-nitrobenzoic acid

The assembly of a carboxylate substituted anthracene derivative with barium(II) salt yielded a 3D luminescent metal-organic framework [Ba2(adda)2(H2adda)(H2O)2]n1 (H2adda = (2E,2′E)-3,3′-(anthracene-9,10-diyl) diacrylic acid), which was structurally characterized by elemental analysis, powdered and single-crystal X-ray diffraction. Compound 1 exhibits a “turn on” luminescence response toward 4-nitrobenzoic acid (4-NBA) different from most nitroaromatic compounds displaying a “turn-off” luminescence stimulus. Increasing luminescence intensities with addition of 4-NBA in 1 dispersed in DMF are attributed to the dissociation of H2adda, evidenced by 1H NMR. Compound 1 is effective as a potential 4-NBA detector by establishing the relationship between the luminescence intensity of 1 and the molar concentration of 4-NBA.

A zirconium-based metal-organic framework with encapsulated anionic drug for uncommonly controlled oral drug delivery

Abstract Oral drug delivery has been recognized as the most common and patient acceptant drug administration. In general, an ideal drug carrier for oral drug delivery should own high drug loading capacity, good biocompatibility, and especially the feature of avoiding drug delivery in stomach (acidic conditions) and promoting the drug release in intestine (neutral conditions). Generally, most of MOFs for drug carriers exhibit the normal pH response in which the drugs are more easily released in acidic condition because of the degradation of the framework or/and the weak host-guest interactions, so they are not suitable for oral drug delivery. Herein, we design and synthesize a new nitrogen heterocycle organic ligand H 2 QDDA ((2E,2′E)-3,3′-(quinoline-5,8-diyl)diacrylic acid) and use it to construct its first Zr-based MOF (termed as ZJU-802 ). The anionic drug encapsulated ZJU-802 exhibit an uncommonly reverse pH response due to the incorporation of N sites in which the anionic drugs can be easily released at pH 7.4 while have a negligible release at pH 2.0 due to the enhanced host-guest interactions between the framework and anionic drugs. This reversed drug release is quite suitable for oral drug delivery. Further, high anionic drug loading capacities (>40%), low cytotoxicity and good biocompatibility of ZJU-802 were fully demonstrated by 1 H NMR, MTT assay and confocal microscopy imaging.

Spencertoxin and spencer acid, new phytotoxic derivatives of diacrylic acid and dipyridinbutan-1,4-diol produced by Spencermartinsia viticola, a causal agent of grapevine Botryosphaeria dieback in Australia

Spencermartinsia viticola is one of the most widespread Botryosphaeriaceae species isolated from grapevines in South Australia and New South Wales vineyards in Australia. A new phytotoxic dipyridine-butane-1,4-diol and a new diacrylic acid derivatives, here named spencertoxin (1) and spencer acid (2), were isolated from the culture filtrates of S. viticola isolate DAR78870 together with p-hydroxybenzaldehyde (3) and 2-(4-hydroxyphenyl) acetic acid (4). Spencertoxin and spencer acid were characterized as 2,3-di(pyridin-3-yl)butane-1,4-diol and (2Z,2′Z)-3,3′-(carbonylbis(oxy))diacrylic acid, respectively, by spectroscopic methods (essentially NMR and HRESIMS). Spencertoxin (1), p-hydroxybenzaldehyde (3) and 2-(4-hydroxyphenyl) acetic acid (4) showed phytotoxicity when the pure compounds were assayed on grapevine leaves of Vitis lambrusca and Vitis vinifera cv. Shiraz.

Formation of By‐products in Pure and Aqueous Acrylic Acid – Kinetic Measurements and Formation Mechanisms

AbstractDuring acrylic acid (AA) storage, a quality loss occurs due to the formation of by‐products such as diacrylic acid (DiAA), triacrylic acid (TriAA), and higher oligomers. This problem intensifies in the presence of water since the formation rate of oligomers increases and further by‐products such as 3‐hydroxypropionic acid (3‐HPA) and 3‐hydroxydiacrylic acid (3‐HDiAA) are formed. However, water is often essential during storage and transport to raise the flash point or reduce the melting point. In this work, the formation kinetics are investigated for all mentioned components in pure and aqueous AA. The formation mechanisms of 3‐HPA and 3‐HDiAA are assumed as acid‐catalyzed ester hydrolyses of DiAA or TriAA. The introduced reactions are modeled with the measured kinetic data in order to confirm the proposed reactions.

Metal-Organic Framework Photosensitized TiO2 Co-catalyst: A Facile Strategy to Achieve a High Efficiency Photocatalytic System.

A 3D metal-organic framework (ADA-Cd=[Cd2 L2 (DMF)2 ]⋅3 H2 O where H2 L is (2E,2'E)-3,3'-(anthracene-9,10-diyl)diacrylic acid) constructed from diacrylate substituted anthracene, sharing structural characteristics with some frequently employed anthraquinone-type dye sensitizers, was introduced as an effective sensitizer for anatase TiO2 to achieve enhanced visible light photocatalytic performance. A facile mechanical mixing procedure was adopted to prepare the co-catalyst denoted as ADA-Cd/TiO2 , which showed enhanced photodegradation ability, as well as sustainability, towards several dyes under visible light irradiation. Mechanistic studies revealed that ADA-Cd acted as the antenna to harvest visible light energy, generating excited electrons, which were injected to the conduction band (CB) of TiO2 , facilitating the separation efficiency of charge carriers. As suggested by the results of control experiments, combined with the corresponding redox potential of possible oxidative species, . O2- , generated from the oxygen of ambient air at the CB of TiO2 was believed to play a dominant role over . OH and h+ . UV/Vis and photoluminescence technologies were adopted to monitor the generation of . O2- and . OH, respectively. This work presents a facile strategy to achieve a visible light photocatalyst with enhanced catalytic activity and sustainability; the simplicity, efficiency, and stability of this strategy may provide a promising way to achieve environmental remediation.

Crystal structures, topological analysis and luminescence properties of three coordination polymers based on a semi-rigid ligand and N-donor ligand linkers

Three new mixed-ligand coordination polymers have been synthesized based on 3,3′-(anthracene-9,10-diyl)diacrylate acid and different N-donor ligands. Complex 2 displays rapid and selective sensing of Fe3+.

Synthesis and characterization of new heat resistance and organosoluble poly(ether-amide)

New series of olefinic poly(ether-amide)s (OPEA)s 6a-f was synthesized from 4,4′-bis(1,4-diphenoxybutane)diacrylic acid 4 and aromatic diamine 5a-f via a direct polycondensation reaction. The resulting polymers were characterized by Fourier transform infrared spectra (FTIR), nuclear magnetic resonance ( 1 H-NMR), solubility test and inherent viscosity. The thermal properties of the polymers 6a-c were investigated by thermogravimetric analysis (TGA). Polymer 6c due to presence of SO 2 group as a polar group shows better thermal properties compare with polymer 6a and 6b . KEY WORDS : Polycondensation, Polyamide, Ether group, Thermal properties Bull. Chem. Soc. Ethiop. 2013 , 27(3), 413-419. DOI: http://dx.doi.org/10.4314/bcse.v27i3.10

New photosensitive semi aramid/organoclay nanocomposite containing cinnamoyl groups: Synthesis and characterization

New poly(ether–amide)/layered silicate nanocomposites (PEAN) containing dibenzalacetone and cinnamoyl moieties were prepared via solution intercalation technique from poly(ether–amide) 6 and organo-MMT in a solution of N,N-dimethylacetamide (DMAc). New dicarboxylic acid 4 was synthesis from two step reactions. At first 4,4′-bis(1,4-diphenoxybutane) dialdehyde 3 was synthesized from 1,4-dibromobutane and 4-hydroxybenzaldehyde, then solvent free reaction using to synthesis 4,4′-bis(1,4-diphenoxybutane) diacrylic acid from dialdehyde 3 and malonic acid. Poly(ether–amide) (PEA) chains were synthesized from 4,4′-bis(1,4-diphenoxybutane)diacrylic acid 4 and 2,5-bis(4-aminobenzylidene)cyclopentanone 5 via a direct polycondensation reaction. The synthesized PEA was characterized by Fourier transform infrared spectra (FTIR), nuclear magnetic resonance (1H NMR), gel permeation chromatography (GPC) and UV–Vis spectroscopy. The distribution of organoclay and nanostructure of the nanocomposites were investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. The thermal properties and flammability of the nanocomposites were investigated by thermogravimetric analysis (TGA), differential scanning calorimetric (DSC) and microscale combustion calorimeter (MCC). In the presence of organoclay shows a good effect on improving the flame retardancy of the PEA, reflecting the decrease in heat release rate (HRR) and the total heat release (THR) of the nanocomposites, while the thermal stability of nanocomposites only changed slightly compared to the neat polymer. With the increase of the loading of organoclay, the nanocomposites showed improved flame retardancy and higher char residues.

Synthesis and characterization of new thermally stable and organosoluble polyamides by direct polycondensation

A series new thermally stable and organosoluble polyamides (PAs) 5a–f and copolyamides 10a–f with good inherent viscosities were synthesized from the direct polycondensation reaction of 1,2-bis(4-carboxyphenoxy)ethane 3 with aromatic diamines 4a–f and from the diacid 3 as a first diacid monomer and 4,4′-bis(1,3-diphenoxypropane) diacrylic acid 9 as a second diacid monomer with aromatic diamines 4a–f, respectively. The dicarboxylic acid 9 was synthesized from the two step reactions. At first 4,4′-bis(1,3-diphenoxypropane) dialdehyde 8 was synthesized from 1,3-dibromopropane 6 and 4-hydroxybenzaldehyde 7, then 4,4′-bis(1,2-diphenoxyethane) diacrylic acid 9 was synthesized from dialdehyde 8 and malonic acid in a solvent free reaction. All of the above polymers were fully characterized by 1H NMR, Fourier transform infrared, elemental analysis, inherent viscosity, solubility tests, differential scanning calorimeter, thermogravimetric analysis, and derivative of thermogravimetric. The resulted PAs have shown admirable good inherent viscosities and thermal stability and solubility.

Preparation and characterization of new organosoluble polyamides with good thermal properties containing photosensitive group in the main chain

AbstractIn this article, we have successfully synthesized a new dicarboxylic acid, from the two step reactions. At first 4,4′‐bis(1,2‐diphenoxyethane) dialdehyde was synthesized from 1,2‐dibromoethane and 4‐hydroxybenzaldehyde , then 4,4′‐bis(1,2‐diphenoxyethane) diacrylic acid was synthesized from 4,4′‐bis(1,2‐diphenoxyethane) dialdehyde and malonic acid in a solvent free reaction. Four new organosoluble and thermally stable polyamides (PAs) with good inherent viscosities containing photosensitive groups were synthesized from the direct polycondensation reaction of 4,4′‐bis(1,2‐diphenoxyethane) diacrylic acid with four various aromatic diamines containing photosensitive group, by two different methods such as direct polycondensation in a medium consisting of N‐methyl‐2‐pyrrolidone (NMP)/triphenyl phosphite (TPP)/calcium chloride (CaCl2)/pyridine (Py) and direct polycondensation in a tosyl chloride (TsCl)/pyridine (Py)/N,N‐dimethylformamide (DMF) system. All of the above polymers were fully characterized by 1H‐NMR, FTIR, gel permeation chromatography (GPC), elemental analysis, inherent viscosity, solubility tests, UV–vis spectroscopy, differential scanning calorimeter (DSC), thermogravimetric analysis (TGA). The resulted polyamides (PAs) have showed admirable good inherent viscosities, thermal stability and solubility. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Effects of High Salt Stress on Secondary Metabolite Production in the Marine-Derived Fungus Spicaria elegans

To obtain structurally novel and bioactive natural compounds from marine-derived microorganisms, the effect of high salt stress on secondary metabolite production in the marine-derived fungal strain, Spicaria elegans KLA-03, was investigated. The organism, which was isolated from marine sediment, produced different secondary metabolites when cultured in 3% and 10% saline conditions. Four characteristic metabolites, only produced in the 10% salinity culture, were isolated, and their structures were identified as (2E,2′Z)-3,3′-(6,6′-dihydroxybiphenyl-3,3′-diyl)diacrylic acid (1), aspulvinone E (2), aspochalasin E (3) and trichodermamide B (6), according to their 1D and 2D NMR spectra. Compound 1 is a new compound. High salt stress may therefore be a promising means to induce the production of new and chlorinated compounds in halotolerant fungi. Compound 1 showed moderate antibacterial activity against Pseudomonas aeruginosa and Escherichia coli with minimum inhibitory concentration (MIC) values of 0.038 and 0.767 mM, respectively.

Catena-Poly[[[aqua(1,10-phenanthroline)zinc(II)]-μ-3,3′-(p-phenylene)diacrylato] hemihydrate

In the title compound, {[Zn(C12H8O4)(C12H8N2)(H2O)]·0.5H2O}n, each ZnII atom is six-coordinated by two N atoms from one 1,10-phenanthroline (phen), three carboxyl­ate O atoms from two different L ligands [H2 L = 3,3′-(p-phenyl­ene)diacrylic acid] and one water mol­ecule in a distorted octa­hedral environment. The two L dianions are situated across inversion centres and bridge neighbouring ZnII centres, yielding a chain propagating parallel to [100]. O—H⋯O hydrogen bonds between the coordinated water molecule, the solvent water molecule (half-occupied) and the carboxylate O atoms further stabilize the structure.