Methyl Cation Research Articles

Fabrication of Co(II)-based coordination polymer for photocatalytic degradation: Selective removal of cationic methyl violet dye

In this study, a new coordination polymer (CP) was designed and synthesized to evaluate the photocatalytic properties for water remediation. The Co(II)-based CP {[Co(HL)(bid)(H2O)]·2H2O}n (1) was hydrothermally synthesized using the ligand 5-(4′-carboxyphenoxy)isophthalic acid (H3L) and 1,4-bis(1-imidazolyl)-2,5-dimethylbenzene (bid). The coordination polymer (1) has been characterized by various spectral techniques, thermogravimetric (TGA), and single crystal X-ray technique. X-ray data revealed that (1) exhibits 2D framework having an octahedral coordination geometry around the Co(II) ions, having μ1:η1-η1 mode with chromophore CoO4N. FT-IR analysis confirmed the asymmetric monodentate binding modes of the carboxylate ligand. The CP 1 has demonstrated optical semiconducting properties, rendering them promising candidates for photocatalytic applications. The catalyst (1) has been effectively utilized in the breakdown of several organic dyes, such as methylene blue (MB), methyl orange (MO), methyl violet (MV), and rhodamine B (RhB). The results showed that at pH 4, with a dosage of 30 mg of catalyst (1), 92.08 % of MV was degraded at a concentration of 20 ppm. Additionally, the mechanistic pathway for light-driven MV decomposition was investigated through experimental approaches, specifically radical trapping experiments.

Structures of hexamethyl-[1,1′-biphenyl]-4,4′-diammonium salts

The crystal structures of nine hexamethyl-[1,1′-biphenyl]-4,4′-diammonium (HMB) salts are described: the iodide (2), triiodide (3), succinate (4), fumarate (5), tetravanadate (6), hydroterephthalate (7) and perylenetetracarboxylate (8), as well as pentamethyl-[1,1′-biphenyl]-4,4′-diammonium iodide (1) and the metal–organic framework sodium diacetylenedisalicylate–HMB (9). HMB carbonate (10) has been synthesized as an important intermediate for a promising anti-metal–organic framework (`anti-MOF'). All the described compounds are characterized by high solubility in water. The results suggest that, during crystallization, crystallohydrates are formed from water. Compounds 6 and 9 are characterized by the presence of a rigid framework; compound 6 has an open framework structure filled with water molecules. Synchronous thermal analyses of compounds 2, 4, 6, 7, 8 and 10 allowed the identification of similarities in the mechanisms of thermolysis. At about 80–180°C, the loss of crystallization water molecules occurs. Between 180 and 250°C, a methyl group (methyl cation) is split off from the quaternary ammonium salt to form tetramethylbenzidinium. In the case of the iodides and salts of organic acids, the second thermolysis product is the methyl ester of this acid (methyliodide, dimethyl carbonate), which easily evaporates. In the range 240–355°C, tetramethylbenzidinium evaporates without decomposition.

N-doped three-dimensional carbon nanosheets: Facile synthesis and high-concentration dye adsorption

Purification of dye-contaminated wastewater has always been a research hotspot, yet also a challenge, due to high concentration and species diversity of pollutants. The present study designs an efficient nitrogen-doped 3D carbon nanosheets (N-3DCNs) adsorbent with 2592.50 m2 g−1 of specific surface area and 2.68 m3/g of average pore volume based on nitrilotriacetic acid trisodium salt by combining calcination and activation techniques. Microstructure and surface potential of N-3DCNs indicate that a large number of N heteroatoms in the lattice of main material can effectively optimize Zeta potential from 1.53 to −31.08 mV with solution pH increases from 3 to 11. So, as-prepared N-3DCNs possesses necessary conditions for efficient and selective adsorption of cationic dyes due to the abundant adsorption sites and strong electrostatic interactions. When 700 mg/L of cationic rhodamine and anionic methyl orange are respectively used as high concentration industrial dye-contaminated wastewater, N-3DCNs shows 97.97 % and 89.13 % of removal efficiency within 60 min. Furthermore, the adsorption capacity of N-3DCNs displays a wider pH tolerance at 1000 mg/L of cationic concentration, with a maximum adsorption capacity of 4888.70 mg/g at pH = 7 and a minimum value of 4203.77 mg/g at pH = 3, only 14 % of attenuation rate. The kinetics mechanism of dye adsorption could be well explained by pseudo-second-order kinetic model, suggesting chemisorption behavior, while fitting better with the linear Langmuir isothermal model. The groundbreaking and exceptional adsorption performances of N-3DCNs can be attributed primarily to the high specific surface area and negatively charged active sites, facilitating synergistic adsorption.

Dynamics of nanofiller–polymer synergy in gel formation via macromolecular crowding: Structure-property relationship of halloysite-integrated hybrid gels with abundant carboxyl groups

Halloysite (Hal) nanotube-reinforced hybrids were designed via mimicing macromolecular crowding for effective adsorption of cationic dyes by copolymerization of N-isopropylacrylamide (NIPA) and pH-responsive methacrylic acid (MA) through thermally initiated free-radical mechanism. A perspective on the synthesis of functional PNIPA-based next-generation hybrids was established using dynamics of nanofiller–polymer synergy in gel formation via incorporation of linear polyacrylamide chains. Since the design of hybrids with high polymer fraction is relatively difficult in gel systems in which the components are simply blended, the optimum gel formation was achieved by combining the advantage of one-pot strategy with the macromolecular crowding created using water-soluble polymer. By interacting with linear polyacrylamide chains via hydrogen bonding interactions, Hal-lumens participate in the formation of hybrid networks and are homogeneously distributed in the polymer matrix, thus significantly improving the physicochemical properties. The reversibility and rapid on-off properties of hybrids with varied Hal-loadings were analyzed depending on pH and ionic strength of surrounding medium. Design of hybrids functionalized with specific groups depends on both the amount of these groups and the nature of their distribution in the network. The swelling of hybrids in pH 9.8 is lower compared to results in 10−5 M KCl solution, while there was an increase in the compressive modulus with a decrease in swelling pH. The effect of potassium salts of different anions on salt-induced swelling and elastic response of hybrids was investigated to understand the interactions between salt ions and hybrid network. The expansion of hybrids was found to follow the reverse order of classical Hofmeister series. Depending on Fick's law, hybrid gels followed non-Fickian kinetics in salt solutions, while Fickian swelling was observed in pH 9.8. The influence of Hal-addition on cationic dye methyl violet (MV) adsorption of hybrids was investigated. While the addition of Hal increased the adsorption capacity, 93.6 % efficiency for MV was obtained in the presence of 5.40 % Hal. The obtained results provided a novel routine for designing alkyl acrylamide-based functional hybrid gels using green one-dimensional tube-like nanoparticles.

Nanowire-like phosphorus modulated carbon-based iron nanozyme with oxidase-like activity for sensitive detection of choline and dye degradation

Choline is mainly supplemented through food intake, lack of choline would result in diseases like liver cirrhosis, hardening of the arteries, or neurodegenerative disorders. The accurate detection of choline is important for human health. Herein, a novel nanowire-like phosphorus/nitrogen co-doped carbon-based iron nanozyme (Fe-NPC) with outstanding oxidase-like activity was synthesized, and the influence of phosphorus doping on oxidase-like activity was explored. Proper phosphorus doping was found to enhance the oxidase-like activity of Fe-NPC by increasing surface defects, promoting iron loading, and modulating chemical environment of central site. The oxidase-like activity of Fe-NPC was successfully applied to colorimetric-fluorescent dual mode detection of choline, and good linear relationship in the ranges of 3–200 μM were achieved with LODs of 1.95 and 1.50 μM, respectively. The fluorescent detection was constructed based on the fluorescence quenching of silicon quantum dots (Si QDs) by quinone-imine. The quenching mechanism was attributed to FRET due to the large spectra overlap, reduced fluorescence lifetime and proper donor−acceptor distance. The successful application to the detection of choline in milk proved the practicability of the proposed sensing method. The oxidase-like properties of Fe-NPC was further used in the degradation of cationic dye methyl blue, high degradation efficiency of 74 % was achieved within 5 min under optimal conditions, proving the enormous potential of Fe-NPC for application in environment protection.

Sodium titanate (Na2Ti4O9) nanoribbons for effective removal of organic dyes from water: Experimental and computational studies

In this work, Na2Ti4O9 nanoribbons (NTRs) were synthesized using the hydrothermal method for its potential application in water treatment. The NTRs were characterized by X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, zeta potential, Fourier Transform infrared spectroscopy, and surface area analyzer. The adsorption of organic dyes, including cationic methyl green (MeG) and methylene blue (MB) model pollutants, onto the NTRs was explored for the first time. Various parameters such as pH, adsorbent dose, initial dye concentration, regeneration, contact time, the effect of temperature, and thermodynamics were studied to determine the efficiency of NTRs for removing both dyes from water. A variety of isotherm and kinetic models were applied to fit the dye adsorption data at pH 7.0, providing insights into the adsorption mechanism and process kinetics. Kinetic data for both dyes fit well with pseudo-second-order and mixed 1,2-order models. The isotherm data agreed well with Langmuir-Freundlich and Sips models. At the studied temperatures of 298.2, 318.2, and 328.2 K, the maximum adsorption capacities for MeG (353.2, 367.7, and 443.2 mg·g−1) are significantly higher than for MB (29.3, 52.6, and 67.2 mg·g−1), indicating a stronger affinity for MeG, with adsorption efficiency improving as temperature increases. The MeG samples at 328.2 K exhibited interesting behavior. After adsorption, the samples became colorless, with a final pH near 7.0, indicating effective dye removal. However, the color faintly reappeared at pH 4.0, suggesting pH-dependent behavior and incomplete dye removal. The adsorption mechanism on the NTRs surface was investigated using Monte Carlo and molecular dynamics simulations.

Facile Preparation of Cross-Linked Moringa oleifera Seed Hulls Powder/Hydroxyapatite Framework Composite for Efficient Removal of Toluidine Blue and Methyl Violet 2B from Aqueous Solution

AbstractIn this study, adsorption of two cationic dyes, Toluidine Blue (TB) and Methyl violet 2B (MV 2B) from an aqueous solution was achieved by using multifunctional composite material. The formulation of the composite (MO@HA) was obtained by using Moringa oleifera seed hull powder, calcium chloride (CaCl2), and ammonium hydrogenophosphate (NH4)2HPO4 salts. Surface morphology, functional groups, specific surface area, and surface charge of the composite were explored using Scanning electron microscopy (SEM), Fourier Transform infrared spectroscopy (FTIR), BET analysis, and point of zero charge (PZC), respectively. The composite material resulted in a structural change in the surface of the adsorbents, increased oxygen vacancies, enhancement of active sites, and a specific surface area of 735.55 m2 g−1. Different adsorption parameters such as pH, contact time, adsorbent dosage, and initial concentration were evaluated. The adsorption study showed that equilibrium was reached after 60 min, and the optimum adsorption pH for both dyes (TB and MV 2B) was 6. Langmuir, Freundlich, Liu, and Temkin were fitted to describe the adsorption isotherm, both TB and MV 2B had best correlation with Liu isotherm. The maximum adsorption capacity of TB and MV 2B were 341.488 and 182.453 mg g−1, respectively. Adsorption-desorption cycling studies on the adsorbent confirmed its regeneration and reusability after 5 cycles. A possible adsorption mechanism involving electrostatic interactions, n-π bonding, and hydrogen bonding was suggested. These findings highlight a new direction in the development of efficient and sustainable adsorbent in environmental remediation, specifically in the removal of dyes from aqueous solution.

Quaternary Biocomposite of Chitosan-Polyvinyl Alcohol/Food Grade Algae/ Montmorillonite Clay for Cationic Methyl Violet 2B Dye Removal: Optimization and Desirability Functions

Quaternary Biocomposite of Chitosan-Polyvinyl Alcohol/Food Grade Algae/ Montmorillonite Clay for Cationic Methyl Violet 2B Dye Removal: Optimization and Desirability Functions

Using natural antioxidant Rhubarb extracts in PVA/chitosan bio-adsorbent films for efficient removal of cationic and anionic dyes from polluted water

In this research, sustainable membrane films were developed for removal of cationic and anionic dyes from wastewater based on polyvinyl alcohol/chitosan (PVA/CS) incorporated with natural antioxidant Rhubarb dye (Rh) extracts. Rh dye was extracted from Rhubarb roots by a green method. Three different quantities of Rh dye extracts (i.e., 2.5, 5, and 10 %) were used to fabricate crosslinked PVA/CS films by solvent-casting approach. The fabricated films subjected to different techniques such as X-ray diffraction (XRD), scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM-EDX), dynamic mechanical analysis (DMA), as well as antioxidant activity. In all cases, the incorporation of Rh dye extracts inside the composite improved the crystallinity, biocompatibility, stress–strain properties, besides the DPPH scavenging activity reached 42.50 % for PVA/CS-10 % Rh membrane compared to PVA/CS blank (i.e., ∼ 2.10 %). Dyes adsorption including different cationic and anionic dyes implemented for all selected membranes. The data revealed that the membrane containing 10 % Rh dye was the optimum for removal of malachite green oxide (MG, 93 %) as cationic dye and methyl orange (MO, 95.70 %) as anionic dye. Moreover, the kinetics of the removal process exhibited that this process followed the Langmuir, Freundlich, Temkin, Dubinin-Radushkevich models, and the pseudo-1st order kinetic model, with an R2 of 0.998 and 0.943 for MG and MG, respectively. Whereas, the adsorption process corresponded to the Freundlich isotherm model, with coefficients R2 was of 0.989 and 0.988 for MO and MG, respectively. Other parameters including dye concentration, contacting time, pH media, and kinetic studies were also applied on PVA/CS-10 % Rh membrane.

Graphene Oxide Decorated with Nickel Cobaltite Nanoparticles as an Adsorbent for Cationic Methyl Green Dye: Kinetic, Isotherm, and Thermodynamic Studies

‎تم في هذه الدراسة ، تزيين ‏رقائق أكسيد الجرافين (‏GO‏) بجسيمات ‏كوبلتيت النيكل النانوية ‏NiCo2O4‎‏(‏NC‏) عن طريق الترسيب في ‏الموقع ، وتم استخدام المتراكب ‏المحضر (‏NC: GO‏) كسطح ماز لإزالة ‏صبغة الميثيل الخضراء ( ‏MG‏) من ‏المحاليل المائية. تم التحقق من ‏التغطية الناجحة لأوكسيد الجرافين ‏بجزيئات كوبلتيت النيكل النانوية ‏‏(‏NC‏) باستخدام دراسات ‏FT-IR‏ وحيود ‏الأشعة السينية (‏XRD‏). كانت أحجام ‏الجسيمات البلورية لل ‏NC‏ و ‏ لل ‏GO‏ المزين ب NCهي ‏‎10.53‎‏ نانوميتر ‏‏9.30 نانومتر على التوالي. تم دراسة ‏تأثير العديد من العوامل التجريبية ‏، بما في ذلك زمن التلامس ، وكمية ‏السطح الماز ، ودرجة الحرارة. كان ‏وقت التلامس الأمثل وكمية السطح 120 ‏دقيقة و 3 مجم / لتر على التوالي. ‏تتلائم بيانات الامتزاز بشكل أفضل مع ‏ايزوثيرم ‏Freundlich‏. تم استخدام ‏أربعة نماذج حركية لتتبع عملية ‏الامتزاز: معادلة زائفة من الدرجة ‏الأولى ، ومعادلة زائفة من الدرجة ‏الثانية ، ومعادلة الانتشار داخل ‏الجسيمات ، ومعادلة بويد. أظهرت ‏نمذجة البيانات التجريبية أن حركية ‏الامتزاز كانت ممثلة بشكل جيد ‏بنموذج الرتبة الثانية الزائفة (‏R2 ‎‎= 0.9945‎‏) مع معدل ثابت سرعة يبلغ 3.2 ‏‏× 10 - 3 (جم / مجم. دقيقة). يتم ‏امتصاص صبغة ‏MG‏ تدريجيًا بواسطة ‏الجسيمات النانوية ‏NC‏ من خلال ‏الانتشار داخل الجسيمات ويتم ‏الاحتفاظ بها بعد ذلك في مسام أصغر. ‏أظهرت قيم التحليل الديناميكي ‏الحراري أن عملية امتزاز صبغة ‏MG‏ ‏كانت ماصة للحرارة بطبيعتها ، و ‏تلقائية وعملية الامتزاز فيزيائية. الكلمات المفتاحية: الانتشار داخل الجسيمات ، المسافات البينية، النموذج الزائف من الدرجة الأولى ، معادلة بويد

Mechanistic investigation of methanol-to-olefins conversion catalyzed by H-ZSM-5 zeolite: a DFT study.

The mechanisms for the formation of the first C - C bond and lower olefins on methanol to olefins (MTO) conversion on H-ZSM-5 had been focused in dispute. In this paper, density functional theory has been used to study the reaction mechanisms of methanol to olefins on ZSM-5. The configurations of reactants, intermediates, products and transition state of the numerous reactions involved in such a process have been optimized, as well as the elementary reactions related to these configurations were determined by the calculation of corresponding activation energy barriers and reaction heats. Here, two different kinds of the mechanisms were proposed for the formation of dimethylether (DME), one involving an associative interaction of two methanol molecules with the zeolite Brønsted acid sites and the other occurring via a surface methoxy species and a methanol molecule. A critical intermediate of the methoxy methyl cation was theoretically verified by the reaction of the methoxy species and dimethylether. Besides, it was found that the first intermediates containing a C - C bond were 1,2-dimethoxyethane and 2-methoxy-ethanolare, in which the former was formed from methoxy species with dimethyl ether and the latter was formed from methanol by onium ions((CH3)2O+CH2CH2OCH3), respectively. For the whole reaction mechanism, the results in this paper indicated that the ethene formation is more favorable than propylene formation due to the low activation energy barrier for ethene formation (123.49 vs. 162.09kJ.mol-1). From these calculations, it would be concluded that ethene is the first alkene product that induces the occurrence of the hydrocarbon pool mechanism. All the periodic density function theory (DFT) calculations were performed by the Vienna Ab Initio Simulation package (VASP). The interaction between nucleus and valence electron was described using the pseudopotentials found in the projector augmented wave (PAW) method. PBE-D3 was used in the whole DFT calculations and CI-NEB was used to locate transition state.

Efficacy of activated carbon using Salvadora persica stem for remediation of potentially toxic dyes from aqueous solution.

Potentially toxic dyes are introduced mainly to rivers through industrial effluents which have a high risk to human health and aquatic life. Activated carbon (AC) from the stem of Salvadora persica was synthesised to take off toxic industrial dyes from an aqueous solution. KOH was used as the activating agent throughout the preparation process for the AC. The morphology and composition of the prepared AC were studied by various analytical methods. From the overall results, it was found that the prepared AC is highly porous and thermal stability gained around 800 ℃. At room temperature, remediation of the dyes (cationic dye, methyl red and anionic dye, methylene blue) using the adsorption method was carried out to ascertain the impact of time and the quantity of AC on methylene blue (MB) and methyl red (MR) removal. During the initial 60min, equilibrium was attained for the optimum dye concentration (200mg/L). The data for adsorption on the AC obtained at equilibrium were examined by the Langmuir and Freundlich isothermmodels. Both the isotherms accurately predicted the data, with regression values of 0.99 for MR and 0.90 for MB, respectively. The equilibrium adsorption data was also analysed by kinetic models. The adsorption data well fittedin2nd order kinetic model. The results of MB and MR adsorption from solutions have demonstrated that the stem of Salvadora persica is one of the cheap and more eco-friendly options for remediation of toxic dyes from aqueous solutions.

Mesoporous Fe3O4/SiO2/poly(2-carboxyethyl acrylate) composite polymer particles for pH-responsive loading and targeted release of bioactive molecules.

pH-responsive polymer microspheres undergoing reversible changes in their surface properties have been proved useful for drug delivery to targeted sites. This paper is aimed at preparing pH-responsive polymer-modified magnetic mesoporous SiO2 particles. First, mesoporous magnetic (Fe3O4) core-particles are prepared using a one-pot solvothermal method. Then, magnetic Fe3O4 particles are covered with a C[double bond, length as m-dash]C functional mesoporous SiO2 layer before seeded emulsion polymerization of 2-carboxyethyl acrylate (2-CEA). The composite polymer particles are named Fe3O4/SiO2/P(2-CEA). The average diameters of the Fe3O4 core and Fe3O4/SiO2/P(2-CEA) composite polymer particles are 414 and 595 nm, respectively. The mesoporous (pore diameter = 3.41 nm) structure of Fe3O4/SiO2/P(2-CEA) composite polymer particles is confirmed from Brunauer-Emmett-Teller (BET) surface analysis. The synthesized Fe3O4/SiO2/P(2-CEA) composite polymer exhibited pH-dependent changes in volume and surface charge density due to deprotonation of the carboxyl group under alkaline pH conditions. The change in the surface properties of Fe3O4/SiO2/P(2-CEA) composite polymer particles following pH change is confirmed from the pH-dependent sorption of cationic methylene blue (MB) and anionic methyl orange (MO) dye molecules. The opening of the pH-responsive P(2-CEA) gate valve at pH 10.0 allowed the release of loaded vancomycin up to 99% after 165 min and p-acetamido phenol (p-AP) up to 46% after 225 min. Comparatively, the amount of release is lower at pH 8.0 but still suitable for drug delivery applications. These results suggested that the mesoporous Fe3O4/SiO2 composite seed acted as a microcapsule, while P(2-CEA) functioned as a gate valve across the porous channel. The prepared composite polymer can therefore be useful for treating intestine/colon cancer, where the pH is comparatively alkaline.

Demethylation C–C coupling reaction facilitated by the repulsive Coulomb force between two cations

Carbon chain elongation (CCE) is normally carried out using either chemical catalysts or bioenzymes. Herein we demonstrate a catalyst-free approach to promote demethylation C–C coupling reactions for advanced CCE constructed with functional groups under ambient conditions. Accelerated by the electric field, two organic cations containing a methyl group (e.g., ketones, acids, and aldehydes) approach each other with such proximity that the energy of the repulsive Coulomb interaction between these two cations exceeds the bond energy of the methyl group. This results in the elimination of a methyl cation and the coupling of the residual carbonyl carbon groups. As confirmed by high-resolution mass spectrometry and isotope-labeling experiments, the C–C coupling reactions (yields up to 76.5%) were commonly observed in the gas phase or liquid phase, for which the mechanism was further studied using molecular dynamics simulations and stationary-point calculations, revealing deep insights and perspectives of chemistry.

Circumventing bottlenecks in H2O2 photosynthesis over carbon nitride with iodine redox chemistry and electric field effects

Artificial photosynthesis using carbon nitride (g-C3N4) holds a great promise for sustainable and cost-effective H2O2 production, but the high carrier recombination rate impedes its efficiency. To tackle this challenge, we propose an innovative method involving multispecies iodine mediators (I−/I3−) intercalation through a pre-photo-oxidation process using potassium iodide (suspected deteriorated “KI”) within the g-C3N4 framework. Moreover, we introduce an external electric field by incorporating cationic methyl viologen ions to establish an auxiliary electron transfer channel. Such a unique design drastically improves the separation of photo-generated carriers, achieving an impressive H2O2 production rate of 46.40 mmol g−1 h−1 under visible light irradiation, surpassing the most visible-light H2O2-producing systems. Combining various advanced characterization techniques elucidates the inner photocatalytic mechanism, and the application potential of this photocatalytic system is validated with various simulation scenarios. This work presents a significative strategy for preparing and applying highly efficient g-C3N4-based catalysts in photochemical H2O2 production.

A smart L‐alanine modified Cd‐NDI metal‐organic framework crystalline material: Photochromic properties and photocatalytic degradation dye applications

1, 4, 5, 8‐naphthalene diimide (NDI)‐based MOFs, due to their tunable structures and properties, have shown promising applications in photochromism, photocatalysis, electrocatalysis, photothermal therapy, etc. Herein, using an L‐alanine modified NDI ligand, i.e. N, N′‐bis(L‐alanine)naphthalenediimide (AlaNDI), a novel Cd‐NDI Cd (AlaNDI)(H2O)]·DMF·H2O (complex 1) was constructed under solvothermal conditions, which has an obvious different structure with the previously reported ones. Structural analysis shows that the packing structure of complex 1 consists of two adjacent Cd atoms sharing two AlaNDI ligands, forming a dimetallic building block [Cd2O8]. Each building block connects a total of four AlaNDI ligands, where two Cd atoms are bridged by two ligands. The building blocks are interconnected by ligands to form a two‐dimensional layered structure. Based on the features of the NDI skeleton, it was found that complex 1 possesses multiple stimulus responses involving sensitivity to light: a reversible photochromism property and good photocatalytic degradation activity against various dyes, especially against cationic dyes crystal violet (CV), methyl violet (MV), and Janus green B (JGB). In addition, the stimulus‐response mechanism was investigated by control experiments. It is revealed that the photocatalytic active species may be related to h+ and •OH.

Bimetal Cu/Ni-BTC@SiO2 metal-organic framework as high performance photocatalyst for degradation of azo dyes under visible light irradiation

There has been significant attention on the efficient degradation of pollutants in wastewater using metal-organic frameworks (MOFs) photocatalytic methods over the past decade. Herein, we examined the elimination of two different types of water-contaminating dyes, specifically cationic dye methylene blue (MB) and anionic dye methyl orange (MO), through the application of bimetal Cu/Ni-BTC@SiO2 MOF as high performance photocatalyst. The bimetal Cu/Ni-BTC@SiO2 photocatalyst was synthesized and characterized by XRD, FTIR, SEM, TEM, TGA, BET, DRS, and VSM techniques. The examination of the impact of different operational factors on the elimination of pollutants involved a comprehensive analysis of variables including the photocatalyst type, initial pollutant concentration, quantity of photocatalyst, and pH levels. The highest removal efficiency for MO and MB dyes by the photocatalyst was found to be 98 and 71%, respectively, within 60 min. In the fifth reaction stage, degradation efficiency for MO and MB was 76 and 56% respectively. Kinetic investigations demonstrated that, in the context of the uptake of MB and MO dyes, the interparticle diffusion, and pseudo-second-order models emerged as possessing the most robust correlation coefficients with the experimental data, registering values of 0.988 and 0.961, respectively. The examination of isotherms reveals that the isotherm models proposed by BET, and Anderson (V) demonstrate the highest level of conformity with the empirical data for the decomposition of MB and MO dyes, correspondingly. The TOC levels decreased significantly from 51 to 14 and 47 to 3 mg/L for MB and MO dyes, indicating the effective mineralization process using Cu/Ni-BTC@SiO2.

Determination of glycyrrhizic acid as sweeteners by dual-wavelength overlapping resonance Rayleigh scattering

This study used cationic dyes methyl violet (MV) and neutral red (NR) as probes, based on dual-wavelength overlapping resonance Rayleigh scattering (RRS), and designed two highly sensitive methods for the determination of the natural sweetener glycyrrhizic acid (GZA). In the Clark-Lubs buffer solution, when only MV or NR was present in the solution, they formed supramolecular polymers through hydrogen bonding. When adding GZA at different concentrations, the formation of ionic association complexes led to a subsequent decrease in RRS intensity at two wavelengths in the MV − GZA system and NR − GZA system, and the amount of the decline was proportional to the GZA concentration. The linear ranges were determined as 0.1 − 0.6 mg/L and 0.1 − 0.7 mg/L, with correlation coefficients of 0.9972 and 0.9996, and limits of detection were 0.052 mg/L and 0.016 mg/L, respectively. For this study, reaction conditions were optimized, potential interfering substances were investigated, and the mechanisms behind RRS generation and intensity decrease were discussed. The proposed methods were sensitive, fast, time-saving and efficient, and have been successfully applied to licorice and dried ginger decoction analysis, yielding satisfactory results.

Diastereo-divergent synthesis of chiral hindered ethers via a synergistic calcium(II)/gold(I) catalyzed cascade hydration/1,4-addition reaction.

Hindered ethers are ubiquitous in natural products and bioactive molecules. However, developing an efficient method for the stereocontrolled synthesis of all stereoisomers of chiral hindered ethers is highly desirable but challenging. Here we show a strategy that utilizes in situ-generated water as a nucleophile in an asymmetric cascade reaction involving two highly reactive intermediates, 3-furyl methyl cations and ortho-quinone methides (o-QMs), to synthesize chiral hindered ethers. The Ca(II)/Au(I) synergistic catalytic system enables the control of diastereoselectivity and enantioselectivity by selecting suitable chiral phosphine ligands in this cascade hydration/1,4-addition reaction, affording all four stereoisomers of a diverse range of chiral tetra-aryl substituted ethers with high diastereoselectivities (up to >20/1) and enantioselectivities (up to 95% ee). This work provides an example of chiral Ca(II)/Au(I) bimetallic catalytic system controlling two stereogenic centers via a cascade reaction in a single operation.

Crucial Roles of Leaving Group and Open-Shell Cation in Photoreaction of (Coumarin-4-yl)methyl Derivatives.

Photoreactions of (coumarin-4-yl)methyl derivatives have been extensively studied in many fields of chemistry, including organic synthesis and photoinduced drug delivery systems. The identification of the reaction intermediates involved in the photoreactions is crucial not only for elucidating the reaction mechanism but also for the application of the photoreactions. In this study, the photoreactions of 7-diethylamino(coumarin-4-yl)methyl thioester 1a [-SC(O)CH3], thionoester 1b [-OC(S)CH3], and ester 1c [-OC(O)CH3] were investigated to clarify the intermediary species and their chemical behavior. While a radical pair [i.e., 7-diethylamino(coumarin-4-yl)methyl radical and CH3C(O)S•] plays an important role in the photoreactions of 1a and 1b, an ion pair [i.e., 7-diethylamino(coumarin-4-yl)methyl cation, and CH3CO2-] was the key in the photoreaction of 1c. 18O-isotope-labeling of 1c revealed a negligible recombination process within the ion pair. The unprecedented observation was rationalized by the open-shell character of the 7-diethylamino(coumarin-4-yl)methyl cation, whose formation was confirmed through product analysis and transient absorption spectroscopy.