Chemical and engineering bases for green H2O2 production and related oxidation and ammoximation of olefins and analogues.

Plastics, fibers and rubber are three mainstream synthetic materials that are essential to our daily lives and contribute significantly to the quality of our lives. The production of the monomers of these synthetic polymers usually involves oxidation or ammoximation reactions of olefins and analogues. However, the utilization of C, O and N atoms in current industrial processes is <80%, which represents the most environmentally polluting processes for the production of basic chemicals. Through innovation and integration of catalytic materials, new reaction pathways, and reaction engineering, the Research Institute of Petroleum Processing, Sinopec Co., Ltd. (RIPP) and its collaborators have developed unique H2O2-centered oxidation/ammoximation technologies for olefins and analogues, which has resulted in a ¥500 billion emerging industry and driven trillions of ¥s' worth of downstream industries. The chemical and engineering bases of the production technologies mainly involve the integration of slurry-bed reactors and microsphere catalysts to enhance H2O2 production, H2O2 propylene/chloropropylene epoxidation for the production of propylene oxide/epichlorohydrin, and integration of H2O2 cyclohexanone ammoximation and membrane separation to innovate the caprolactam production process. This review briefly summarizes the whole process from the acquisition of scientific knowledge to the formation of an industrial production technology by RIPP. Moreover, the scientific frontiers of H2O2 production and related oxidation/ammoximation processes of olefins and analogues are reviewed, and new technological growth points are envisaged, with the aim of maintaining China's standing as a leader in the development of the science and technologies of H2O2 production and utilization.

Preclinical evidence of the anti-inflammatory effect and toxicological safety of aryl-cyclohexanone in vivo.

BACKGROUND: Respiratory distress syndrome is a complex inflammatory condition defined by the presence of acute hypoxemia and cellular infiltration with diffuse alveolar injury following a tissue injury, such as acute lung injury. The inflammatory process involved in this pathology is a defense mechanism of the body against infectious agents and/or tissue injuries. However, when the condition is not reversed, it becomes a significant cause of tissue damage, sometimes leading to loss of function of the affected organ. Therefore, it is essential to understand the mechanisms underlying inflammation, as well as the development of new therapeutic agents that reduce inflammatory damage in these cases. Aryl-cyclohexanone derivatives have previously shown significant anti-inflammatory activity linked to an immunomodulatory capacity in vitro and may be good candidates for therapies in which inflammation plays a central role. METHODS: Was evaluated the anti-inflammatory capacity of a synthesized molecule aryl-cyclohexanone in the murine model of lipopolysaccharide (LPS)-induced acute lung injury. The assessment of acute oral toxicity follows the Organization for Economic Co-operation and Development (OECD) guideline 423. RESULTS: The results demonstrated that the studied molecule protects against LPS-induced inflammation. We observed a decrease in the migration of total and differential leukocytes to the bronchoalveolar lavage fluid (BALF), in addition to a reduction in exudation, myeloperoxidase (MPO) activity, nitric oxide metabolites, and the secretion of pro-inflammatory cytokines (alpha tumor necrosis factors [TNF-α], interleukin-6 [IL-6], interferon-gamma [IFN-γ], and monocyte chemoattractant protein-1 [MCP-1]). Finally, aryl cyclohexanone did not show signs of acute oral toxicity (OECD 423). CONCLUSIONS: The results prove our hypothesis that aryl-cyclohexanone is a promising molecule for developing a new, safe anti-inflammatory drug.

Electrocatalytic coupled biofilter for treating cyclohexanone-containing wastewater: Degradation, mechanism and optimization.

Electrocatalytic coupled biofilter (EBF) technology organically integrates the characteristics of electrochemistry and microbial redox, providing ideas for effectively improving biological treatment performance. In this study, an EBF system was developed for enhanced degradation of cyclohexanone in contaminated water. Experimental results show that the system can effectively remove cyclohexanone in contaminated water. Under the optimal parameters, the removal rates of cyclohexanone, TP, NH4+-N and TN were 97.61 ± 1.31%, 76.31 ± 1.67%, 94.14 ± 2.13% and 95.87 ± 1.01% respectively. Degradation kinetics studies found that electrolysis, adsorption, and biodegradation pathways play a major role in the degradation of cyclohexanone. Microbial community analysis indicates that voltage can affect the structure of the microbial community, with the dominant genera shifting from Acidovorax (0 V) to Brevundimonas (0.7 V). Additionally, Acidovorax, Cupriavidus, Ralstonia, and Hydrogenophaga have high abundance in the biofilm and can effectively metabolize cyclohexanone and its intermediates, facilitating the removal of cyclohexanone. In summary, this research can guide the development and construction of highly stable EBF systems and is expected to be used for advanced treatment of industrial wastewater containing cyclohexanone.

Comparative Bioremediation of Tetradecane, Cyclohexanone and Cyclohexane by Filamentous Fungi from Polluted Habitats in Kazakhstan.

Studying the fates of oil components and their interactions with ecological systems is essential for developing comprehensive management strategies and enhancing restoration following oil spill incidents. The potential expansion of Kazakhstan's role in the global oil market necessitates the existence of land-specific studies that contribute to the field of bioremediation. In this study, a set of experiments was designed to assess the growth and biodegradation capacities of eight fungal strains sourced from Kazakhstan soil when exposed to the hydrocarbon substrates from which they were initially isolated. The strains were identified as Aspergillus sp. SBUG-M1743, Penicillium javanicum SBUG-M1744, SBUG-M1770, Trichoderma harzianum SBUG-M1750 and Fusarium oxysporum SBUG-1746, SBUG-M1748, SBUG-M1768 and SBUG-M1769 using the internal transcribed spacer (ITS) region. Furthermore, microscopic and macroscopic evaluations agreed with the sequence-based identification. Aspergillus sp. SBUG-M1743 and P. javanicum SBUG-M1744 displayed remarkable biodegradation capabilities in the presence of tetradecane with up to a 9-fold biomass increase in the static cultures. T. harzianum SBUG-M1750 exhibited poor growth, which was a consequence of its low efficiency of tetradecane degradation. Monocarboxylic acids were the main degradation products by SBUG-M1743, SBUG-M1744, SBUG-M1750, and SBUG-M1770 indicating the monoterminal degradation pathway through ß-oxidation, while the additional detection of dicarboxylic acid in SBUG-M1768 and SBUG-M1769 cultures was indicative of the fungus' ability to undertake both monoterminal and diterminal degradation pathways. F. oxysporum SBUG-M1746 and SBUG-M1748 in the presence of cyclohexanone showed a doubling of the biomass with the ability to degrade the substrate almost completely in shake cultures. F. oxysporum SBUG-M1746 was also able to degrade cyclohexane completely and excreted all possible metabolites of the degradation pathway. Understanding the degradation potential of these fungal isolates to different hydrocarbon substrates will help in developing effective bioremediation strategies tailored to local conditions.

Liquid- liquid (Cyclohexanone: Cyclohexanol) separation using augmented tight nanofiltration membrane: A sustainable approach.

Organic solvent nanofiltration (OSN) is an incipient technology in the field of organic liquid-liquid separation. The incomplete separations and complexity involved in these, forces many organic liquids to be released as effluents and the adverse effects of these on environment is enormous and irreparable. The work prominences on the complete separation of industrially significant cyclohexanone: cyclohexanol (keto-alcohol oil) and heptane: toluene mixtures. The separations of these above-mentioned organic liquid mixtures were carried out using the fabricated Lewis acid modified graphitic carbon nitride (Cu2O@g-C3N4) incorporated polyvinylidene difluoride (PVDF) composite membranes. These fabricated membranes showed a separation factor of 18.16 and flux of 1.62 Lm-2h-1 for cyclohexanone: cyclohexanol mixture and separation of heptane and toluene mixture (with heptane flux of 1.52 Lm-2h-1) showed a separation factor of 9.9. The selectivity and productivity are based on the polarity and size of the organic liquids. The role of Cu2O@g-C3N4 is influencing the pore size distribution, increased divergence from solubility parameters, polarity, solvent uptake and porosity of the composite membranes. The developed composite membranes are thus envisioned to be apt for a wide range of liquid-liquid separations due to its implicit nature.

Polyvinyl chloride solvent cement poisoning: a case report.

BACKGROUND: S-lon® (S) is a locally produced polyvinyl chloride-based solvent cement. It is a clear, slightly viscous liquid. Other constituents include 1-cyclohexanone, 3-butanone, and 1-acetone. It is used ubiquitously for building construction in Sri Lanka. Although the clinical effects of the compound have not yet been ascertained, the constituents have been implicated in neurotoxicity, respiratory tract, eye and skin irritation, and delayed liver and renal injury. CASE DESCRIPTION: A 42-year-old South Asian male presented following self-ingestion of S. His vital parameters were stable and initially managed symptomatically. A few hours later, he developed central nervous system depression and stridor requiring elective intubation. Examination of the upper airway revealed inflammation and edema. He was sedated and ventilated, and intravenous dexamethasone was administered. Attempts at removal of the nasogastric tube after extubation on day 3 failed. The patient had to be reintubated and sedated owing to extreme agitation not responding to routine doses of sedatives. The nasogastric tube had been amalgamated after reacting with S, forming a solid clump, later found after removal. The posterior pharynx and nasopharynx were packed and later removed before extubation. The patient made a full recovery and was transferred to the ward on day 5. CONCLUSION: Ingestion of a sufficient quantity of S could result in gut absorption with central nervous system depression, coma, and even death. No antidote is available for toxicity, and management is largely supportive. As witnessed in our patient, chemical laryngitis and upper airway inflammation may lead to upper airway obstruction. Chemical reactions with medical equipment may lead to unforeseen outcomes.

Polymer Beads Increase Field Responses to Host Attractants in the Dengue Vector Aedes aegypti.

This study investigates the efficacy of three different olfactory cues - cyclohexanone, linalool oxide (LO), and 6-methyl-5-heptan-2-one (sulcatone) - in attracting Aedes aegypti, the primary vector of dengue, using BG sentinel traps in a dengue-endemic area (urban Ukunda) in coastal Kenya. Two experiments were conducted. Experiment 1 compared solid formulations of the compounds in polymer beads against liquid formulations with hexane as the solvent. CO2-baited traps served as controls. In Experiment 2, traps were baited with each compound in the polymer beads, commercial BG-Lure, and CO2. Our results indicate that CO2-baited traps recorded the greatest Ae. aegypti captures in both Experiment 1 and 2, whereas trap captures with polymer beads and solvent-based treatments were comparable. In experiment 2, polymer bead-based treatments yielded significantly greater female captures, each recording ~ 2-fold more captures than traps baited with the BG-Lure. There was no significant difference, however, between the treatments. Female Ae. aegypti captured in CO2-baited traps were mainly unfed (91%), with fewer gravid mosquitoes (6.4%) compared to traps with test compounds (range; 12.7-21.1%). Male captures were lower in LO and BG-Lure baited traps compared to other treatments. Gravimetric analysis showed LO had a slower release rate compared to other compounds. The findings suggest that host-associated compounds loaded on polymer beads are more effective in trapping Ae. aegypti than commercial BG-Lure and reveal sex-specific differences in mosquito responses. These results have implications for mosquito surveillance and control programs, highlighting the potential for selective trapping strategies.

Structure-Guided Evolution of Cyclohexanone Monooxygenase Toward Bulky Omeprazole Sulfide: Substrate Migration and Stereoselectivity Inversion.

Structure-guided engineering of a CHMO from Amycolatopsis methanolica (AmCHMO) was performed for asymmetric sulfoxidation activity and stereoselectivity toward omeprazole sulfide. Initially, combinatorial active-site saturation test (CASTing) and iteratively saturation mutagenesis (ISM) were performed on 5 residues at the "bottleneck" of substrate tunnel, and MT3 was successfully obtained with a specific activity of 46.19 U/g and R-stereoselectivity of 99 % toward OPS. Then, 4 key mutations affecting the stereoselectivity were identified through multiple rounds of ISM on residues at the substrate binding pocket region, resulting MT8 with an inversed stereoselectivity from 99 % (R) to 97 % (S). MT8 has a greatly compromised specific activity of 0.08 U/g. By introducing additional beneficial mutations, MT11 was constructed with significantly increased specific activity of 2.29 U/g and stereoselectivity of 97 % (S). Enlarged substrate tunnel is critical to the expanded substrate spectrum of AmCHMO, while reshaping of substrate binding pocket is important for stereoselective inversion. Based on MD simulation, pre-reaction states of MT3-OPSproR, MT8-OPSproS, and MT11-OPSproS were calculated to be 45.56 %, 17.94 %, and 28.65 % respectively, which further confirm the experimental data on activity and stereoselectivity. Our results pave the way for engineering distinct activity and stereoselectivity of BVMOs toward bulky prazole thioethers.

A Family of Hexacopper Phenylsilsesquioxane/Acetate Complexes: Synthesis, Solvent-Controlled Cage Structures, and Catalytic Activity.

Convenient self-assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich-like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4-cyclic and Si6-condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6-complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30 %. The compound 4 was also tested as catalyst in the Baeyer-Villiger oxidation of cyclohexanone by m-chloroperoxybenzoic acid: maximum yields of 88 % and 100 % of ϵ-caprolactone were achieved upon conventional heating at 50 °C for 4 h and MW irradiation at 70 or 80 °C during 30 min, respectively. It was also possible to obtain the lactone (up to 16 % yield) directly from the cyclohexane via a tandem oxidation/Baeyer-Villiger oxidation reaction using the same oxidant.

Isomorphic Insertion of Ce(III)/Ce(IV) Centers into Layered Double Hydroxide as a Heterogeneous Multifunctional Catalyst for Efficient Meerwein-Ponndorf-Verley Reduction.

The development of highly active acid-base catalysts for transfer hydrogenations of biomass derived carbonyl compounds is a pressing challenge. Solid frustrated Lewis pairs (FLP) catalysis is possibly a solution, but the development of this concept is still at a very early stage. Herein, stable, phase-pure, crystalline hydrotalcite-like compounds were synthesized by incorporating cerium cations into layered double hydroxide (MgAlCe-LDH). Besides the insertion of well-isolated cerium centers surrounded by hydroxyl groups, the formation of hydroxyl vacancies near the aluminum centers, which were formed by the insertion of cerium centers into the layered double hydroxides (LDH) lattice, was also identified. Depending on the initial cerium concentration, LDHs with different Ce(III)/Ce(IV) ratios were produced, which had Lewis acidic and basic characters, respectively. However, the acid-base character of these LDHs was related to the actual Ce(III)/Ce(IV) molar ratios, resulting in significant differences in their catalytic performance. The as-prepared structures enabled varying degrees of transfer hydrogenation (Meerwein-Ponndorf-Verley MPV reduction) of biomass-derived carbonyl compounds to the corresponding alcohols without the collapse of the original lamellar structure of the LDH. The catalytic markers through the test reactions were changed as a function of the amount of Ce(III) centers, indicating the active role of Ce(III)-OH units. However, the cooperative interplay between the active sites of Ce(III)-containing specimens and the hydroxyl vacancies was necessary to maximize catalytic efficiency, pointing out that Ce-containing LDH is a potentially commercial solid FLP catalysts. Furthermore, the crucial role of the surface hydroxyl groups in the MPV reactions and the negative impact of the interlamellar water molecules on the catalytic activity of MgAlCe-LDH were demonstrated. These solid FLP-like catalysts exhibited excellent catalytic performance (cyclohexanol yield of 45%; furfuryl alcohol yield of 51%), which is competitive to the benchmark Sn- and Zr-containing zeolite catalysts, under mild reaction conditions, especially at low temperature (T = 65 °C).

Using an inexpensive RGB color sensor for field quantitative assessment of soil accessible Cu(â ¡).

Field rapid determination of soil accessible Cu(Ⅱ) was important for environmental safety and human health risk assessment. In this study, an inexpensive red, green, and blue (RGB) color sensor was used for quantitative color difference analysis of the colored solution for soil accessible Cu(Ⅱ) with bis-cyclohexanone oxalydihydrazone as color reagent to develop a new method for analyzing soil accessible under field conditions. First, the calibration curve for RGB color sensor method was established in the standard solutions of Cu(II). Then the "hand shaking + standing" field extraction method for accessible Cu(Ⅱ) was developed. Finally, the method was applied in contaminated soils in the laboratory and in the field, and set the values determined by atomic absorption spectroscopy (AAS) as the standard ones. Results indicated that in the range of 0.1-5 mg L-1 Cu(II), the RGB Euclidean chromogenic difference values were directly linear correlated with the concentration of Cu(II) (R2 > 0.999). The interference of Fe(Ⅲ) and Mn(Ⅱ) could be eliminated by adding citric acid. The "hand shaking + standing" field extraction method could effectively extract the accessible Cu(Ⅱ) from soil with the high extraction rates. The concentrations of accessible Cu(II) in various polluted soils determined by RGB color sensor method were consistent with that determined by AAS, with the relative error within ±5%, the relative standard deviation ≤ 20%. The recovery of Cu(II) in RGB color sensor method was between 97% and 105%, which could meet the requirements of trace analysis of accessible Cu(Ⅱ) in the field. The high accuracy and precision of RGB color sensor method was reconfirmed in the rapid field quantitative assessment of soil accessible Cu(Ⅱ). Due to that the RGB color sensor was low cost, rechargeable, portable, mobile, ambient light resistant, the method would have a great potential for the determination of accessible Cu(Ⅱ) in contaminated soils.

Identification and evaluation of antiviral activity of novel compounds targeting SARS-CoV-2 virus by enzymatic and antiviral assays, and computational analysis.

The viral genome of the SARS-CoV-2 coronavirus, the aetiologic agent of COVID-19, encodes structural, non-structural, and accessory proteins. Most of these components undergo rapid genetic variations, though to a lesser extent the essential viral proteases. Consequently, the protease and/or deubiquitinase activities of the cysteine proteases Mpro and PLpro became attractive targets for the design of antiviral agents. Here, we develop and evaluate new bis(benzylidene)cyclohexanones (BBC) and identify potential antiviral compounds. Three compounds were found to be effective in reducing the SARS-CoV-2 load, with EC50 values in the low micromolar concentration range. However, these compounds also exhibited inhibitory activity IC50 against PLpro at approximately 10-fold higher micromolar concentrations. Although originally developed as PLpro inhibitors, the comparison between IC50 and EC50 of BBC indicates that the mechanism of their in vitro antiviral activity is probably not directly related to inhibition of viral cysteine proteases. In conclusion, our study has identified new potential noncytotoxic antiviral compounds suitable for in vivo testing and further improvement.

Evaluation of fumigant toxicity of cyclohexanone to 5 species of insect pests.

Cyclohexanone is a major precursor for nylon production and is also used as a pesticide solvent. In this study, cyclohexanone was evaluated as a fumigant against rice weevil adults, confused flour beetle adults, western flower thrips larvae and adults, spotted wing drosophila adults, and subterranean termite workers. Cyclohexanone fumigation was effective against all 5 insects, and there were considerable variations in susceptibility to cyclohexanone fumigation among the 5 species. At 20 °C, complete control of spotted wing drosophila adults was achieved in 1-h fumigation with 25 µl/l of cyclohexanone and complete control of eastern subterranean termite workers was achieved in 3-h fumigations with 50 µl/l dose of cyclohexanone. Stored-product insects confused flour beetle, and rice weevil adults were more tolerant to cyclohexanone fumigation. Fumigations of 24 h with 75 µl/l dose of cyclohexanone caused 100% mortality of rice weevil adults and 98% mortality of confused flower beetle adults. Even at a 100 µl/l dose, the 24-h fumigations did not achieve 100% mortality of confused flour beetle adults. At 5 °C, complete control of western flower thrips was achieved in 3- and 6-h fumigations with 100 and 50 µl/l doses of cyclohexanone, respectively. Cyclohexanone vapor concentrations were measured using cyclohexanone detector tubes. Vapor concentrations were far below the expected saturation concentration indicating that most cyclohexanone did not exist as vapor in fumigation chambers. The results of effective control of all 5 insect species suggest that cyclohexanone has the potential to be used as a fumigant for postharvest pest control.

Efficient Eu3+-Integrated UiO-66 Probe for Ratiometric Fluorescence Sensing of Styrene and Cyclohexanone.

The development of probes with sensitive and prompt detection of volatile organic compounds (VOCs) is of great importance for protecting human health and public security. Herein, we successfully prepared a series of bimetallic lanthanide metal-organic framework (Eu/Zr-UiO-66) by incorporating Eu3+ for fluorescence sensing of VOCs (especially styrene and cyclohexanone) using a one-pot method. Based on the multiple fluorescence signal responses of Eu/Zr-UiO-66 toward styrene and cyclohexanone, a ratiometric fluorescence probe using (I617/I320) and (I617/I330) as output signals was developed to recognize styrene and cyclohexanone, respectively. Benefitting from the multiple fluorescence response, the limits of detection (LODs) of Eu/Zr-UiO-66 (1:9) for styrene and cyclohexanone were 1.5 and 2.5 ppm, respectively. These are among the lowest reported levels for MOF-based sensors, and this is the first known material for fluorescence sensing of cyclohexanone. Fluorescence quenching by styrene was mainly owing to the large electronegativity of styrene and fluorescence resonance energy transfer (FRET). However, FRET was accounted for fluorescence quenching by cyclohexanone. Moreover, Eu/Zr-UiO-66 (1:9) exhibited good anti-interference ability and recycling performance for styrene and cyclohexanone. More importantly, the visual recognition of styrene and EB vapor can be directly realized with the naked eyes using Eu/Zr-UiO-66 (1:9) test strips. This strategy provides a sensitive, selective, and reliable method for the visual sensing of styrene and cyclohexanone.

Computational design, molecular properties, ADME, and toxicological analysis of substituted 2,6-diarylidene cyclohexanone analogs as potent pyridoxal kinase inhibitors.

Leishmaniasis is one of the tropical diseases which affects over 12 million people mainly in the tropical regions of the world and is caused by the leishmanial parasites transmitted by the female sand fly. The lack of vaccines to prevent leishmaniasis, as well as limitations of existing therapies necessitated this study which was focused on a combined virtual docking screening and 3-D QSAR modeling approach to design some diarylidene cyclohexanone analogs, while also performing pharmacokinetic analysis and Molecular Dynamic (MD) simulation to ascertain their drug-ability. As a result, the built 3-D QSAR model was found to satisfy the requirement of a good model with R2 = 0.9777, SDEC = 0.0593, F-test = 105.028, and Q2 LOO = 0.6592. The template (compound 9, MolDock score = - 161.064) and all seven newly designed analogs were found to possess higher docking scores than the reference drug (Pentamidine, Moldock score = - 137.827). The results of the pharmacokinetic analysis suggest 9 and the new molecules (9a, b, c, e, and f) as orally bioavailable with good ADME and safe toxicological profiles. These molecules also showed good binding interactions with the receptor (pyridoxal kinase). Additionally, the MD simulation result confirmed the stability of the tested protein-ligand complexes, with an estimated ∆G binding (MM/GBSA) of - 65.2177 kcal/mol and - 58.433 kcal/mol for 9_6K91 and 9a_6K91 respectively. Hence, the new compounds, especially 9a could be considered potential anti-leishmanial inhibitors.

Development of pH-Responsive N-benzyl-N-O-succinyl Chitosan Micelles Loaded with a Curcumin Analog (Cyqualone) for Treatment of Colon Cancer.

This work aimed at preparing nanomicelles from N-benzyl-N,O-succinyl chitosan (NBSCh) loaded with a curcumin analog, 2,6-bis((3-methoxy-4-hydroxyphenyl) methylene) cyclohexanone, a.k.a. cyqualone (CL), for antineoplastic colon cancer chemotherapy. The CL-loaded NBSCh micelles were spherical and less than 100 nm in size. The entrapment efficiency of CL in the micelles ranged from 13 to 39%. Drug release from pristine CL was less than 20% in PBS at pH 7.4, whereas the release from CL-NBSCh micelles was significantly higher. The release study of CL-NBSCh revealed that around 40% of CL content was released in simulated gastric fluid at pH 1.2; 79 and 85% in simulated intestinal fluids at pH 5.5 and 6.8, respectively; and 75% in simulated colonic fluid at pH 7.4. CL-NBSCh showed considerably high selective cytotoxicity towards mucosal epithelial human colon cancer (HT-29) cells and lower levels of toxicity towards mouse connective tissue fibroblasts (L929). CL-NBSCh was also more cytotoxic than the free CL. Furthermore, compared to free CL, CL-NBSCh micelles were found to be more efficient at arresting cell growth at the G2/M phase, and induced apoptosis earlier in HT-29 cells. Collectively, these results indicate the high prospective potential of CL-loaded NBSCh micelles as an oral therapeutic intervention for colon cancer.

Solvatochromism, Acidochromism and Photochromism of the 2,6-Bis(4-hydroxybenzylidene) Cyclohexanone Derivative.

In this paper, we studied the photophysical behavior of 2,6-bis(4-hydroxybenzylidene) cyclohexanone (BZCH) under the influence of various stimuli. The photophysical properties were correlated with different solvent parameters, such as the Kamlet-Abraham-Taft (KAT), Catalán, and Laurence solvent scales, suggesting that the behavior of BZCH is influenced by both nonspecific and specific solvent-solute interactions. The Catalán solvent dipolarity/polarizability parameters were found to have a significant role in the solvatochromic behavior, which is also confirmed by the KAT and Laurence models. The acidochromism and photochromism properties of this sample in dimethylsulfoxide and chloroform solutions were also investigated. The compound showed reversible acidochromism after the addition of dilute NaOH/HCl solutions, accompanied by a change in color and the appearance of a new absorption band (514 nm). The photochemical behavior was also examined by irradiating BZCH solutions with both 254 and 365 nm light.

Crosslinked Aggregates of Fusion Enzymes in Microaqueous Organic Media.

Baeyer-Villiger monooxygenases (BVMOs) are attractive for selectively oxidizing various ketones using oxygen into valuable esters and lactones. However, the application of BVMOs is restrained by cofactor dependency and enzyme instability combined with water-related downsides such as low substrate loading, low oxygen capacity, and water-induced side reactions. Herein, we described a redox-neutral linear cascade with in-situ cofactor regeneration catalyzed by fused alcohol dehydrogenase and cyclohexanone monooxygenase in aqueous and microaqueous organic media. The cascade conditions have been optimized regarding substrate concentrations as well as the amounts of enzymes and cofactors with the Design of Experiments (DoE). The carrier-free immobilization technique, crosslinked enzyme aggregates (CLEAs), was applied to fusion enzymes. The resultant fusion CLEAs were proven to function in microaqueous organic systems, in which the enzyme ratios, water contents (0.5-5 vol. %), and stability have been systematically studied. The fusion CLEAs showed promising operational (up to 5 cycles) and storage stability.

Therapeutic potential of two formulated novel chitosan derivatives with prominent antimicrobial activities against virulent microorganisms and safe profiles toward fibroblast cells.

The development of new antimicrobial agents has been drawing considerable attention due to the extreme escalation of multi-drug resistant microorganisms. We thus sought to ameliorate the antimicrobial activities of the chitosan (Cs) biopolymer by coupling chitosan with cyclohexanone and 2-N-methyl pyrrolidone, synthesizing two novel Schiff bases (CsSB1 and CsSB2), respectively. FT-IR, TGA, DSC, SEM, and potentiometric titration were employed to characterize the formulated chitosan derivatives. The findings exposed that the degrees of deacetylation were 88.12% and 89.98% for CsSB1 and CsSB2, respectively. The antimicrobial capacities of CsSB1 and CsSB2 were substantially enhanced compared with prime chitosan. Furthermore, the CsSB1 and CsSB2 demonstrated minimum inhibitory concentrations (MIC) of 50 µg/ml in relation to all studied microorganisms, whereas chitosan revealed MIC value of 50 µg/ml only for E. coli. Furthermore, CsSB1 with a concentration of 250 µg/ml manifested the highest antibacterial activity against Gram-positive bacteria. Correspondingly, CsSB2 revealed a comparable trend of microbial hindrance with lower activities. Besides, the two derivatives could thwart the growth of Candida albicans (C. albicans). The cytotoxicity assay of the biomaterials accentuated their biocompatibility with fibroblasts. Collectively, the two formulated chitosan derivatives could competently rival the native chitosan, particularly for future applications in wound healing.

Dehydrogenation of Cyclohexanones to Phenols: A Mini Review.

BACKGROUND: Phenol and its derivatives are important intermediates in the chemical industry, especially the pharmaceutical and electronic industries. The synthesis of phenols has attracted the attention of scientists due to their importance. Dehydrogenation of cyclohexanones is one of the promising aromatization strategies for phenols manufacture because the raw materials are low cost and stable. In recent years, some efficient and green methods with the use of H2, O2 and air, alkene, H2 and O2-free are described. OBJECTIVE: This mini-review will summarize some recent developments relating to the dehydrogenation of cyclohexanones to phenols, along with their interesting mechanism aspects. The challenges and future trends of the transformation will be prospected. CONCLUSION: The synthesis of phenols from the dehydrogenation of cyclohexanones has recently attracted much attention. Some synthetic methods have been established, and interesting mechanisms have been proposed in some cases. Lots of catalysts were developed for the transformation to afford the corresponding product. Although the present methods still have drawbacks and limitations, it is supposed that many novel methods would probably be developed in the near future.