Isophthalic acid

Two Mixed-Ligand Co(II) Complexes as Luminescent Materials and Loaded with Temozolomide-gel Particles in Nursing Against Glioma.[Pubmed:38625573]

J Fluoresc. 2024 Apr 16.

By employing a mixed-ligand strategy, we synthesized two new coordination polymers (CPs) featuring Co(II): Co(H(2)L)(bib)].2H(2)O(n) (1) and Co(L)(bib)(2)].2H(2)O(n) (2), where H(4)L represents 5-(3,5-dicarboxybenzyloxy) Isophthalic acid, and bib denotes 1,4-bis(1-imidazolyl)benzene. These CPs were obtained through the reaction of H(4)L, a flexible carboxylic acid ligand, with Co(NO(3))(2).6H(2)O in various solvent mixtures, along with the N-donor co-ligand bib. Complexes 1 and 2 are formed through distinct coordination modes, resulting in their distinct structural features and excellent fluorescent properties. Based on ligand-centered fluorescence emission and the blue shift (CP 1) along with red shift (CP 2) characteristics, both complexes show promise for applications in fields such as blue fluorescence sensing materials and luminescent materials. After successfully synthesizing two CPs, CP 1 was chosen as the carrier for loading temozolomide (TMZ). Subsequently, leveraging the unique advantages of hydrogels, we developed a novel metal gel formulation loaded with TMZ. The inhibitory effect of this formulation on the growth of glioblastoma was evaluated. Our results demonstrate a significant suppression of glioblastoma cell proliferation by this system, providing an effective avenue for glioblastoma treatment.

A series of isostructural metal-organic frameworks for an enhanced electro-catalytic oxygen evolution reaction.[Pubmed:38529572]

Dalton Trans. 2024 Apr 16;53(15):6568-6574.

Three new isostructural MOFs (ZnTIA, CoTIA and CdTIA) were synthesized by the solvothermal synthesis of the organic linker 5-triazole Isophthalic acid (5-TIA) with the transition metals Zn(II), Co(II) and Cd(II) in the presence of the structure directing agent tetramethyl ammonium chloride (TMA). These three MOFs were characterized thoroughly by ScXRD, PXRD, FT-IR, TGA, BET and SEM. They have excellent thermal and water stabilities. Among all these MOFs mentioned, pristine CoTIA exhibited excellent electrocatalytic activity toward the oxygen evolution reaction (OER). It exhibits a Tafel slope of 68.9 mV dec(-1) with an overpotential of 337 mV at 10 mA cm(-2) current density. The OER activity of the CoTIA MOF is relatively equivalent to that of the state-of-the-art catalyst (RuO(2)). Furthermore, the mechanical stability of crystalline ZnTIA, CoTIA and CdTIA MOFs was tested under ball mill pressure. The result showed that all the MOFs exhibit low tolerance to mechanical force because their structure was highly distorted or collapsed under such pressure, which is reflected by their poor electrocatalytic OER activity.

Enhancing the efficient degradation of BPS using the BPNS-CdS composite catalyst under visible light.[Pubmed:38485073]

Environ Res. 2024 Mar 12;251(Pt 2):118690.

Black phosphorus nanosheets (BPNS), a novel two-dimensional nanomaterial, find extensive applications in the field of photocatalysis. With the prohibition of bisphenol A (BPA), the utilization of bisphenol S (BPS), which is more resistant to degradation than BPA, has been steadily increasing. In this study, few-layer BPNS was prepared using an improved liquid-phase exfoliation method, showcasing its commendable specific surface area and notable adsorption capacity. Subsequently, a new type of nanocomposite material, BPNS-Cadmium sulfide (CdS), was hydrothermal synthesized involving BPNS and CdS. We conducted comparative assessments of BPNS, CdS, and their composite materials to identify the most efficient catalysts. Ultimately, we found that the composite material BPNS-CdS exhibited the highest capability for degrading BPS in an alkaline environment, achieving an impressive degradation rate of 86.9%. Notably, the degradation rate remained higher in an acidic environment compared to a neutral one. Through Electron Spin Resoance (ESR) experiments, it is revealed that BPNS-CdS, when exposed to visible light, generates *O(2)(-), *OH, and h(+) as confirmed. Additionally, we tested and validated the carrier separation and migration abilities of BPNS-CdS while also calculating the band gap for each material. Building upon these results, a possible photocatalysis mechanism experiment was proposed. Finally, the degradation products were analyzed using High-Performance Liquid Chromatography-Mass Spectrometry (HPLC-MS) and put forth a plausible pathway for the BPS degradation, and it was found that 4-Phenolsulfonic acid, Ethyl protocatechuate and Isophthalic acid are the main intermediates of BPS. This study contributes to a deeper understanding of the synergy between non-metallic catalysts like BPNS and metal catalysts like CdS. It also offers new insights into the degradation mechanisms and pathways for BPS.

Finely Tuning Metal Ion Valences of [Fe(3-x)M(x)(mu(3)-OH)(Carboxyl)(6)(pyridyl)(2)] Cluster-Based ant-MOFs for Highly Improved CO(2) Capture Performances.[Pubmed:38301151]

ACS Appl Mater Interfaces. 2024 Feb 14;16(6):8077-8085.

Solvothermal reactions of different trinuclear precursors and 5-(pyridin-4-yl)Isophthalic acid (H(2)L) successfully led to four anionic ant topological MOFs as Fe(3-x)M(x)(mu(3)-OH)(CH(3)COO)(2)(L)(2).(DMA(+)).DMF [M = Mn(II), Fe(II), Co(II), x = 0, 1, 2 and 3], namely, NJTU-Bai79 [NJTU-Bai = Nanjing Tech University Bai's group, Mn(3)(mu(3)-OH)], NJTU-Bai80 [Fe(2)Mn(mu(3)-OH)], NJTU-Bai81 [Fe(3)(mu(3)-OH)], and NJTU-Bai82 [Fe(2)Co(mu(3)-OH)], which possess the narrow pores (2.5-6.0 A). NJTU-Bai80-82 is able to be tuned to the neutral derivatives [NJTU-Bai80-82(-ox), ox = oxidized] with M(2+) ions oxidized to M(3+) ones in the air and the OH(-) ions coordinated on M(3+) ions. Very interestingly, selective CO(2)/N(2) adsorptions of NJTU-Bai80-82(-ox) are significantly enhanced with the CO(2) adsorption uptakes more than about 6 times that of NJTU-Bai79. GCMC simulations further revealed that neutral NJTU-Bai80-82(-ox) supplies more open frameworks around the -CH(3) groups at separate spaces to the CO(2) gas molecules with relatively more pores available to them after the removal of counterions. For the first time, finely tuning metal ion valences of metal clusters of ionic MOFs and making them from electrostatic to neutral were adopted for greatly improving their CO(2) capture properties, and it would provide another promising strategy for the exploration of high-performance CO(2) capture materials.

Effect of Calcium Oxide on Stress Crack Resistance and Light Transmittance in PET Containers for Packaging Carbonated Beverages.[Pubmed:38284055]

ACS Omega. 2024 Jan 8;9(3):3491-3498.

For polyethylene terephthalate (PET) bottles, a material used for food packaging, light transmission and mechanical performance, particularly environmental stress cracking (ESC), are essential characteristics. For this purpose, following extrusion of PET/CaO granules, preforms were manufactured using the injection technique, and bottles were produced by a stretch-blow-molding process. With incorporation of calcium oxide (CaO), light transmittance increased by around 25%, and ESC went from 0.3 to 11 min. In addition, whereas acetaldehyde (AA) and carboxylic acid (COOH) decomposition values rose with increasing CaO content, diethylene glycol and Isophthalic acid values did not significantly change. Moreover, the maximum crystallization temperature and crystallinity both exhibited an upward trend with the CaO content.

Solar-Driven Ammonia Production through Engineering of the Electronic Structure of a Zr-Based MOF.[Pubmed:38270093]

Inorg Chem. 2024 Feb 5;63(5):2327-2339.

As a hydrogen carrier and a vital component in fertilizer production, ammonia (NH(3)) is set to play a crucial role in the planet's future. While its industrial production feeds half of the global population, it uses fossil fuels and emits greenhouse gases. To tackle this issue, photocatalytic nitrogen fixation using visible light is emerging as an effective alternative method. This strategy avoids carbon dioxide (CO(2)) emissions and harnesses the largest share of sunlight. In this work, we successfully incorporated a 5-nitro Isophthalic acid linker into MOF-808 to introduce structural defects and open metal sites. This has allowed modulation of the electronic structure of the MOF and effectively reduced the band gap energy from 3.8 to 2.6 eV. Combination with g-C(3)N(4) enhanced further NH(3) production, as these two materials possess similar band gap energies, and g-C(3)N(4) has shown excellent performance for this reaction. The nitro groups serve as acceptors, and their integration into the MOF structure allowed effective interaction with the free electron pairs on N-(C)(3) in the g-C(3)N(4) network nodes. Based on DFT calculations, it was concluded that the adsorption of N(2) molecules on open metal sites caused a decrease in their triple bond energy. The modified MOF-808 showed superior performance compared with the other MOFs studied in terms of N(2) photoreduction under visible light. This design concept offers valuable information about how to engineer band gap energy in MOF structures and their combination with appropriate semiconductors for solar-powered photocatalytic reactions, such as N(2) or CO(2) photoreduction.

Fluorescent MOF and Its Gel Composite for the Fluorescence Recovery "Turn-On" Detection of Al(3+) Ions and "Turn-Off" Detection of Oxo-Anions.[Pubmed:38267375]

Inorg Chem. 2024 Feb 5;63(5):2352-2362.

The exploration of smart sensors is of great significance for the selectivity, sensitivity, and ability to show the low detection limit for the target analyte. Here, we have used the linker H(2)L (5-((anthracen-9-ylmethyl)amino)Isophthalic acid) for the construction of [Cd(L)(DMF)(H(2)O)(2)].H(2)O(n) (1) which is in order with the chromophore anthracene moiety and the free -NH functionality as a guest interaction site. This framework showed the luminescence recovery "turn-on" detection of the Al(3+) ion in an aqueous solution. An exhaustive mechanism study disclosed that the Lewis acid-base-type interaction between the Al(3+) ion and the -NH functionality of the linker in the framework revealed that the absorbance caused an enhancement for the "turn-on" sensing event. Besides the "turn-on" sensing event, the "turn-off" sensing phenomenon of 1 is also noticed when it detects the hazardous oxo-anions (MnO(4)(-) and CrO(4)(2-)) with limit of detection values of 17.08 and 19.91 ppb, respectively. The detection of these diverse analytes are very fast (10 s) and they can also be recognized through a colorimetric response. The sensing mechanisms for these analytes are established by photoinduced electron transfer, Forster resonance energy transfer, and inert filter effect along with theoretical investigation. Furthermore, to show the sensing application of 1 in a versatile podium, a MOF gel composite, 1@AA (AA = Agar-Agar), was developed from 1 with AA. Interestingly, 1@AA showed the colorimetric detection of these analytes under UV light. Therefore, sensor 1 behaves as a smart sensory material for the recognition of the above analytes through a simultaneous "turn-on" and "turn-off" effect.

Co(II) Metal-Organic Complex: Fluorescence Performances and Loaded With Drug Vitamin B2 Hydrogels Against Recurrent Oral Ulcers.[Pubmed:38252214]

J Fluoresc. 2024 Jan 22.

A new coordination polymer (CP) based on Co(II), namely, [Co(3)(L)(2)(4,4'-bipy)(DMA)(2)].H(2)O(n) (1) has been synthesized after reacting Co(NO(3))(2).6H(2)O with H(3)L ligand in the existence of N-donor ligand 4,4'-bipyridine (4,4'-bipy), via utilizing a flexible tricarboxylic acid ligand 5-((formic acid-3-sulfur)methyl)Isophthalic acid (H(3)L) with -S-CH(2)- joint. Additionally, the excellent blue fluorescence properties of CP 1 were confirmed through fluorescence spectroscopy compared to the original ligand. Using natural polysaccharide hyaluronic acid (HA) and carboxymethyl chitosan (CMCS) as raw materials, HA/CMCS hydrogel was prepared by chemical synthesis method. Taking vitamin B2 as the drug model, we designed and synthesized gels loaded with vitamin B2 metal framework and evaluated their efficacy in the treatment of recurrent oral ulcer.

Fluorescence-quenching mechanisms of novel isomorphic Zn/Cd coordination polymers for selective nitrobenzene detection.[Pubmed:38086232]

Spectrochim Acta A Mol Biomol Spectrosc. 2024 Mar 5;308:123729.

Nitroaromatic compounds in aqueous undermine environmental sustainability and affect human health. The development of a fluorescent sensor capable of efficiently and selectively detecting trace amounts of nitroaromatic compounds presents a considerable challenge. This study introduced Zn/Cd isomeric coordination polymers (Zn-H(2)CIA-1/Cd-H(2)CIA-2), which are synthesized using 5-((4-carboxybenzyl)oxy)Isophthalic acid (5-H(3)CIA) and 1,10-phenanthroline (Phen). The polymers have zero-dimensional discrete crystal structure with a six-coordinated scissor-like shape. The two coordination polymers can be used as fluorescent sensors for detecting nitrobenzene (NB) and demonstrated favorable sensitivity, with detection limits of 1.95 x 10(-8) and 4.66 x 10(-7) mol/L, respectively. Zn-H(2)CIA-1 exhibited stronger fluorescence and a more sensitive response to NB compared with Cd-H(2)CIA-2. To elucidate their fluorescence-quenching mechanisms, we analyzed Zn-H(2)CIA-1 by performing DFT and TD-DFT calculations. The pore structure, density of states, excitation energy, hole-electron distribution, and orbital composition were analyzed. The suitable size of pores in Zn-H(2)CIA-1 is the main reason for its high NB selectivity. Moreover, intermolecular pi-pi stacking interactions result in an orbital overlap between Zn-H(2)CIA-1 and NB, enabling the transfer of electrons from Zn-H(2)CIA-1 to NB. This electron transfer is identified as the fundamental cause of fluorescence quenching in Zn-H(2)CIA-1.

Halogen Bonding in the Decoration of Secondary Coordination Sphere of Zinc(II) and Cadmium(II) Complexes: Catalytic Application in Cycloaddition Reaction of CO(2) with Epoxides.[Pubmed:38024759]

ACS Omega. 2023 Nov 1;8(45):42290-42300.

Three new zinc(II) complexes [Zn(H(2)L(3))(2)(H(2)O)(3)] (Zn2), [Zn(H(3)L(2a))(H(2)O)(3)](n) (Zn3) (H(3)L(2a) = 2,4-diiodo-5-(2-(2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)hydrazineyl)isophthalate) and [Zn(HL(4))(DMF)(H(2)O)](n) (Zn4) were synthesized by the reaction of Zn(II) salts with 5-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl) Isophthalic acid (H(3)L(3)), 2,4,6-triiodo-5-(2-(2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)hydrazineyl) Isophthalic acid (H(5)L(2)) (in the presence of NH(2)OH.HCl) and 5-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl)-2,4,6-triiodoIsophthalic acid (H(3)L(4)), respectively. According to the X-ray structural analysis, the intramolecular resonance-assisted hydrogen bond ring remains intact, with N...O distances of 2.562(5) and 2.573(5) A in Zn2, 2.603(6) A in Zn3, and 2.563(8) A in Zn4. In the crystal packing of Zn3, the cooperation of I...O and I...I types of halogen bonds between tectons leads to a one-dimensional supramolecular polymer, while I...O interactions aggregate 1D chains of coordination polymer Zn4. These new complexes (Zn2, Zn3, and Zn4) and known [Zn(H(3)L(1))(H(2)O)(2)](n) (Zn1) (H(3)L(1) = 5-(2-(2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene) hydrazineyl)isophthalate), [Zn(H(3)L(1))(H(2)O)(3)].3H(2)O(n) (Zn5), [Cd(H(3)L(1))(H(2)O)(2)](n) (Cd1), [Cd(HL(3))(H(2)O)(2)(DMF)].H(2)O(n) (Cd2), [Cd(H(3)L(3))](n) (Cd-3), [Cd(2)(mu-H(2)O)(2)(mu-H(2)L(4))(2)(H(2)L(4))(2)].2H(2)O(n) (Cd4), and [Cd(H(3)L(1))(H(2)O)(3)].4H(2)O(n) (Cd5) were tested as catalysts in the cycloaddition reaction of CO(2) with epoxides in the presence of tetrabutylammonium halides as the cocatalyst. The halogen-bonded catalyst Zn4 is the most efficient one in the presence of tetrabutylammonium bromide by affording a high yield (85-99%) of cyclic carbonates under solvent-free conditions after 48 h at 40 bar and 80 degrees C.

A Multifunctional Co-Based Metal-Organic Framework as a Platform for Proton Conduction and Ni trophenols Reduction.[Pubmed:38015879]

Inorg Chem. 2023 Dec 11;62(49):20325-20339.

The design and development of proton conduction materials for clean energy-related applications is obviously important and highly desired but challenging. An ultrastable cobalt-based metal-organic framework Co-MOF, formulated as [Co(2)(btzip)(2)(mu(2)-OH(2))] (namely, LCUH-103, H(2)btzip = 4, 6-bis(triazol-1-yl)-Isophthalic acid) had been successfully synthesized via the hydrothermal method. LCUH-103 exhibits a three-dimensional framework and a one-dimensional microporous channel structure with scu topology based on the binuclear metallic cluster Co(2). LCUH-103 indicated excellent chemical and thermal stability; peculiarly, it can retain its entire framework in acid and alkali solutions with different pH values for 24 h. The excellent stability is a prerequisite for studying its proton conductivity, and its proton conductivity sigma can reach up to 1.25 x 10(-3) S.cm(-1) at 80 degrees C and 100% relative humidity (RH). In order to enhance its proton conductivity, the proton-conducting material Im@LCUH-103 had been prepared by encapsulating imidazole molecules into the channels of LCUH-103. Im@LCUH-103 indicated an excellent proton conductivity of 3.18 x 10(-2) S.cm(-1) at 80 degrees C and 100% RH, which is 1 order of magnitude higher than that of original LCUH-103. The proton conduction mechanism was systematically studied by various detection means and theoretical calculations. Meanwhile, LCUH-103 is also an excellent carrier for palladium nanoparticles (Pd NPs) via a wetness impregnation strategy, and the nitrophenols (4/3/2-NP) reduction in aqueous solution by Pd@LCUH-103 indicated an outstanding conversion efficiency, high rate constant (k), and exceptional cycling stability. Specifically, the k value of 4-NP reduction by Pd@LCUH-103 is superior to many other reported catalysts, and its k value is as high as 1.34 min(-1) and the cycling stability can reach up to 6 cycles. Notably, its turnover frequency (TOF) value is nearly 196.88 times more than that of Pd/C (wt 5%) in the reaction, indicating its excellent stability and catalytic activity.