Synthesis Of Acrylamide Research Articles

Synthesis and biological evaluation of some new heterocyclic compounds incorporating sulfapyridine as potential antimicrobial agents

This study investigated the cyanoacylation of the sulfapyridine moiety using cyanoacetyl pyrazole as a key synthetic intermediate for the construction of diverse bioactive scaffolds. The intermediate, 2-cyano-N-(4-(N-pyridin-2-yl) sulfamoyl) phenylacetamide, served as a valuable precursor for the synthesis of acrylamide, thiophene, thiazole, chromene, pyridone, 1,2,4-triazine, and hydrazone derivatives all incorporating the sulfapyridine core. The structural elucidation of the synthesized compounds was achieved using infrared (IR), nuclear magnetic resonance (1H and 13C), and mass spectrometry techniques. The biological activity of the newly synthesized compounds was evaluated against a panel of microorganisms, including Gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis), Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa), and the fungus Candida albicans. Notably, the thiol derivative (compound 12), the pyrazole derivative (compound 15), and the 1,2,4-triazine derivatives (compound 21) exhibited significant to good antibacterial and antifungal activity. Interestingly, compounds 12 and 15 displayed a broader spectrum of activity, demonstrating efficacy against all tested microbial strains.

Modular and Diverse Synthesis of Acrylamides by Palladium‐Catalyzed Hydroaminocarbonylation of Acetylene

AbstractThe development of all kinds of covalent drugs had a major impact on the improvement of the human health system. Covalent binding to target proteins is achieved by so‐called electrophilic warheads, which are incorporated in the respective drug molecule. In the last decade, specifically acrylamides emerged as attractive warheads in covalent drug design. Herein, a straightforward palladium‐catalyzed hydroaminocarbonylation of acetylene has been developed, allowing a modular and diverse synthesis of bio‐active acrylamides. This general protocol features high atom efficiency, wide functional group compatibility, high chemoselectivity and proceeds additive free under mild reaction conditions. The synthetic utility of this protocol is showcased in the synthesis of ibrutinib, osimertinib, and other bio‐active compound derivatives.

Modular and Diverse Synthesis of Acrylamides by Palladium-Catalyzed Hydroaminocarbonylation of Acetylene.

The development of all kinds of covalent drugs had a major impact on the improvement of the human health system. Covalent binding to target proteins is achieved by so-called electrophilic warheads, which are incorporated in the respective drug molecule. In the last decade, specifically acrylamides emerged as attractive warheads in covalent drug design. Herein, a straightforward palladium-catalyzed hydroaminocarbonylation of acetylene has been developed, allowing a modular and diverse synthesis of bio-active acrylamides. This general protocol features high atom efficiency, wide functional group compatibility, high chemoselectivity and proceeds additive free under mild reaction conditions. The synthetic utility of this protocol is showcased in the synthesis of ibrutinib, osimertinib, and other bio-active compound derivatives.

Acrylamides from 1,2-dichloroethane via palladium-catalyzed carbonylation

An efficient strategy for the synthesis of acrylamides via palladium-catalyzed carbonylation, using 1,2-dichloroethane and amines as starting materials has been developed.

Acrylamide–Fat Correlation in Californian-Style Black Olives Using Near-Infrared Spectroscopy

Californian-style is one of the most important black table olive elaborations. During its processing, table olives produce acrylamide, a potential carcinogen compound generated during sterilization. In the present study, total fat and acrylamide content in Californian-style table olives were determined and a regression between them was performed (acrylamide concentration range: below limit of detection—2500 ng g−1 and 8–22% for total fat). Nowadays, there are fast and efficient new techniques, such as Near-Infrared Spectroscopy (NIRS) to measure fat content parameters. In that sense, NIRS was used to perform a fat content quantification model in olives in order to indirectly determine acrylamide content. Calibration models for fat quantification were obtained in defatted olive pastes from a unique variety and for olive pastes from different varieties. In the first case, best results were obtained since only one variety was used (R2 = 0.9694; RMSECV = 1.31%; and REP = 8.4%). However, in the second case, results were still acceptable R2 = 0.678, RMSECV = 2.3%, REP = 17.7% and RMSEV = 2.17%. Regression coefficients showed the most influence variables corresponded with fat. The determination coefficient for the fat and acrylamide correlation was high (r = 0.877), being an efficient approach to find out the contribution of fat degradation to acrylamide synthesis in table olives.

Biocatalysts and Processes of Enzymatic Conversion of Substrates Into Valuable Products of Chemical Organic Synthesis (Review of Domestic Developments)

Biocatalysis, both in homogeneous and heterogeneous modes, is an independent interdisciplinary direction of scientific and practical research of predominantly one-stage processes of conversion of initial reagents (substrates) into valuable products that are in demand on the market, with the participation, as a rule, of one enzyme as a catalyst. Biocatalytic single-enzyme processes, which have all the specific features of enzymatic catalysis, are alternative and quite competitive compared to traditional chemical production. This review provides information on the investigations and success of Russian research groups/laboratories that have been actively and productively working in the field of the biocatalysis over the past decades and have practical developments protected by Russian patents, which, under favorable circumstances, can be offered to commercial enterprises/companies for testing and use on a laboratory and/or semi-industrial scale with the prospect of industrial scale-up. In the review, special attention is paid to targeted systematic studies of lipolytic enzymes (lipases), which have a unique ability to catalyze reactions in organic solvents, including esterification and transesterification, which result in the production of valuable products of organic synthesis such as various esters. Lipases are active components of heterogeneous biocatalysts (BCs) prepared by attachment (immobilization) of these enzymes on the surface of solid supports and adsorbents. The review briefly describes the results of study by domestic research teams, provides a complete bibliography of their works, which contains information about the methods for preparing BCs, their catalytic properties (enzymatic activity, substrate specificity, operational stability), as well as the conditions for carrying out biocatalytic processes involving developed BCs such as the synthesis of acrylamide and various esters. Taking into account the average activity (A), close to the activity measured at the half-inactivation time (t1/2), and operational stability, characterized by the value t1/2, a rather rough assessment of the productivity of the BCs was carried out based on the amount of produced valuable product (in tons) per 1 kg of developed biocatalyst.

Microwave-assisted Synthesis of Acrylamide Grafted Polymeric Blend of Fenugreek Gum and its Characterization

Objective: In this study, fenugreek gum (isolated from fenugreek seed) was modified into a grafted form using a microwave-assisted method. Acrylamide was used as a monomer, and ceric ammonium nitrate (CAN), potassium persulfate (KPS), and ammonium persulfate (APS) were used as redox initiators. Methods: The experimental design (Taguchi OA) was used to optimize the synthesis of the grafted copolymer of fenugreek gum. In this model, seven independent variables were selected on the basis of their preliminary study. These were monomer concentration (X1), gum concentration (X2), initiator concentration (X3), irradiation power (X4), speed (X5), time (X6), temperature (X7), and three response variables as % yield (Y1), % grafting (Y2), and % grafting efficiency (Y3) were identified. The optimized copolymers of grafted gum were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), NMR studies, surface morphology and swelling index. Results: The yield of fenugreek gum after extraction was found to be 55.99±0.015% w/w. The percentage grafting of 50.20±4.0, along with grafting efficiency of 83.7±0.1, was obtained with the selected concentration of acrylamide as 15 mg, grafted gum as 0.25 mg, and ammonium persulfate as 0.2 mg after 60 sec. of irradiation time. Conclusion: In the present study, the graft copolymers of fenugreek gum were synthesized. After optimization of the grafting batch, the design (Taguchi OA) was combined with a desirability function. The results underline the importance of graft polymerization techniques for modifying the properties of a polymer.

Characterization of Polyphenol and Volatile Fractions of Californian-Style Black Olives and Innovative Application of E-nose for Acrylamide Determination.

Californian-style black olives require a sterilization treatment that produces a carcinogenic contaminant, acrylamide. Thus, this compound was evaluated in two different olive cultivars using an electronic nose (E-nose). The sterilization intensity had a significant influence on the final phenol concentrations, acrylamide content, and volatile compounds. Increasing the sterilization intensity from 10 to 26 min (F0) reduced the phenol content, but it promoted acrylamide synthesis, leading to a wide range of this toxic substance. The Ester and phenol groups of volatile compounds decreased their content when the sterilization treatment increased; however, aldehyde and other volatile compound groups significantly increased their contents according to the thermal treatments. The compounds 4-ethenyl-pyridine, benzaldehyde, and 2,4-dimethyl-hexane are volatile compounds with unpleasant odours and demonstrated a high amount of influence on the differences found after the application of the thermal treatments. The “Manzanilla Cacereña” variety presented the highest amount of phenolic compounds and the lowest acrylamide content. Finally, it was found that acrylamide content is correlated with volatile compounds, which was determined using multiple linear regression analysis (R2 = 0.9994). Furthermore, the aroma of table olives was analysed using an E-nose, and these results combined with Partial Least Square (PLS) were shown to be an accurate method (range to error ratio (RER) >10 and ratio of performance to deviation (RPD) >2.5) for the indirect quantification of this toxic substance.

Crystal violet dye sorption over acrylamide/graphene oxide bonded sodium alginate nanocomposite hydrogel

The synthesis of acrylamide bonded sodium alginate (AM-SA) hydrogel and acrylamide/graphene oxide bonded sodium alginate (AM-GO-SA) nanocomposite hydrogel was successfully performed using the free radical method. The AM-SA and AM-GO-SA hydrogels were applied as composited adsorbents in crystal violet (CV) dye removal. The adsorption process experiments were performed discontinuously and the acquired data showed that the efficiency is more dependent on pH than other factors. The C–O, CO, and CC groups were detected in the produced hydrogels. The amount of surface area was computed to be 44.689 m2/g, 0.0392 m2/g, and 6.983 m2/g for GO, AM-SA, and AM-GO-SA nanocomposite hydrogel, respectively. The results showed that the experimental data follow the Redlich-Peterson isotherm model. Also, the maximum adsorption capacity of monolayer for CV dye adsorption was determined using AM-SA hydrogel and AM-GO-SA nanocomposite hydrogel 62.07 mg/g and 100.30 mg/g, respectively. In addition, the parameters RL, n, and E showed that the processes of adsorption of CV dye using both types of adsorbents are physical and desirable. Thermodynamically, the CV elimination was exothermic and spontaneous. Besides, thermodynamic results showed that the adsorption process is better proceeding at low temperatures. The experimental data followed a pseudo- second- order (PSO) kinetic model. Also, the Elovich model showed that AM-GO-SA nanocomposite hydrogel has more ability to absorb CV dye. Therefore, according to the obtained results, it can be stated that the produced hydrogels are efficient and viable composited adsorbent in removing CV dye from aqueous solution.

Nitrile hydratase‐mediated conversion of acrylonitrile by Rhodococcus rhodochrous (RS‐6)

AbstractBACKGROUNDAcrylamide is an important monomer for the synthesis of polyacrylamide, which has wide applications in industries. This molecule can be produced by the hydration of acrylonitrile, catalyzed by the enzyme nitrile hydratase (NHase) secreted by microorganisms. Herein, synthesis of acrylamide was carried out by soil isolate Rhodococcus rhodochrous (RS‐6) contains NHase. The critical parameters affecting the bioconversion process such as pH, temperature, substrate concentration, resting cell concentration and acrylamide concentration were optimized by changing one parameter at a time.RESULTSThe optimum conditions for acrylonitrile conversion to acrylamide were observed at pH 7.0, temperature 15 °C, substrate concentration 1250 mmol L–1 and 1.4 mg dcw mL–1 concentration of resting cells. Under these improved conditions the entire bioconversion of acrylonitrile to acrylamide was observed within 75 min of incubation. The NHase of resting cells of R. rhodochrous (RS‐6) showed tolerance to acrylonitrile (7% w/v) and acrylamide up to 30%. Laboratory‐scale production by fed‐batch method resulted in an accumulation of 574 g L−1 acrylamide in 9 h.CONCLUSIONThe NHase‐containing resting cells of R. rhodochrous (RS‐6) catalyzed the maximum conversion of acrylonitrile to acrylamide under optimized conditions. © 2020 Society of Chemical Industry

Synthesis and characterization of a novel cationic polyacrylamide-based flocculants to remove Congo red efficiently in acid aqueous environment

Dye treatments in industrial wastewaters causes numerous obstacles while stains exist normally constant to radiance as well as corrosion and thus, aerobic digestion. The removal of Congo red dye in low concentration from acidic aqueous solution is the main objective of present work. Synthesis of Acrylamide (AM), Diallyl Dimethyl Ammonium Chloride Propylene (DADMAC) and Acryloyloxyethyltrimethyl ammonium chloride (DAC) (PADD) were carried by UV-initiated polymerization, and polyacrylamide (PAM) as contrast sample. Several analytical techniques existed employed to characterization and demonstrate the productive synthesize of PADD, characteristics and composition of the flocculants was studied through FTIR, 1HNMR while thermal stability of PADD in addition PAM was studied by TGA. In addition, the strong structure of surface morphology was confirmed by scanning electronic microscopy (SEM). Established effective process was used to evaluate the flocculation behaviour with special characteristics. Measuring the parameters, dosage of flocculants, flocculation time, temperature, flocculants initial concentration of Congo red dye, stirring speed and zeta potential in removal of Congo red efficiently in acid aqueous environment. These factors presented that in the condition of strong acidity, low concentration and charge neutralization, the adsorption and bridging effect of PADD on Congo red dye was dominant. Under the idyllic conditions concentration of dye 3.0 mg L−1 and pH 6.0, the maximum removal rates of Congo red dye have been 96.45% and 81.10%, PADD and PAM, respectively. PADD provides a scientific basis platform for the removal of Congo red dye efficiently.

Telescoped continuous flow synthesis of phenyl acrylamide

Functional acrylamides are valuable intermediates for organic synthesis and building blocks in many industrial areas, like polymer synthesis, fine chemicals and pharmaceutics. The conventional batch reaction copes with some safety issues, due to the intrinsic reactivity and careful handling of the reagents. Moreover, the hazardous solvents used and the energy consumed have an enormous environmental impact. The development of an efficient and robust continuous flow process, allowing a safe and on-demand synthesis of acrylamides with high yield leads the way to a more sustainable chemistry. Two alternative synthesis routes for the preparation of N-phenyl acrylamide, but applicable as a continuous production process, are presented: both based on the Schotten-Baumann reaction, one starting from 3-chloropropanoyl chloride and the other starting from acrylic acid. The latter reaction, with a laboratory throughput of 16.5 g·h−1, low operation temperatures and the use of less hazardous chemicals, provides an efficient and sustainable alternative synthesis route of the desired acrylamides, minimizing side-products and enabling a safe and convenient scale-up.

Processing strategies to decrease acrylamide formation, reducing sugars and free asparagine content in potato chips from three commercial cultivars

Potato chips are among the highest contributors to the dietary intake of acrylamide, a potent neurotoxin and likely carcinogen in heat-processed foods. The present study aimed to determine the effects of frying conditions and additive treatments on reducing sugars, asparagine levels, and acrylamide formation in fried potato chips. Three commercially important chipping cultivars (Atlantic, Snowden, and Vigor) were tested using different frying times (3, 5, and 7 min) and temperatures (160, 170, 180, and 190 °C). Acrylamide formation in chips was found to be cultivar-specific and increased with increasing frying time and temperature. The acrylamide levels were significantly lower in chips processed at high temperatures for short frying times than in those processed at low temperatures for long frying times. In all cultivars, acrylamide synthesis was accompanied by significant decreases in the levels of reducing sugars and asparagine. The cultivar exhibiting the lowest acrylamide levels in the processed potato chips was Snowden, while the conditions most conducive to acrylamide formation in all cultivars were frying at 190 °C for 7 min. Using a 7 min frying time, decreasing the frying temperature from 190 to 160 °C mitigated the acrylamide formation in potato chips processed from Atlantic, Snowden and Vigor by 84, 67, and 78%, respectively. We also examined the effects of additives, such as 1% acetic acid, 1% citric acid, 0.1 M sodium chloride, 0.1 M calcium chloride, 0.5% ascorbic acid, or 1 M l-glycine, during the blanching of potato slices prior to frying. Blanching in distilled water led to the greatest decreases (19–59%) in acrylamide formation in all cultivars. Our findings provide the basis for new processing strategies to mitigate acrylamide formation and improve the quality of chips from these, and possibly other, potato cultivars.

Sodium Chloride Inhibits Acrylamide Formation During Deep Fat Frying Of Plantain

Processing is often essential in order for food to become comestible and delectable e.g. addition of salt to food during frying to improve its taste. Acrylamide is formed during processes which occur at high temperature. This study ascertains that sodium chloride (NaCl) prevents the formation of acrylamide. It also compares the effects of different concentrations of table salt on formation of acrylamide during deep frying process of plantain. Test samples were treated by immersion in 1%, 5% and 10% sodium chloride for 60 minutes at room temperature before frying. Fried and raw plantain samples were evaluated for their asparagine and acrylamide content. The results showed frying causes acrylamide synthesis in plantain. The acrylamide concentration decreased with reducing pH values and increasing sodium chloride concentration. At 5% and 1% concentration of NaCl, there was no significant difference in the amount of acrylamide formed. The result of this study also revealed that the concentration of acrylamide in plantain significantly decreased (p<0.05) by 98.9% in ripe plantain and 35.4 % in unripe with the addition of 10% sodium chloride. Hence, sodium chloride at a high concentration reduces the formation of acrylamide.

Synthesis of Acrylamides via the Doebner-Knoevenagel Condensation.

A selective synthesis of acrylamides had been developed using the Doebner-Knoevenagel condensation. The reaction occurs under mild conditions at ambient temperatures, tolerates a wide array of functional groups, and affords the E-isomer with high selectivity. The reported method expands the scope of this classic reaction to a class of industrially important products and as well as to the use of aliphatic aldehydes. An organocatalytic mechanism has been proposed, and the ability to scale the process has been demonstrated.

Acrylamide grafted chitosan based ion imprinted polymer for the recovery of cadmium from nickel-cadmium battery waste

Spent nickel-cadmium (Ni-Cd) batteries are classified as hazardous waste due to the presence of toxic cadmium (Cd). Sustainable solution to this problem can be adoption of resource recovery methods for the reuse of Cd. This has been attempted in the present work using the biopolymer chitosan having inherent affinity for metals. Stability of chitosan in acidic medium was improved by grafting it with a suitable grafting agent and crosslinking. Further, it was used for the synthesis of acrylamide grafted chitosan based Cd ion imprinted polymer (CdIIP) using Cd as template and epichlorohydrin (EPI) as crosslinker for the selective recovery of Cd. Density functional theory (DFT) confirmed acrylamide as the best grafting agent with ΔG of −17.98 Kcal/mol for the acrylamide grafted chitosan. FTIR confirmed the grafting of acrylamide on chitosan as well as successful synthesis of CdIIP. EPI proved to be a better crosslinking agent as compared to glutaraldehyde (GLA) for CdIIP as confirmed by EDS. Adsorption of Cd on CdIIP was influenced by pH, time, initial Cd concentration and CdIIP dose. The kinetic data fitted well to pseudo-second-order equation than first order with R2 equals to 0.997. The monolayer adsorption capacity for Cd (167 mg/g) calculated using Langmuir isotherm model was in close approximation to the experimental adsorption capacity of 152 ± 3 mg/g. The thermodynamic data confirmed exothermic and spontaneous nature of adsorption. 84.3% of Cd could be recovered by CdIIP from the acidic leachate of the Ni-Cd battery waste. CdIIP could be effectively reused for five cycles.

Hydrolysis of nitriles by soil bacteria: variation with soil origin.

The aim of this study was to explore bacterial soil diversity for nitrile biocatalysts, in particular, those for hydrolysis of β-substituted nitriles, to the corresponding carboxamides and acids that may be incorporated into peptidomimetics. To achieve this, we needed to compare the efficiency of isolation methods and determine the influence of land use and geographical origin of the soil sample. Nitrile-utilizing bacteria were isolated from various soil environments across a 1000km long transect of South Africa, including agricultural soil, a gold mine tailing dam and uncultivated soil. The substrate profile of these isolates was determined through element-limited growth studies on seven different aliphatic or aromatic nitriles. A subset of these organisms expressing broad substrate ranges was evaluated for their ability to hydrolyse β-substituted nitriles (3-amino-3-phenylpropionitrile and 3-hydroxy-4-phenoxybutyronitrile) and the active organisms were found to be Rhodococcus erythropolis from uncultivated soil and Rhodococcus rhodochrous from agricultural soils. The capacity for hydrolysis of β-substituted nitriles appears to reside almost exclusively in Rhodococci. Land use has a much greater effect on the biocatalysis substrate profile than geographical location. Enzymes are typically substrate specific in their catalytic reactions, and this means that a wide diversity of enzymes is required to provide a comprehensive biocatalysis toolbox. This paper shows that the microbial diversity of nitrile hydrolysis activity can be targeted according to land utilization. Nitrile biocatalysis is a green chemical method for the enzymatic production of amides and carboxylic acids that has industrial applications, such as in the synthesis of acrylamide and nicotinamide. The biocatalysts discovered in this study may be applied to the synthesis of peptidomimetics which are an important class of therapeutic compounds.

The effect of heat treatments on the synthesis of acrylamide and its quantification by gas chromatography with a nitrogen-phosphorus detetector

In this paper, the influence of thermal treatment (cooking, baking and frying) on the content of acrylamide in potato was followed by gas chromatography with nitrogen - phosphorus detector (GC-NPD). Sample preparation was performed in the conventional manner, applying heat treatment as follows: in boiling water at 110 0C for 30 minutes, by baking in an oven for 30 minutes at 2200 C, and frying in oil for 15 minutes at 250 0C. Quantification of acrylamide are preceded: homogenization of the sample, extraction, and evaporation of the extract. The calibration is performed in the concentration range 0-10 mg/kg and obtained value for R2 was higher than 0,99. Llimit of detection and limit of quantification were determined and obtained values were 0,26 mg/kg and 0,41 mg/kg, respectively. Recovery values were ranged from 102% to 110% and confirmed that metod is accurate. The proposed GC-NPD method is simple, reliable, and accurate for determination of the content of acrylamide in food samples. Obtained results show that the content of acrylamide in potato prepared by heat-cooking were below LOD while for samples trathed by baking or frying were in range from 0,6 mg/kg to 2,7 mg/kg. By comparing the content of acrylamide in potato we concluded that heat treatment has a major impact on the synthesis of acrylamide and it would be desirable to develop a process for the preparation of French fries and potato chips with low or no acrylamide content with textured attractive for consummation.

ChemInform Abstract: Aldehyde‐Promoted One‐Pot Regiospecific Synthesis of Acrylamides Using an in situ Generated Molybdenum Tetracarbonyl Amine [Mo(CO)4(amine)2] Complex.

AbstractThe molybdenum‐amine system acts as both a complexing agent and a CO donor.

Overproduction of the Escherichia coli Chaperones GroEL-GroES in Rhodococcus ruber Improves the Activity and Stability of Cell Catalysts Harboring a Nitrile Hydratase.

Three combinations of molecular chaperones from Escherichia coli (i.e., DnaK-DnaJ-GrpEGroEL- GroES, GroEL-GroES, and DnaK-DnaJ-GrpE) were overproduced in E. coli BL21, and their in vitro stabilizing effects on a nitrile hydratase (NHase) were assessed. The optimal gene combination, E. coli groEL-groES (ecgroEL-ES), was introduced into Rhodococcus ruber TH3. A novel engineered strain, R. ruber TH3G was constructed with the native NHase gene on its chromosome and the heterologous ecgroEL-ES genes in a shuttle plasmid. In R. ruber TH3G, NHase activity was enhanced 37.3% compared with the control, TH3. The in vivo stabilizing effect of ecGroEL-ES on the NHase was assessed using both acrylamide immersion and heat shock experiments. The inactivation behavior of the in vivo NHase after immersion in a solution of dynamically increased concentrations of acrylamide was particularly evident. When the acrylamide concentration was increased to 500 g/l (50%), the remaining NHase activity in TH3G was 38%, but in TH3, activity was reduced to 10%. Reactivation of the in vivo NHases after varying degrees of inactivation was further assessed. The activity of the reactivated NHase was more than 2-fold greater in TH3G than in TH3. The hydration synthesis of acrylamide catalyzed by the in vivo NHase was performed with continuous acrylonitrile feeding. The final concentration of acrylamide was 640 g/l when catalyzed by TH3G, compared with 490 g/l acrylamide by TH3. This study is the first to show that the chaperones ecGroEL-ES work well in Rhodococcus and simultaneously possess protein-folding assistance functions and the ability to stabilize and reactivate the native NHases.