Acetic Anhydride Research Articles

Design, Synthesis, Antibacterial, and Antifungal Evaluation of a New Series of Quinazoline - Thiazole and/or Quinazoline - Triazole Hybrids as Bioactive Heterocycles.

Herein, a one-pot reaction between cyclohexanone, thiourea, and 2,5-dimethoxybenzaldehyde allowed to prepare hexahydroquinazoline-2(1H)-thione4 firstly, which followed by reacting with hydrazine hydrate to produce the corresponding 2-hydrazinylhexahydroquinazoline 6. Interesting analogs of thiazolo[3,2-a]quinazoline 713 where obtained when hexahydroquinazoline-2(1H)-thione 4 reacted with 1,2-dibromoethane, chloroacetyl chloride, bromoacetic acid, bromoacetic acid/4-chlorobenzaldehyde, 2-bromopropionic acid, ethyl bromo cyanoacetate, and/or bromomalononitrile; respectively. While triazolo[4,3-a] quinazoline 14-16 were created when 2-hydrazinylhexahydroquinazoline 6 reacted with triethyl orthoformate, acetic anhydride, and carbon disulfide respectively. Numerous spectroscopy tests, including FT-IR, NMR (1H &13 C), and MS spectrum, proved all the newly produced analogs. Additionally, the new analogs were examined for their antibacterial and antifungal properties against Escherichia coli, Staphylococcus aureus, and Candida albicans. It was discovered that triazolo[4,3-a] quinazoline analogs 14-16 have superior bacterial and fungal activity when compared to the corresponding conventional doses of Streptomycin andGriseofulvin. Towards Candida albicans; compounds 14, 15, and 16 increase activity with 1.14 %, 1.15 %, and 1.21 %, respectively more than griseofulvin.While, for Staphylococcus aureus; compounds 14, 15, and 16 increase activity with 1.5 %, 1.5 %, and 1.7 %, respectively more than streptomycin. Morever, for Escherichia coli; compounds 14, 15, and 16 increase activity with 1.19 %, 1.21 %, and 1.22 %, respectively more than streptomycin. Finally, structure activity relationships show that quinazoline derivatives exhibit higher activity when fused to pyrazole ring 14-16 as compared when fused thiophene ring 7-13.

CaFe2O4@SiO2-Cu as a novel and highly efficient nanocatalyst for direct conversion of epoxides to β-acetoxy esters

Direct conversion of structurally various epoxides to the related β-acetoxy esters was investigated using catalytic amounts of CaFe2O4@SiO2-Cu. The reactions were accomplished in the presence of acetic anhydride under solvent-free conditions within 0.5–2 h to give desired products in high yields. Initially, the CaFe2O4 nanoparticles were manufactured through a chemical coprecipitation reaction of calcium nitrate and hydrated iron (III) nitrate in the presence of ammonium hydroxide solution, and then calcined at 800 ºC. Next, to protect the prepared CaFe2O4 from oxidation and aggregation, its surface was covered with a silica layer to give CaFe2O4@SiO2. Eventually, by adding copper chloride solution followed by potassium borohydride solid powder, Cu nanoparticles were successfully immobilized on the silica surface and the new CaFe2O4@SiO2-Cu nanocomposite was obtained. FT-IR, SEM, EDX, VSM, ICP-OES, TGA, TEM and XRD techniques were employed to characterize the newly synthesized nanostructure. In addition, durability of the catalyst was considered for several sequential reaction cycles without the notable loss of catalytic activity. The absence of hazardous organic solvents, high product yields, short reaction times and recoverability of the magnetic catalyst are among the remarkable advantages of the introduced procedure.

Thermophilic and mesophilic anaerobic digestion of soybean molasses: A performance vs. stability trade-off

One of the factors that has a direct impact on anaerobic digestion is the applied organic loading rate (OLRA). Increasing OLRA can boost methane production but can also cause process failure. As a result, establishing the appropriate OLRA for the procedure is critical. This study evaluated the effect of increasing the OLRA using soybean molasses in a thermophilic anaerobic reactor (R-Thermo), as well as the effect of feeding strategy and co-processing with okara. Furthermore, the performance versus stability trade-off between R-Thermo and mesophilic anaerobic digestion (R-Meso) was investigated. The increase of OLRA from 10 to 15 and 20 kg-COD/m³/d led to a decrease in COD removal efficiency (90, 86, and 75%), methane yield (12.0, 11.6, and 9.9 mol-CH4/kg-COD) and an increase in total volatile acids concentration (251, 456, and 1393 mg-HAc/L, respectively). At 15 kg-COD/m³/d, R-Meso performed similarly to R-Thermo, and at 20 kg-COD/m3/d, R-Meso outperformed (81% COD removal efficiency, 9.3 mol-CH4/kg-CODrem and 154.5 mol-CH4/m3/d). Temperature greatly influenced the distribution of metabolic pathways, as shown by thermodynamic and kinetic analyses, thus impacting bacterial diversity. At 55 °C, amongst the bacterial genera, Tepidiphilus stood out (>28.2%), followed by Acetomicrobium, Coprothermobacter and Candidatus_Caldatribacterium. The OLRA clearly impacted the archaeal community; Methanothermobacter (77.4%) was favored over Methanosarcina (14.8%). Under thermophilic temperature, it seems that syntrophic acetate oxidation (SAO) bacteria might have competed for substrate with acetoclastic methanogens, while in R-Meso microorganisms responsible for the initial steps of organic matter breakdown, such as members of the Firmicutes and Proteobacteria phyla (at least 67%), were dominant. In summary, R-Meso, characterized by a more uniform distribution of metabolic pathways, as well as a diverse and well-adapted microbial consortium, have exhibited enhanced stability and outperformed R-Thermo at high-loads.

Isolation of antibodies to hypochlorite-modified low-density lipoproteins from human serum and study of their specificity

BACKGROUND: Modified low-density lipoproteins have immunogenic properties and induce the production of antibodies. In this case, HOCl promotes the formation of subsequent active halogen-containing compounds interacting with proteins and lipid parts of low-density lipoproteins, which leads to their modification and the production of antibodies to them. AIM: The aim of this work is to isolate antibodies to hypochlorite modified low-density lipoproteins from human blood sera and study their specificity. MATERIALS AND METHODS: Malondialdehyde, acetic anhydride and sodium hypochlorite were used to obtain modified low-density lipoproteins. IgG antibodies to hypochlorite modified low-density lipoproteins were isolated by affinity chromatography. The total IgG fraction antibodies was previously isolated from human blood serum using MabSelect Xtra. The specific antibodies to hypochlorite modified low-density lipoproteins were isolated from this IgG pool by affinity chromatography. CNBr-Sepharose 4B conjugated with human serum albumin modified with NaOCl was used as a sorbent. The specificity of antibodies against hypochlorite modified low-density lipoproteins was tested using a competitive enzyme-linked immunosorbent assay. The competitors were hypochlorite modified low-density lipoproteins, acetic anhydride modified low-density lipoproteins and malondialdehyde modified low-density lipoproteins in concentrations (1–250 μg/ml). RESULTS: IgG antibodies against hypochlorite-modified proteins that interact with hypochlorite modified low-density lipoproteins were detected in human blood. According to ELISA date the binding of the isolated antibodies to hypochlorite modified low-density lipoproteins was almost completely inhibited only by appropriately modified low-density lipoproteins, that is, hypochlorite modified low-density lipoproteins, but not native low-density lipoproteins or acetic anhydride modified low-density lipoproteins. Malondialdehyde modified low-density lipoproteins also showed some competitive activity, but much weaker than hypochlorite modified low-density lipoproteins. Hypochlorite modified low-density lipoproteins itself and, to a lesser extent, malondialdehyde modified low-density lipoproteins competed for binding with antibodies of human serum to hypochlorite modified low-density lipoproteins. Acetic anhydride modified low-density lipoproteins and native low-density lipoproteins did not reduce the efficiency of antibody binding to their antigen. CONCLUSIONS: Hypochlorite modified low-density lipoproteins forms epitopes independent of other low-density lipoproteins modifications studied. These epitopes are responsible for the formation of specific antibodies.

Preparation of Novel Hierarchical Catalysts by Simultaneous Generation of β-Zeolite and Mesoporous Silica for Catalytic Cracking.

The gel skeletal reinforcement (GSR) method was applied at the preparation stage of β-zeolite to prepare a novel hierarchical catalyst. A solution of hexamethyldisiloxane (HMDS) and acetic anhydride, a GSR reagent, was added to the mixture of colloidal silica, sodium aluminate, tetraethylammonium hydroxide, sodium hydroxide and water, and successive aging and hydrothermal treatment gave microporous β-zeolite surrounded by mesoporous silica like core-shell structure. Its properties were characterized by XRD, nitrogen adsorption and desorption, NH3-TPD, TEM, and TG-DTA measurements, and further characteristics of the catalysts produced were clarified by the catalytic cracking of n-dodecane. The hierarchical structure of microporous zeolite and mesoporous silica was shown from GSR-2.9HS-H-Beta to GSR-3.2HS-H-Beta, where the molar ratio of HMDS and silica source of β-zeolite was 2.9~3.2 : 100. It was found that in the catalytic cracking of n-dodecane, the relative activity (the conversion per the amount of zeolite crystals) increased with the increase in mesopore volume and surface area. The result indicated that the introduction of mesopores was effective even in catalytic cracking of small molecule of n-dodecane.

Study on the Thermal Safety of 3,7‐Dinitro‐1,3,5,7‐Tetraazabicyclo[3.3.1]nonane Synthesized by Nitrolysis of Hexamine

AbstractThe thermal flow curves of the nitrolysis for the synthesis of 3,7‐dinitro‐1,3,5,7‐tetraazabicyclo[3.3.1]nonane (DPT) from hexamine in the presence of different amounts of acetic anhydride were obtained using reaction calorimetry. The maximum heat release rates during the feeding process, the corresponding maximum adiabatic temperature rises, and the Maximum Temperature of the Synthesis Reaction (MTSR) were determined, respectively. The thermal stability of the reaction product DPT and the reaction mixture was analyzed, and data on their thermal decomposition characteristics were obtained. The thermal decomposition kinetic model was utilized to simulate the stability under adiabatic conditions. TD24 (The temperature corresponding to the time required to reach the maximum reaction rate under adiabatic conditions for 24 hours) of the reaction mixture was calculated as 69.65°C. According to the thermal hazard parameters of the reaction, the process's hazard level under various acetic anhydride addition conditions was determined to be level 5 using the cooling failure scenario method.

Optimizing Lemon Balm (Melissa Officinalis L.) Cultivation: Effects of Different Manures on Plant Growth and Essential Oil Production During Consecutive Harvests

This study examined the impact of organic manures from different sources (poultry, sheep, and cattle) on lemon balm (Melissa officinalis L., Lamiaceae) during different harvests. Manure application increased the photosynthetic pigments levels (chlorophyll-a, 9–41%; chlorophyll-b, 24–60%), biomass (41–60%), and essential oil yield (60–71%). Sheep manure treatment exhibited the highest antioxidant capacity among all the manures tested. Through GC-MS and GC-FID analysis, 10 chemical constituents were identified in the essential oil, accounting together for 91–95% of the total composition. The primary chemical component was geranial (39–46%), followed by neral (28–35%), (E)-caryophyllene (4.7–11%), geranyl acetate (2.7–5.9%), and caryophyllene oxide (1.7–4.8%). The utilization of livestock manures significantly improved the quality of the essential oil in terms of neral and geranial percentages compared to the control. Notably, during mid-August and early October, there was a substantial rise in these valuable compounds. However, a decrease in geranyl acetate and oxygenated monoterpenes resulted in a decline of the antioxidant capacity to 3%. Consequently, it is recommended to utilize essential oils from the second and third harvests for industrial purposes. Overall, the use of livestock manures, especially sheep manure, as a nutrient source for lemon balm cultivation, proves to be a viable approach for producing high-quality essential oils.

Regarding Bioanalysis Lasting a Few Minutes: Automated Cooling-SPME and Fast-GC for Urinary 2-Phenyl-2-Propanol Monitoring.

An innovative SPME head space GC-MS method, in cooling mode, using a fully automated routine, was developed to detect 2-phenyl-2-propanol, a representative urinary metabolite of cumene. Following an acid hydrolysis and derivatization step with lowered quantities of reagents, acetic anhydride and pyridine, a 30 μm polydimethylsiloxane SPME fiber was used to sample derivatized 2-phenyl-2-propanol, such as benzenemethanol,α,α-dimethyl-acetate, from the headspace. Performances of the method, optimized through experimental design, provide an LOD of 0.034 mg/L and an LOQ 0.10 mg/L, with a short sampling time necessary per sample. The method, developed on standard solutions, will be applied to both occupationally exposed and non-exposed populations.

Thermodynamics-driven metabolic and microbial preference for lactate methanization at different operational temperatures

Lactate-dominant organic acids released from acidified feedstocks inhibit anaerobic digestion processes, which can result in decreased biomethane (CH4) yield or even complete process failure. Herein, this study focus on exploring the effects of temperature (35 °C, 38 °C, 41 °C, 44 °C, 47 °C, 50 °C, and 55 °C) on the thermodynamics of microbial communities to assess the thermodynamics or microbial flora in driving the concurrent bioreactions involved in organic acid degradation. The findings revealed a prevalence of species such as Syntrophaceticus schinkii, DTU014, and Methanosarcina at 38 °C-44 °C. These species are known for their abilities in propionate and butyrate degradations, acetate oxidation, and methanation, respectively. Conversely, at thermophilic temperatures (47 °C, 50 °C, and 55 °C), this study observed higher abundance of thermophilic microorganisms like Defluviitoga and Methanoculleus, although these organisms are adapted to higher temperatures, their lactate utilization and methane production were less efficient than mesophilic species. Despite higher ΔG values for lactate, propionate, and butyrate degradation at 38 °C–44 °C compared with thermophilic temperatures, the relative abundance of functional enzymes (specifically, propionate and butyrate degrading enzymes) was found to be marginally higher than 47 °C–55 °C. As a result, 41 °C–44 °C induced remarkable thermodynamic effects that not only facilitated organic acid degradation but also promoted subsequent methanation, indicating the suitability of these temperatures for the methanation of biowaste acidified by lactate. Overall, this study provides insight into the temperature-dependent response of organic acid degradation, specifically focusing on the mechanisms involved in overcoming energy barriers, shaping the microbial flora, and ultimately improving the efficiency and stability of anaerobic digestion, especially for lactate-acidified feedstock.

Coupling Fe3O4 and micro-hydrogen for enhancing the anaerobic bio-conversion of phenol: Methanogenesis pathway and interspecies electron transfer

Low anaerobic biological conversion rate is a challenge in the anaerobic biological treatment of phenol wastewater. The dominant syntrophic acetate oxidation and hydrogenotrophic methanogenesis (SAO-HM) pathway is expected to solve the problem. However, there are raw studies on artificially simulating a dominant SAO-HM pathway for enhancing the anaerobic bio-conversion of phenol. In this study, Fe3O4 and micro-hydrogen (Fe3O4/H2) was used to strengthen the anaerobic bio-conversion of phenol by simulating the dominant SAO-HM pathway. The results suggested Fe3O4 and H2 had a coupling promotion on the anaerobic bio-conversion of phenol and Fe3O4/H2 increased the relative abundance of Syntrophus (29.35%), Syntrophorhabdu (3.27%), Clostridium (3.01%) and Methanobacterium (65.74%), indicating Fe3O4/H2 formed a dominant SAO-HM pathway. However, Fe3O4/H2 obviously reduced the conductivity of sludge, the extracellular protein and the functional gens pilA, pilB and OmcS, implying direct interspecies electron transfer (DIET) generated by Fe3O4 was interfered by micro hydrogen in extracellular electron transport process which reduced the efficiency of extracellular electron transport. This study remind that extracellular electron transport cannot be ignored in the dominate SAO-HM pathway for the anaerobic bio-conversion of phenol.

Reduction and structural modification of MoOx/γ-Al2O3 catalysts through acetic acid treatment for green diesel production from corn distiller’s oil

Enabling new environmentally-friendly resources for fuels and platform chemicals is crucial to fulfill our future energy demands while enhancing circularity. Corn distiller’s Oil (CDO) − as a coproduct of the ethanol industry, serves as a sustainable supply of carbon that may be converted into energy, fuels and specialty chemicals. A current challenge in using renewable oxygenated feedstocks is the high amount of coking and catalyst fouling that occurs. This study examined the hydrothermal deoxygenation of CDO into green diesel using molybdenum oxide (MoOx) catalysts in a continuous process without using any external hydrogen. The possibility of reduction and developing oxygen-deficient surfaces on molybdenum oxide (MoOx) catalysts through acetic acid treatment or adding ceria (CeO2) was investigated in order to enhance the acidity of catalysts as well as catalytic activity and stability required for the production of green diesel from CDO. Results showed that the acidity of these catalysts as measured by NH3 temperature programmed desorption (NH3-TPD) had a strong correlation between the degree of deoxygenation and catalyst stability. Acetic acid treatment of the 7.5 wt% MoO3/γ-Al2O3 catalyst reduced MoO3 to MoO3-x, increased the Mo5+ species from 8.7 % to 22 %, created Mo4+ species and increased the catalyst surface acidity in the range of low to moderate strength by approximately 17 %. The use of acetic acid-treated molybdenum oxide (Hac-7.5 wt% MoO3/γ-Al2O3) catalyst enabled nearly complete (99.9 %) deoxygenation of CDO and heavy hydrocarbons cracking to produce diesel-like fuels. A moderate increase in catalyst surface acidity by acetic acid treatment also increased the selectivity of diesel-like fuel through hydrocracking of long-chain hydrocarbons. This low-cost modification step of catalyst improvement is promising for industrial application. However, cracking of hydrocarbons generated amorphous coke (no graphitic coke was observed) on the catalyst surface, which required periodic removal by controlled calcination of the catalyst in presence of air for further use.

C–H Activation: A Versatile Tool for the Synthesis of Niclosamide and Its Derivatives

AbstractA novel strategy has been developed for the direct and regioselective ortho-acetoxylation of N-(2-benzoylphenyl)benzamides through C–H activation using a catalytic amount of Pd(OAc)2 (5 mol%) and a stoichiometric amount of PhI(OAc)2 in a mixture of acetic anhydride and acetic acid. By using this protocol, a new series of niclosamide derivatives was produced in good yields. This is the first report on the synthesis of niclosamide and its derivatives by means of C–H functionalization. This newly developed method offers several advantages such as high regioselectivity, operational simplicity, and good to excellent yields. It provides a short three-step process for the synthesis of niclosamide involving acid–amine coupling, ortho-acetoxylation through C–H activation, and deacylation.

Implementation of gas chromatography tandem mass spectrometry for the analysis of six high boiling point polyhydric alcohols in cosmetics and toothpaste based on precolumn derivatization

Based on precolumn derivatization, an analytical method has been developed for the determination of six high boiling point polyhydric alcohols (HBPAs, b.p. > 300 ℃) in cosmetics and toothpaste, including erythritol, xylitol, Pro-Xylane-S, inositol, mannitol, and sorbitol. The water dispersion and oil in water samples were extracted by distilled water. The water in oil sample was firstly pre-dispersed with acetone, and then extracted by distilled water. The extract was concentrated to dry under nitrogen, and derivatized with acetic anhydride under the dispersion and catalysis of anhydrous pyridine. The derivatives were detected by gas chromatography-tandem mass spectrometry in the selected reaction monitoring mode, and quantified using arabinitol as internal standard. The experimental conditions such as the selection of columns, extraction procedures, and derivative conditions were optimized. This method was properly validated under the optimized conditions, and obtained excellent analytical features. Specifically, the correlation coefficients in the range of 0.02 ∼ 0.5 mg/L all exceed 0.992. The method limits of detection and quantification were 0.25 and 0.8 mg/kg, respectively. The average recoveries in toothpaste, cosmetics with oil in water and water in oil were 81.8 ∼ 107.1 %, with the relative standard deviation were 3.1 ∼ 7.2 %. The established method was successfully applied to commercial samples of different matrices, showing the advantages of simplicity, sensitivity, and good reproducibility, and can be used for the determination of HBPAs in cosmetics and toothpaste. The proposed methodology solves the problem that there is no detection method for HBPAs in cosmetics.

Anti-Cancer Activity, DFT and molecular docking study of new BisThiazolidine amide

In this study, a series of bis amide thiazolidine derivatives (Q1-Q6) were synthesized and their anticancer activity was evaluated against prostate (PC3) and breast (MCF7) cancer cells and normal cells line activity was evaluated against breast (MCF10), prostate (PNT1A) and living human cells (HUVEC) cancer cells. The thiazolidine rings were built from penicillamine and aromatic aldehydes (A1-A6), then converted to acetyl thiazolidines (B1-B6) using acetic anhydride, and finally linked with phenylene diamine to form the final compounds (Q1-Q6). Notably, compounds Q1 and Q3 displayed the highest activity against PC3, with IC50 values of 81 and 89 µg/ml, respectively. Docking simulations were performed for Q1, Q4, and Q5 against protein structures related to cancer (2FVD and 1SJ0). Additionally, DFT calculations were used to determine various molecular properties like HOMO/LUMO energies, band gap, and other descriptors, providing insights into the compounds’ stability and reactivity.

SYNTHESIS OF NEW FRAMEWORK PHOSPHONATES BY THE INTERACTION OF 2-ETHOXYVINYL DICHLOROPHOSPHONATE WITH 4-ETHYLRESORCINOL

A simple, new and promising approach to obtaining previously unknown phosphorus-containing framework compounds by the developed original synthesis method is proposed. The proposed method is based on the condensation reaction of 2-ethoxyvinylphosphonic acid dichloride with resorcinol and its derivatives in toluene in the presence of trifluoroacetic acid. The article presents the results of a study of the reaction of 2-ethoxyvinyl dichlorophosphonate with 4-ethylresorcinol. It was found that this reaction results in the formation of a mixture of two regioisomers. The structure and construction of the obtained regioisomeric framework phosphonates were studied using 31P and 1H NMR. The regioisomeric framework phosphonates obtained as a result of the reaction of vinylphosphonate with 4-ethylresorcinol were separated by acylation of the mixture with acetic anhydride, using as a medium and a reagent. One functionalized regioisomer was isolated as an individual product, which was white crystals with good solubility in acetone-water and DMSO mixtures. The structure and composition of the obtained regioisomer were confirmed by 1H, 31P, 13C NMR, IR spectroscopy, mass spectrometry (MALDI) and elemental analysis. It was found that the reaction of 2-ethoxyvinyl dichlorophosphonate with 4-ethylresorcinol in the presence of an equimolar amount of trifluoroacetic acid in toluene resulted in the formation of a regioisomeric mixture of framework phosphonates in a 4:1 ratio. It was shown that acylation of this regioisomeric mixture with acetic anhydride allowed one of the regioisomers to be isolated individually.

An Efficient Multi‐Component Double Friedel‐Crafts Alkylation of Isatin: Access to Unsymmetrical and Symmetrical 3, 3‐Diaryl oxindoles

AbstractAcetic acid‐mediated three‐component double Friedel–Crafts alkylation reaction for the synthesis of α, α‐diaryl oxindole derivatives is demonstrated. The reaction is successful with various isatin, indole, and N, N‐disubstituted aniline derivatives. The efficiency of the reaction is further enhanced by a four‐component reaction of isatin, electrophiles and acetic anhydride for the synthesis of N‐acylated 3,3‐diaryl oxindole derivatives facilitated by dual activation of C3 and N1 acetylation in a single‐step. Various unsymmetrical and symmetrical 3,3‐diaryl oxindoles were prepared in single‐step MCR reaction under easy to operate reaction conditions.

Examination of Phytochemical Composition using GC-MS and Assessment of Antibacterial Efficacy of Indian Geranium Oil against Aeromonas Caviae

Geranium oil, extracted from the leaves and flowers of the geranium plant, holds a significant position for its potential health benefits. This essential oil has found utility in both traditional and alternative medicinal practices, showcasing its versatility across diverse healthcare methodologies. This study systematically analyzed the chemical composition of geranium oil, identifying a diverse array of compounds. Notably, Aminoacetonitrile, 3-Nitro-2-methyl propene, and 2,6-Octadiene (E,E) emerged as predominant components in the analysis. These compounds, including acetic anhydride, serve as vital precursors in pharmaceutical drug synthesis and other organic compound formations. The antibacterial efficacy of geranium oil against Aeromonas caviae was evaluated, revealing notable inhibitory effects of 17 mm at an elevated concentration of 30 µg/µl. The mechanisms underlying this antibacterial activity may be attributed to bioactive compounds present in geranium oil, such as citronellol, geraniol, and linalool, each known for their antimicrobial properties. Further research is essential to precisely elucidate these mechanisms and comprehensively evaluate the safety and efficacy of geranium oil for potential therapeutic applications.

The GaCl3-Catalyzed Knoevenagel Condensation To Achieve Acceptor-Donor-Acceptor Small-Molecule Acceptors: A DFT Mechanistic Study.

Herein, the reaction mechanism for the GaCl3-catalyzed Knoevenagel condensation of 2-formylindacenodithieno[3,2-b]thiophene (ITIC-CHO) and active methylene compound 1,1-dicyanomethylene-3-indanone (IC) to synthesize ITIC in the presence of acetic anhydride was investigated using the density functional theory (DFT) method. The calculated results indicate that this reaction follows a bimolecular GaCl3 catalytic mechanism. The free energy span for the monomolecular GaCl3 catalytic mechanism is the highest (31.8 kcal/mol), followed by the trimolecular GaCl3 catalytic mechanism (26.4 kcal/mol) and the bimolecular GaCl3 catalytic mechanism (26.3 kcal/mol). The trimolecular GaCl3 path and bimolecular GaCl3 path are competitive, but the former path is limited by the concentration of GaCl3. The inclusion of GaCl3 could stabilize the transition states of C-H activation. Compared to the GaCl3-catalyzed Knoevenagel condensation, that catalyzed by pyridine is not advantageous, owning a high energy span of 31.7 kcal/mol. These agree well with experimental results. This work could provide a novel theoretical understanding of the Knoevenagel condensation, which could inspire the development of a synthesis strategy for electron acceptor materials.

Ultrasound-assisted Synthesis of Novel 4-[3-acetyl-2-(N-alkyl(aryl)acetamido)-1,3, 4-thiadiazol-5-yl]-3-(2-oxo-2H-chromen-3-yl)-1-(4-phenylthiazol-2-yl)-1H-pyrazoles: Anticancer Activities, Apoptotic, Cell Cycle, Molecular Docking, and ADMET Studies

Abstract: A novel series of 4-[3-acetyl-2-(N-alkyl(aryl)acetamido)-1,3,4-thiadiazol-5-yl]-3-(2-oxo-2Hchromen- 3-yl)-1-(4-phenylthiazol-2-yl)-1H-pyrazoles (2a-i) and 3 was synthesized in good yields. The methodology was depended on a one-pot four-components reaction of hydrazine hydrate, alkyl(aryl) isothiocyanate, 3-(2-oxo-2H-chromen-3-yl)-1-(4-phenylthiazol-2-yl)-1H-pyrazole-4-carboxaldehyde (1), and acetic anhydride in acetic acid under ultrasound irradiation. The spectral tools confirmed the structures of all synthesized compounds. Using the standard SRB method, the designed compounds were screened for their in vitro cytotoxicity properties against PC3, HepG2, and HCT116 human cancer cell lines. Products 2a and 2c worked best against all cancer cells tested, as well as doxorubicin. Apoptosis and cell cycle analyses were performed for the bioactive products 2a and 2c. Both products strongly impacted all tumor cells in the late apoptotic pathway and significantly inhibited all cancer cell types under investigation in both the S and G2 phases. After that, a molecular docking study was carried out on products 2a and 2c to investigate how they interact with the CDK-8 receptor. The ADMET prediction suggested that these bioactive products may be effective anticancer treatments.

Novel Methods for the Formation of Free Carbyne Radicals in Solution.

Carbyne free radicals RC⋮ (RC) are usually associated with high-energy processes, thus research on their preparation, chemical reactivity, and prevalence under mild conditions is scarce. Recently, it was reported that metallo-complexes containing CR ligands may undergo spontaneous degradation in aqueous solutions to produce free RC radicals. These highly reactive species may react with each other to form the corresponding alkyne and other products. The reaction of 1,1,1 halo-carbo-hydrates with Cr(II) ions also forms RC radicals under mild conditions. Herein, we report two additional synthetic routes that produce free RC radicals under mild conditions. First, the reaction between metallic zinc and acetic anhydride produces 2-butyne and several other C2, C3, and C4 compounds. Isotopic-labeling experiments indicate that the formation of 2-butyne results from an inter-molecular reaction in which two RC moieties from two acetic anhydride molecules combine in solution. In addition, the degradation of the tri-molybdenum complex [Mo3(H3CC≡CCH3)(OAc)(H2O)2Br7], in which a 2-butyne ligand is coordinated to the Mo3 framework in a μ3-η2 (⊥) binding mode in aqueous solution produces several C2, C3, C4 and C5 molecules. This indicates the formation of free CH3C radicals by a homolytic cleavage of the carbon-carbon triple bond.