Benzonic Acid Research Articles

Solvo-thermal synthesis of a unique cluster-based nano-porous zinc(II) luminescent metal-organic framework for highly sensitive detection of anthrax biomarker and dichromate

In this work a flexible multi-dentate 4,4′-(1H-1,2,4-triazole-1-yl) methylene-bis(benzonic acid) (H2L) ligand has been employed, a unique cluster-based nano-porous luminescent zinc(II) metal-organic framework {[Zn(μ6-L)]·(DMAC)2}n (1) (DMAC = Dimethylacetamide) has been isolated under solvo-thermal conditions. The H2L ligand adopts hexa-dentate coordination modes via one triazole nitrogen atom and four aromatic carboxylate oxygen atoms, which bridge the neighboring six-coordinated ZnII centers, leading to a three-dimensional (3D) nano-porous metal organic framework. A PLATON program analysis suggests the total potential solvent area volume is 2028.9 Å3, which occupy 62.5% percent of the unit cell volume (3248.4 Å3). PXRD Patterns of the as-synthesized samples 1 have been determined confirming the purity of the bulky samples. Photo-luminescent properties indicate strong fluorescent emissions of 1 at the room temperature. Further photo-luminescent measurements show that 1 can exhibit highly sensitive real-time luminescence sensing of anthrax biomarker dipicolinic acid (DPA) with high quenching efficiency (KSV = 1.48 × 105 M−1) and low detection limit (0.298 μM (S/N = 3)). Meanwhile 1 also exhibits highly selective and sensitive luminescence sensing for Cr2O72- ions in aqueous solutions with high quenching efficiency KSV = 1.22 × 104 L·mol−1 and low detection limit (0.023 μM (S/N = 3)). Therefore 1 can be used a unique multi-functional 3D cluster-based metal organic material in sensitive detection and effective detection of environment pollutants and biomarker molecules.

Improved antibody adsorption performance of phenyl-based mixed-mode adsorbents by adjusting the functional group of ligand

The present work is aimed to improve the antibody adsorption performance of phenyl-based mixed-mode adsorbents by adjusting the functional group of ligand. Two new mixed-mode adsorbents coupled with 4-(aminomethyl)phenol (AMP) and 4-(aminomethyl)benzonic acid (AMA) were designed based on the structure of benzylamine (BA), where a hydroxyl or carboxyl group was introduced. Bovine serum Immunoglobulin G (IgG) and bovine serum albumin (BSA) were used as the model proteins. The adsorption isotherms of IgG and BSA were investigated at different pH values ranging from 4.0–8.9 to evaluate the adsorption performance, and protein-ligand molecular interactions were explored through addition of sodium chloride and glycerol. The results showed that both of adsorbents coupled with AMP or AMA had lower saturated binding capacities (Qm) towards BSA and higher adsorption capacity ratio of IgG to BSA when compared to BA-based adsorbents. The contributions of electrostatic interactions and hydrophobic interactions to proteins binding were different among these phenyl-based mixed mode adsorbents. Finally, AMP-based adsorbent possessing high adsorption capacity ratio of IgG to BSA and salt tolerance was selected to separate IgG from mimetic serum with purity higher than 96 %. The results indicated adjusting the functional groups of ligand to regulate the electrostatic and hydrophobic interactions of protein-ligand was useful to improve the antibody separation performance of mixed-mode adsorbents.

A Co(II)-Based Coordination Polymer: Photocatalytic Studies, Treatment and Nursing Values on Diabetic Foot by Regulating the Insulin Receptor on the Vascular Cells

In the present study, a reaction between Co(NO3)2·6H2O and 4,4′‐(1H‐1,2,4‐triazol‐1‐yl)methylene‐bis(benzonic acid) (H2tzmb), an aromatase inhibitor letrozole derivative, in the water and DMF mixed solvent affords a new Co(II)-bearing coordination polymer {[Co(tzmb)(H2tzmb)]·H2O}n (1). The photocatalytic investigations reflect that complex 1 reveals outstanding degradation activity to 4 kinds of organic dyes (namely, Orange IV (OIV), Methyl orange (MO), Rhodamine B (RhB) and methylene blue (MB)). Its treatment and nursing values on the diabetic foot was determined and the detail mechanism was discussed as well. The body blood glucose levels of the animal were determined, and the relative expression levels of the insulin receptor on the vascular cells were also determined with real time RT-PCR under the compound treatment. Molecular docking simulation was performed using INSR protein as the probe, the simulated results indicate that the biological activity was from the carboxyl oxygen.

Self‐Assembly of ZnII/CdII/PbII Coordination Polymers with a Tripodal Ligand Derived from Aromatase Inhibitor Letrozole Derivative

Reactions of the aromatase inhibitor letrozole derivative 4,4'‐(1H‐1,2,4‐triazol‐1‐yl)methylene‐bis(benzonic acid) (H2tzmb) with ZnII, CdII, or PbII salts under similar conditions resulted in the generation of three coordination polymers, namely, {[Zn(tzmb)(H2tzmb)]·H2O}n (1), [Cd(tzmb)(H2O)2]n (2), and {[Pb(tzmb)(H2O)]·DMF}n (3), respectively. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analysis, IR spectroscopy, powder X‐ray diffraction, and thermogravimetric analyses. Complex 1 features a twofold 2D → 2D interpenetrated network based on corrugated 63‐hcb layers, and complex 2 exhibits a flat 2D 4.82‐fes network, whereas complex 3 presents a 3D hex net based on infinite rod‐shaped secondary building units. The remarkable structural diversity may illustrate the powerful effect of metal ions on coordination assemblies. The spectroscopic, thermal, and photoluminescent properties of complexes 1–3 were investigated. In addition, the catalytic activity of 1 in the solvent‐free ring‐opening polymerization of ε‐caprolactone was also discussed.

A multi-responsive regenerable water-stable two-dimensional cadmium (II) fluorescent probe for highly selective, sensitive and real-time sensing of nitrofurazone and cupric ion

In recent years, luminescent metal organic frameworks (MOFs) materials have attracted widespread attention in the field of fluorescence sensing. In this work, a novel two-dimensional (2D) micro-porous water-stable coordination material {[Cd(μ3-HL)2(H2O)]⋅2.3H2O}n (1, H2L = 4,4′-(1H-1,2,4-triazol-1-yl)methylene-bis (benzonic acid)) has been prepared through the powerful solvo-thermal approaches, which has been characterized by single crystal X-ray diffraction analysis, PXRD, scanning electron microscope (SEM) and Transmission electron microscopy (TEM) characterization. Crystal structural analysis also reveals the partly de-pronated μ3-coordinated HL− adopted tri-dentate bridging mode, which link these cadmium (II) centers, eventually forming the two-dimensional (2D) micro-porous coordination framework of 1. 1D channel with diemsionality of 12.216(3) Å × 8.578(11) Å that can be observed along the crystallographic a axis. It is noted that 1 has good chemical stability and maintains structural integrity not only in various solvents, but also in aqueous solutions with pH values varying from 2 to 12. Additionally, 1 has the unique advantages such as high detection sensitivity for Nitrofurazone (NZF) and Cupric ion (Cu2+) (Ksv quenching efficiency for NZF: 5.0 × 106 M−1 and Cu2+ 5.6 × 106 M−1) and low detection limits (NZF: 1.21 μM and Cu2+: 1.07 μM), good selectivity and good real-time performance. The result of photo-luminescent experiment demonstrates that 1 can realize high sensitivity and real-time chemical discrimination of antibiotics and ions, and has good reusability. To the best of our knowledge, 1 is the first example of the ultra-stable 2D cadmium (II) micro-porous coordination material as a renewable chemical sensor for NZF and Cu2+.

Synthesis, crystal structures and dye removal properties of a series of metal-organic frameworks based on N-heterocyclic carboxylic acid ligands

Abstract Six functional metal-organic frameworks build by 4,4'-(1H-1,2,4-triazol-1-yl)methylenebis (benzonic acid) (H2tmlb), namely: [Zn4(tmlb)4(H2O)]n (1), [Ni4(tmlb)4(H2O)]n (2), [Cu(tmlb)]n (3), [Co(tmlb)]n (4), [Pb(tmlb)(H2O)]n (5), {[Zn(tmlb)(H2tmlb)]H2O}n (6), have been successfully synthesized. The X-ray diffraction analysis show that the complexes 1 and 2 exhibited a two interpenetrating (3, 6, 6)-connected framework with a Schlafli symbol of (4·62)2 (42·610·83) topology. The complexes 3 and 4 show a two interpenetrating (3, 6)-connected net with (611·84) (63)2 topology. The complex 5 shows a (3, 8)-connected network with a point symbol of (4·62)2 (42·615·78·8·92) topology. The complex 6 exists a 2-fold interpenetrating topology framework and the point symbol is (6·6·6). Moreover, the photocatalytic studies show that complexes 1–5 have highly photocatalytic ability to degrade methylene blue (MB). In addition, the complex 6 can efficiently adsorb Congo red through H-bonds and the adsorption kinetic have been discussed.

Syntheses, characterization and properties of three coordination polymers with interpenetrating structures comprising 4,4'-(1H-1,2,4-triazol-1-yl)methylene-bis(benzonic acid).

Three new coordination polymers (CPs), {[Pb(tmdb)](H2O)}n (1), {[Zn(tmdb)(bimb)0.5]}n (2) and {[Zn3(tmdb)3(bpmb)1.5](H2O)6}n (3) (H2tmdb = 4,4′-(1H-1,2,4-triazol-1-yl)methylene-bis(benzonic acid), where bpmb = 1,4-bis(pyridin-4-ylmethoxy)benzene and bimb = 1,4-bis(imidazoly-1-yl)benzene), have been solvothermally or hydrothermally synthesized. Compound 1 is a 2D network with the point symbol (4·6·8)(4·62) and compound 2 is a 4-fold interpenetrating 3D network with spiral chains. The topological type of 2 is dmc (topos&RCSR.ttd) with the point symbol (4·82)(4·85). Compound 3 is a 3-fold interpenetrating 3D network with the point symbol (63)2(8·65)2(10·62)(8·10·64). The electrochemiluminescence (ECL) behaviors of 2 and 3 were studied. The applications of CP 2 and 3 in detecting ions were explored, and the results show that they can be used as fluorescent probes to selectively detect and identify Fe3+ ions in water. In addition, the applications of CP 2 and 3 in the adsorption and separation of dyes were researched. Furthermore, the gas adsorption of 3 was studied.

A penetrating metal-organic framework based on N-heterocyclic carboxylic acid with sensing properties toward Cr(VI)/Fe(III) and nitrobenzene

A luminescent metal-organic framework, [Cd(tmlb)(bbibp)]n (1) (H2tmlb = (1H-1,2,4-triazol-1-yl)methylenebis(benzonic acid), bbibp = bis(benzoimidazo-1-ly)biphenyl), has been solvothermally synthesized and characterized by elemental analysis, infra-red spectroscopy, single-crystal X-ray diffraction, thermogravimetric analysis, and powder X-ray diffraction. Complex 1 exhibits two interpenetrating uninodal 4-connected 3-D frameworks with a (65·8) topology. The luminescence studies reveal that the complex displays sensitive and selective luminescence sensing toward Cr(VI) (CrO42− and Cr2O72−) anions, Fe(III) cation, and nitrobenzene. The potential quench mechanism was discussed.

Fluorescent and magnetic properties of three complexes based on 4,4′-(1H-1,2,4-triazol-1-yl)methylene-bis(benzonic acid)

Three new complexes, namely, {[Cd(TZMB)(1,3-bimb)]·(H2O)2}n (1), {[Mn2(TZMB)2(1,4-bib)0.5(H2O)2]·(H2O)2(DMA)}n (2), {[Co2(TZMB)2(1,4-bib)]·(H2O)1.5}n (3), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction analysis, elemental analysis (EA), IR spectra (IR), powder X-ray diffraction (PXRD) and thermogravimetric (TG) analysis. Single X-ray diffraction analysis reveals that complex 1 is a 5-connected net 2D network with the point symbol of (48·62), complex 2 is a 3,3,3,5,9-connected net 3D framework with the point symbol of {3·4·5}{3·43·53·62·7}{3·45·54·611·711·83·9}{4·5·6}{42·6} and complex 3 is a 3,4-connected 3D framework. The topological type of 3 is dmc (topos&RCSR.ttd) with the point symbol of (4·82)(4·85). Furthermore, luminescent properties of 1 and the magnetic properties of complexes 2 and 3 were also investigated.

Two novel luminescent Cd(II)/Zn(II) coordination polymers based on 4,4′-(1H-1,2,4-triazol-1-yl)methylene-bis(benzonic acid) for sensing organic molecules and Fe3+ ion

Two novel coordination polymers, {[Cd(TZMB)(1,4-bib)0.5]·(H2O)1.5} (1) and {[Zn(TZMB)(1,4-bib)0.5]}n (2), have been synthesized under solvothermal conditions. Complex 1 displays a 3D structure with the (47.84)(4.72.83) topology and Complex 2 is a 3D structure with the point symbol of {4.82}{4.85}. And complex 1 shows good luminescent quenching effect for organic solvent molecules (actone and p-nitrophenol) and Fe3+.

Syntheses, structures and luminescent properties of two novel Zn (II) coordination polymers

Two new coordination polymers, namely [Zn(TZMB)]n (1) and {[Zn(TZMB)](H2TZMB)]·(C2H5OH)0.5(H2O)2.5}n (2), (H2TZMB = 4,4′-(1H-1,2,4-triazol-1-yl)methylene-bis(benzonic acid), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction analysis, elemental analysis (EA), IR spectrum analysis (IR), powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Single X-ray diffraction analysis reveals that complex 1 is a 3D 3,6-connected net with the point symbol of (6110.84)(63)2 and complex 2 is a 2D 3-connected net with the point symbol of (63). Furthermore, luminescent properties of complexes 1 and 2 were also investigated in detail.

スチレンを中心とした高校有機化学授業の展開 (II) : 安息香酸のエステル化とケン化反応および分解反応

スチレンを中心とした高校有機化学授業の展開 (II) : 安息香酸のエステル化とケン化反応および分解反応

Tuning the Morphologies of MnO/C Hybrids by Space Constraint Assembly of Mn-MOFs for High Performance Li Ion Batteries.

Morphology controllable fabrication of electrode materials is of great significance but is still a major challenge for constructing advanced Li ion batteries. Herein, we propose a novel space constraint assembly approach to tune the morphology of Mn(terephthalic acid) (PTA)-MOF, in which benzonic acid was employed as a modulator to adjust the available MOF assembly directions. As a result, Mn(PTA)-MOFs with microquadrangulars, microflakes, and spindle-like microrods morphologies have been achieved. MnO/C hybrids with preserved morphologies were further obtained by self-sacrificial and thermal transformation of Mn(PTA)-MOFs. As anodes for Li ion batteries, these morphologies showed great influence on the electrochemical properties. Owing to the abundant porous structure and unique architecture, the MnO/C spindle-like microrods demonstrated superior electrochemical properties with a high reversible capacity of 1165 mAh g-1 at 0.3 A g-1, excellent rate capability of 580 mAh g-1 at 3 A g-1, and no considerable capacity loss after 200 cycles at 1 A g-1. This strategy could be extended to engineering the morphology of other MOF-derived functional materials in various structure-dependent applications.

Triple Helical Molecular Braid and Parallel Packed Wavy Chain-Based Supramolecular Organic Frameworks with Conformation- and Packing-Dependent Luminescent Properties

Two three-dimensional supramolecular organic frameworks, [(H2bpdc)0.5(bipy)0.5] (1) and [(H3dpob)(bipy)·3H2O] (2), have been successfully constructed and structurally characterized (H2bpdc = 2,2′-biphenyldicarboxylic acid; H3dpob = 3-(2′,3′-dicarboxylphenoxy)benzonic acid; bipy = 4,4′-bipydine). 1 is driven by C–H···π hydrogen-bonded packing to three dimension. 2 origins form parallel-packed wavy chains and show π–π stacking-directed structure. After the SOFs are formed via weak noncovalent interaction, 1 and 2 show an enhancement in thermostability. The different conformations of bipy induced by weak noncovalent interactions are responsible for the huge dissimilarity of structural and luminescence behavior between them. Under the excitation of 365 nm ultraviolet light, 1 and 2 show stronger blue-white and green-white luminescent emissions in the solid state, respectively. In comparison with 2, supramolecular organic framework 1 shows superior performance in aggregation-induced emission (AIE) activity, wh...

Determination of Food Preservatives in Drinks by Dispersive Liquid-Liquid Microextraction Coupled to Capillary Gas Chromatography

This study describes an analytical method employing capillary gas chromatography (GC) using flame ionization detection (FID) that has been developed for the simultaneous determination of food preservatives in drinks, including sorbic acid (SA), benzonic acid (BA) and methyl paraben (MP). For this purpose, dispersive liquid-liquid microextraction (DLLME) was applied as a sample preparation technique. The DLLME conditions such as the types and volume of extraction solvent, the types and volume of the disperser solvent, pH value and salt addition were investigated and optimized. The method was linear in the ranges from 0.5 to 100.0 μg·mL-1for abovementioned preservatives withR2≥ 0.9991. The DLLME procedure allowed efficient recovery of the analyted preservatives ranging between 91 % and 108 % with a relative standard deviation (RSD) ≤ 6.1 for the blank samples spiked with 20, 40 and 80 μg·mL-1of preservatives, respectively. The developed procedure was demonstrated to be a effective method for the analysis of preservatives in drinks. Furthermore, the method is simple, reproducible, envioronmentally friendly and inexpensive.

Mitigative effect of micribial degradation on autotoxicity of Panax ginseng

Continuously cropping obstacle restricts ginseng production and rational use of land resource severely, and autotoxicity is one of the most important factors. In our previous work, ginseng autotoxin degrading bacteria were isolated, in the present re- search, plate culturing method and traditional physiological and biochemical method were used to analyze biological indices and protective enzyme activities, in order to elucidate the mitigative effect of autotoxin degrading bacteria on autotoxicity of P. ginseng. Results indicated that, except for palmitic acid, autotoxicity of benzonic acid, diisobutyl phthalate, diisobutyl succinate, and 2,2-bis (4- hydroxyphenyl) propane on the growth of ginseng seeds was significantly alleviated after autotoxins degrading bacteria was inoculated, and which have no evident difference with control. Except for benzoic acid, enzyme activity of SOD, POD and CAT in other autotoxin degrading treatments decreased significantly. The present research showed that, microbial degradation could alleviate the autotoxicity of autotoxins on ginseng seeds effectively, and which will be helpful for the resolution of ginseng continuously cropping obstacle problem.

Selective and simultaneous extraction and determination of hydroxybenzoic acids in aqueous solution by magnetic molecularly imprinted polymers

Two novel magnetic molecularly imprinted polymers (MMIPs) based on benzonic acid (BA)/4-hydroxybenzoic acid (4-HBA) as template have been successfully developed to selectively and simultaneously extract and determine five hydroxybenzoic acids [BA, 4-HBA, salicylic acid (SA), protocatechuic acid (PCA), and gallic acid (GA)] in aqueous solution. Various parameters affecting adsorption/desorption behavior are evaluated for achieving optimal recovery. Under optimum conditions, adsorption process between MA/4-HBA and MMIPs follows Langumuir adsorption isotherm and pseudo-second-order reaction kinetics. Thermodynamic parameters reveal that adsorption process is spontaneous, endothermic and entropy driven one. Both MMIPs show high adsorption capacity, good selectivity, rapid kinetic binding (40min) and magnetic separation (10 s), favorable reproducibility (RSD<4% for batch-to-batch evaluation), and stability (only 6% decrease after six cycles). The adsorption capacities of 4-HBA, PCA and GA on 4-HBA-MMIPs are higher because of higher molecular analog degree to template, whereas BA and SA with higher capacities on BA-MMIPs are observed. Spiked recoveries of five hydroxybenzoic acids on BA-MMIPs and 4-HBA-MMIPs range from 83.2% to 103.0% with RSD less than 6.9%. Results demonstrate that both resulting MMIPs could be reliably applied to direct extraction and determination of hydroxybenzoic acids from real aqueous solution.

Preparation of magnetic dummy molecularly imprinted polymers for selective extraction and analysis of salicylic acid in Actinidia chinensis

Compounds with strong intramolecular hydrogen bonds (e.g., salicylic acid) have weak intermolecular hydrogen bonding interactions between them and functional monomers in the imprinting process. Consequently, the corresponding molecularly imprinted polymers (MIPs) have no specific adsorption ability. Here, the first magnetic dummy MIPs (MDMIPs) based on benzonic acid as dummy template are successfully developed and evaluated with respect to the applications in selective enrichment and analysis of salicylic acid from complex mixtures. Various parameters affecting absorption/desorption were evaluated for achieving optimal recovery and reducing nonspecific interactions. The prepared MDMIPs showed high adsorption capacity, good selectivity, rapid kinetic binding (40min) and magnetic separation (5s), high reproducibility (RSD< 4% for batch-to-batch evaluation), and stability (only 4% decrease after 6cycles). Owing to the efficacy in specific binding and removal of interference, trace level salicylic acid was quantified (0.2μg/g of fresh mass) in Actinidia chinensis by high-performance liquid chromatography.

Preparation and characterization of ortho-biguanidinyl benzoyl chitosan hydrochloride and its antibacterial activities

A novel derivative of chitosan (CTS), ortho-biguanidinyl benzoyl chitosan hydrochloride (o-BGBCH), was prepared with CTS and ortho-biguanidinyl benzoyl chloride, which was synthesized by acid chloride reaction of ortho-biguanidinyl benzonic acid hydrochloride (o-BGBA), as starting material in the medium consisted of methylsulfonic acid (MeSO3H) and dimethyl sulfoxide. Structure of o-BGBCH was characterized by FT-IR and 1H NMR, molecular weight of o-BGBCH was determined through gel permeation chromatography, and degree of substitution (DS) of guanidinylation of o-BGBCH was measured using elemental analysis technique. Meanwhile, the minimum inhibitory concentration of o-BGBCHs against Escherichia coli, a Gram-negative bacterium, and Staphylococcus aureus, a Gram-positive bacterium, were ascertained by agar plate method. Compared with CTS hydrochloride, o-BGBCHs had much stronger antimicrobial activities, and these activities improved with the increase of their DS of guanidinylation. When the DS of o-BGBCH reached or exceeded 32.7 %, its antibacterial activities against the tested bacteria were higher than that of Bromo-Geramium.

Preparation, characterization, and antibacterial activities of para-biguanidinyl benzoyl chitosan hydrochloride

Para-biguanidinyl benzoyl chitosan hydrochloride (p-BGBC) is prepared with chitosan (CTS) and para-biguanidinyl benzoyl chloride, which is synthesized by acidchloride reaction of para-biguanidinyl benzonic acid hydrochloride (p-BGBA), as starting material in the medium consisted of MeSO3H and dimethyl sulfoxide (DMSO). Structure of p-BGBC is characterized by FT-IR, 1H NMR and gel permeation chromatography (GPC), and its antimicrobial activities are evaluated against a Gram-negative bacterium Escherichia coli (E. coli) and a Gram-positive bacterium Staphylococcus aureus (S. aureus). Compared with CTS hydrochloride, p-BGBC has much stronger antimicrobial activities, which increase with the increase of its degree of substitution (DS) of guanidinylation. When the DS of p-BGBC achieves or exceeds 36.8%, its antibacterial activities against the tested bacteria are higher than that of Bromo-Geramium. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012