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1.
Int J Mol Sci ; 25(12)2024 Jun 07.
Article in English | MEDLINE | ID: mdl-38928034

ABSTRACT

The electrophilic activation of various substrates via double or even triple protonation in superacidic media enables reactions with extremely weak nucleophiles. Despite the significant progress in this area, the utility of organophosphorus compounds as superelectrophiles still remains limited. Additionally, the most common superacids require a special care due to their high toxicity, exceptional corrosiveness and moisture sensitivity. Herein, we report the first successful application of the "Brønsted acid assisted Brønsted acid" concept for the superelectrophilic activation of 2-hydroxybenzo[e][1,2]oxaphosphinine 2-oxides (phosphacoumarins). The pivotal role is attributed to the tendency of the phosphoryl moiety to form hydrogen-bonded complexes, which enables the formation of dicationic species and increases the electrophilicity of the phosphacoumarin. This unmasks the reactivity of phosphacoumarins towards non-activated aromatics, while requiring only relatively non-benign trifluoroacetic acid as the reaction medium.


Subject(s)
Organophosphorus Compounds , Catalysis , Organophosphorus Compounds/chemistry , Hydrogen Bonding , Acids/chemistry , Molecular Structure
2.
Int J Biol Macromol ; 273(Pt 2): 133224, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38897518

ABSTRACT

In recent years, with the booming of the edible mushroom industry, chitin production has become increasingly dependent on fungi and other non-traditional sources. Fungal chitin has advantages including superior performance, simpler separation processes, abundant raw materials, and the absence of shellfish allergens. As a kind of edible mushroom, flammulina velutipes (F. velutipes) also has the advantages of wide source and large annual yield. This provided the possibility for the extraction of chitin. Here, a procedure to extract chitin from F. velutipes waste be presented. This method comprises low-concentration acid pretreatment coupled with consolidated bioprocessing with Aspergillus niger. Characterization by SEM, FTIR, XRD, NMR, and TGA confirmed that the extracted chitin was ß-chitin. To achieve optimal fermentation of F. velutipes waste (80 g/L), ammonium sulfate and glucose were selected as nitrogen and carbon sources (5 g/L), with a fermentation time of 5 days. The extracted chitin could be further deacetylated and purified to obtain high-purity chitosan (99.2 % ± 1.07 %). This chitosan exhibited a wide degree of deacetylation (50.0 % ± 1.33 % - 92.1 % ± 0.97 %) and a molecular weight distribution of 92-192 kDa. Notably, the yield of chitosan extracted in this study was increased by 56.3 % ± 0.47 % compared to the traditional chemical extraction method.


Subject(s)
Aspergillus niger , Chitin , Fermentation , Flammulina , Aspergillus niger/metabolism , Flammulina/chemistry , Chitin/chemistry , Chitin/isolation & purification , Waste Products , Acids/chemistry , Molecular Weight
3.
Sci Rep ; 14(1): 12655, 2024 06 02.
Article in English | MEDLINE | ID: mdl-38825597

ABSTRACT

Potato peel waste (PPW) is an underutilized substrate which is produced in huge amounts by food processing industries. Using PPW a feedstock for production of useful compounds can overcome the problem of waste management as well as cost-effective. In present study, potential of PPW was investigated using chemical and thermochemical treatment processes. Three independent variables i.e., PPW concentration, dilute sulphuric acid concentration and liberation time were selected to optimize the production of fermentable sugars (TS and RS) and phenolic compounds (TP). These three process variables were selected in the range of 5-15 g w/v substrate, 0.8-1.2 v/v acid conc. and 4-6 h. Whole treatment process was optimized by using box-behnken design (BBD) of response surface methodology (RSM). Highest yield of total and reducing sugars and total phenolic compounds obtained after chemical treatment was 188.00, 144.42 and 43.68 mg/gds, respectively. The maximum yield of fermentable sugars attained by acid plus steam treatment were 720.00 and 660.62 mg/gds of TS and RS, respectively w.r.t 5% substrate conc. in 0.8% acid with residence time of 6 h. Results recorded that acid assisted autoclaved treatment could be an effective process for PPW deconstruction. Characterization of substrate before and after treatment was checked by SEM and FTIR. Spectras and micrographs confirmed the topographical variations in treated substrate. The present study was aimed to utilize biowaste and to determine cost-effective conditions for degradation of PWW into value added compounds.


Subject(s)
Industrial Waste , Plant Extracts , Solanum tuberosum , Chemistry Techniques, Analytical/methods , Chemistry Techniques, Analytical/standards , Solanum tuberosum/chemistry , Plant Extracts/chemistry , Plant Extracts/isolation & purification , Industrial Waste/analysis , Food Industry , Fermentation , Sugars/analysis , Sugars/isolation & purification , Phenols/analysis , Phenols/isolation & purification , Acids/chemistry , Steam , Spectroscopy, Fourier Transform Infrared
4.
Article in English | MEDLINE | ID: mdl-38805241

ABSTRACT

This study presents a method based on acid transesterification and the purification by solid-phase extraction (SPE) coupled with gas chromatography-tandem mass spectrometry for quantifying 3- and 2-monochloropropanediol esters (3-MCPDE, 2-MCPDE) and glycidyl esters (GE) in nutritional foods. The fat was extracted by liquid-liquid extraction with petroleum ether and diethyl ether after the sample was hydrolysed with ammonia. Then the extract was purified by a SPE cartridge filled with the aminopropyl sorbents. It was demonstrated that the optimal elution volume for 3-MCPDE, 2-MCPDE and GE greatly depended on the sample matrix and varied from 6 to 12 mL for four different kinds of food matrices. All three analytes in the sample solution could be fully collected in the first 10-12 mL of eluate. By this way, monoacylglycerols commonly present in the samples were fully removed. Therefore, the overestimation of GE quantification was effectively eliminated. The modified analytical procedure was fully validated in a single laboratory and has been recommended as a Chinese Food Safety National Standard. In addition, two derivatisation agents, heptafluorobutyrylimidazole and phenylboronic acid, were proved to be equivalent in method accuracy and precision for the quantification of three analytes.


Subject(s)
Esters , Food Analysis , Food Contamination , Gas Chromatography-Mass Spectrometry , Propanols , Solid Phase Extraction , Tandem Mass Spectrometry , Esters/analysis , Hydrolysis , Food Contamination/analysis , Propanols/analysis , Propanols/chemistry , Epoxy Compounds/analysis , Epoxy Compounds/chemistry , alpha-Chlorohydrin/analysis , Acids/analysis , Acids/chemistry
5.
Chemistry ; 30(38): e202401402, 2024 Jul 05.
Article in English | MEDLINE | ID: mdl-38719730

ABSTRACT

Amidations employing mixed (carbonic) anhydrides have long been favoured in peptide synthesis because of their cost-effectiveness and less waste generation. Despite their long history, no study has compared the effects of additives on the activation of mixed anhydrides and carbonic anhydrides. In this study, we investigated the amidation of mixed (carbonic) anhydride in the presence of a base and/or Brønsted acids. The use of NMI⋅HCl significantly improved the conversion of the mixed carbonic anhydride, while expediting nucleophilic attacks on the desired carbonyl group. In contrast, in the case of mixed anhydrides, neither the conversion nor the desired nucleophilic attack improved significantly. We developed a C-terminus-free N-methylated peptide synthesis method using mixed carbonic anhydrides in a micro-flow reactor. Fourteen N-alkylated peptides were synthesized in moderate to high yields (55-99 %) without severe racemization (<1 %). Additionally, a significant enhancement in the amidation between mixed carbonic anhydrides and bis-TMS-protected N-methyl amino acids with the inclusion of NMI⋅HCl was observed for the first time. In addition, we observed unexpected C-terminal epimerization of the C-terminus-free N-methyl peptides.


Subject(s)
Anhydrides , Peptides , Peptides/chemistry , Anhydrides/chemistry , Methylation , Acids/chemistry , Alkylation
6.
J Agric Food Chem ; 72(20): 11652-11662, 2024 May 22.
Article in English | MEDLINE | ID: mdl-38738910

ABSTRACT

Pectin lyases (PNLs) can enhance juice clarity and flavor by degrading pectin in highly esterified fruits, but their inadequate acid resistance leads to rapid activity loss in juice. This study aimed to improve the acid resistance of Aspergillus niger PNL pelA through surface charge design. A modification platform was established by fusing pelA with a protein tag and expressing the fusion enzyme in Escherichia coli. Four single-point mutants were identified to increase the surface charge using computational tools. Moreover, the combined mutant M6 (S514D/S538E) exhibited 99.8% residual activity at pH 3.0. The M6 gene was then integrated into the A. niger genome using a multigene integration system to obtain the recombinant PNL AM6. Notably, AM6 improved the light transmittance of orange juice to 45.3%, which was 8.39 times higher than that of pelA. In conclusion, AM6 demonstrated the best-reported acid resistance, making it a promising candidate for industrial juice clarification.


Subject(s)
Aspergillus niger , Fruit and Vegetable Juices , Fungal Proteins , Polysaccharide-Lyases , Aspergillus niger/enzymology , Aspergillus niger/genetics , Fruit and Vegetable Juices/analysis , Polysaccharide-Lyases/genetics , Polysaccharide-Lyases/metabolism , Polysaccharide-Lyases/chemistry , Fungal Proteins/genetics , Fungal Proteins/metabolism , Fungal Proteins/chemistry , Hydrogen-Ion Concentration , Food Handling , Acids/chemistry , Acids/metabolism , Acids/pharmacology , Citrus sinensis/chemistry , Pectins/chemistry , Pectins/metabolism , Enzyme Stability
7.
Bioresour Technol ; 402: 130775, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38701984

ABSTRACT

Acidification recovery in anaerobic digestion of food waste is challenging. This study explored its in-situ recovery using a co-substrate of food waste and waste activated sludge. Fe3O4 and bentonite were used as conductor and carrier, respectively, to enhance AD performance under severe acidification. The application of Fe3O4-bentonite resulted in a 152% increase in cumulative methane in the Fe3O4-bentonite 10 digester, demonstrating its effectiveness in restoring the acidified AD system. In acidified systems, bentonite enhanced the diversity and richness of microbial communities due to its buffering capacity. The excessive non-conductive polysaccharides excreted by bacteria in extracellular polymeric substances reduced the possibility of electron transfer by Fe3O4. However, in the synergistic application of Fe3O4 and bentonite, this resistance was alleviated, increasing the possibility of direct interspecies electron transfer, and accelerating the consumption of volatile fatty acids. This approach of integrating carrier and conductive materials is significant for in-situ restoration of acidified systems.


Subject(s)
Bentonite , Methane , Sewage , Bentonite/chemistry , Anaerobiosis , Methane/metabolism , Hydrogen-Ion Concentration , Food , Fatty Acids, Volatile , Bioreactors , Acids/chemistry , Waste Products , Ferric Compounds/chemistry , Food Loss and Waste
8.
J Agric Food Chem ; 72(18): 10487-10496, 2024 May 08.
Article in English | MEDLINE | ID: mdl-38683727

ABSTRACT

The current study aimed to improve the acid resistance and thermostability of Bacillus velezensis α-amylase through site-directed mutagenesis, with a specific focus on its applicability to the feed industry. Four mutation sites, P546E, H572D, A614E, and K622E, were designed in the C domain of α-amylase, and three mutants, Mut1 (E), Mut2 (ED), and Mut3 (EDEE), were produced. The results showed that the specific activity of Mut3 was 50 U/mg higher than the original α-amylase (Ori) after incubation at 40 °C for 4 h. Compared to Ori, the acid resistance of Mut3 showed a twofold increase in specific activity at pH 2.0. Moreover, the results of preliminary feed hydrolysis were compared between Ori and Mut3 by designing three factors, three levels of orthogonal experiment for enzymatic hydrolysis time, feed quantity, and amount of amylase. It was observed that the enzymatic hydrolysis time and feed quantity showed an extremely significant difference (p < 0.01) in Mut3 compared to Ori. However, the amount of enzyme showed significant (p < 0.05) improvement in the enzymatic hydrolysis in Mut3 as compared to Ori. The study identified Mut3 as a promising candidate for the application of α-amylase in the feed industry.


Subject(s)
Bacillus , Bacterial Proteins , Mutagenesis, Site-Directed , alpha-Amylases , Acids/metabolism , Acids/chemistry , Acids/pharmacology , alpha-Amylases/genetics , alpha-Amylases/chemistry , alpha-Amylases/metabolism , Animal Feed , Bacillus/enzymology , Bacillus/genetics , Bacterial Proteins/genetics , Bacterial Proteins/metabolism , Bacterial Proteins/chemistry , Enzyme Stability , Hot Temperature , Hydrogen-Ion Concentration , Hydrolysis , Kinetics
9.
PLoS One ; 19(4): e0298266, 2024.
Article in English | MEDLINE | ID: mdl-38573921

ABSTRACT

A mechanical device inspired by the pistol shrimp snapper claw was developed. This technology features a claw characterized by a periodic opening/closing motion, at a controlled frequency, capable of producing oscillating flows at transitional Reynolds numbers. An innovative method was also proposed for determining the corrosion rate of carbon steel samples under oscillating acidic streams (aqueous solution of HCl). By employing very-thin carbon steel specimens (25 µm thickness), with one side coated with Zn and not exposed to the stream, it became possible to electrochemically sense the Zn surface once the steel sample was perforated, thus providing the average dissolution rate into the most relevant pit on the steel surface. Furthermore, a laser light positioned beneath the metallic sample, along with a camera programmed to periodically capture images of the steel surface, facilitated the accurate counting of the number of newly formed pits. The system consisting of the thin steel sample and the Zn coating can be seen as a type of corrosion sensor. Furthermore, the proposed laser illumination method allows corroborating the electrochemical detection of pits and also establishing their location. The techniques crafted in this study pave the way for developing alternative corrosion sensors that boast appealing attributes: affordability, compactness, and acceptable accuracy to detect in time and space localized damage.


Subject(s)
Carbon , Steel , Carbon/chemistry , Steel/chemistry , Corrosion , Rivers , Acids/chemistry
10.
Int J Biol Macromol ; 269(Pt 1): 131881, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38677705

ABSTRACT

This work focuses on the precipitation of lignin from kraft black liquor (BL) along with its valorization into lignin nanoparticles (LNP). Two organic acids namely, acetic acid, and lactic acid were used for the precipitation of lignin as an alternative to sulfuric acid. An optimization study was carried out to determine the effect of three key variables, namely acid type, temperature, and pH, on the isolation yield and purity of lignin. The study showed that all factors primarily influenced the lignin yield, while the purity of precipitated lignin varied only around 1 % between minimum to maximum purity. Further, the acid precipitation method was selected for the preparation of LNP. The study aimed to observe the effect of pH, lignin concentration, and surfactant concentration over the properties of the prepared nanoparticles. The results showed that a smaller nanoparticle size and maximization of phenolic content was achieved with a lignin concentration of 35 mg/mL, a surfactant concentration of 10 % (w/w lignin), and a pH of 5. Additionally, the antibacterial activity of LNPs against Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa bacteria was evaluated. The results showed only minor activity against Staphylococcus aureus. Overall, the study demonstrates the potential method for precipitation and valorization of lignin through the production of LNP with desirable properties.


Subject(s)
Chemical Precipitation , Lignin , Nanoparticles , Lignin/chemistry , Nanoparticles/chemistry , Hydrogen-Ion Concentration , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacology , Temperature , Acids/chemistry , Surface-Active Agents/chemistry
11.
Int J Biol Macromol ; 267(Pt 2): 131462, 2024 May.
Article in English | MEDLINE | ID: mdl-38614163

ABSTRACT

The rapid development of the industry has led to the destruction of the earth's ozone layer, resulting in an increasingly serious problem of excessive ultraviolet radiation. Exploring effective measures to address these problems has become a hot topic. Lignin shows promise in the design and preparation of anti-ultraviolet products due to its inherent properties. However, it is important to investigate way to enhance the reactivity of lignin and determine its application form in related products. In this study, phenolic reactions with tea polyphenols were conducted through acid-catalyzed conversion, utilizing organic solvent lignin as the primary material. The phenolic hydroxyl content of the original lignin increased significantly by 218.8 %, resulting in notable improvements in UV resistance and oxidation resistance for phenolic lignin. Additionally, micro-nanocapsule emulsions were formed using phenolic lignin particles as surfactants through ultrasonic cavitation with small-molecule sunscreens. A bio-based sunscreen was prepared with phenolated lignin micro-nanocapsules as the active ingredient, achieving an SPF 100.2 and demonstrating excellent stability. The sunscreen also exhibited strong antioxidant properties and impermeability, ensuring user safety. This research offers a current solution for improving the application of lignin in sunscreens while also broadening the potential uses of plant-based materials in advanced functional products.


Subject(s)
Lignin , Oxidation-Reduction , Polyphenols , Sunscreening Agents , Tea , Ultraviolet Rays , Lignin/chemistry , Polyphenols/chemistry , Catalysis , Tea/chemistry , Sunscreening Agents/chemistry , Sunscreening Agents/pharmacology , Antioxidants/chemistry , Antioxidants/pharmacology , Acids/chemistry
12.
Bioresour Technol ; 400: 130702, 2024 May.
Article in English | MEDLINE | ID: mdl-38615968

ABSTRACT

The bioconversion of lignocellulosic biomass into novel bioproducts is crucial for sustainable biorefineries, providing an integrated solution for circular economy objectives. The current study investigated a novel microwave-assisted acidic deep eutectic solvent (DES) pretreatment of waste cocoa pod husk (CPH) biomass to extract xylooligosaccharides (XOS). The sequential DES (choline chloride/citric acid, molar ratio 1:1) and microwave (450W) pretreatment of CPH biomass was effective in 67.3% xylan removal with a 52% XOS yield from total xylan. Among different XOS of varying degrees of polymerization, a higher xylobiose content corresponding to 69.3% of the total XOS (68.22 mg/g CPH) from liquid fraction was observed. Enzymatic hydrolysis of residual xylan from pretreated CPH biomass with low commercial xylanase (10 IU/g) concentration yielded 24.2% XOS. The MW-ChCl/citric acid synergistic pretreatment approach holds great promise for developing a cost-effective and environmentally friendly method contributing to the sustainable production of XOS from agricultural waste streams.


Subject(s)
Biomass , Cacao , Deep Eutectic Solvents , Glucuronates , Microwaves , Oligosaccharides , Oligosaccharides/chemistry , Cacao/chemistry , Cacao/metabolism , Hydrolysis , Deep Eutectic Solvents/chemistry , Xylans , Biotechnology/methods , Acids/chemistry , Solvents/chemistry
13.
J Hazard Mater ; 470: 134221, 2024 May 15.
Article in English | MEDLINE | ID: mdl-38615651

ABSTRACT

Constructed wetlands (CWs) are a promising approach for treating acid mine drainage (AMD). However, the extreme acidity and high loads of heavy metals in AMD can easily lead to the collapse of CWs without proper pre-treatment. Therefore, it is considered essential to maintain efficient and stable performance for AMD treatment in CWs. In this study, pre-prepared attapulgite-soda residue (ASR) composites were used to improve the substrate of CWs. Compared with CWs filled with gravel (CWs-G), the removal efficiencies of sulfate and Fe, Mn, Cu, Zn Cd and Pb in CWs filled with ASR composites (CWs-ASR) were increased by 30% and 10-70%, respectively. These metals were mainly retained in the substrate in stable forms, such as carbonate-, Fe/Mn (oxide)hydroxide-, and sulfide-bound forms. Additionally, higher levels of photosynthetic pigments and antioxidant enzyme activities in plants, along with a richer microbial community, were observed in CWs-ASR than in CWs-G. The application of ASR composites alleviated the adverse effects of AMD stresses on wetland plants and microorganisms. In return, the increased bacteria abundance, particularly SRB genera (e.g., Thermodesulfovibrionia and Desulfobacca), promoted the formation of metal sulfides, enabling the saturated ASR adsorbed with metals to regenerate and continuously capture heavy metals. The synergistic adsorption of ASR composites and microbial sulfate reduction maintained the stable and efficient operation of CWs. This study contributes to the resource utilization of industrial alkaline by-products and promotes the breakthrough of new techniques for low-cost and passive treatment systems such as CWs.


Subject(s)
Magnesium Compounds , Metals, Heavy , Mining , Silicon Compounds , Sulfates , Water Pollutants, Chemical , Wetlands , Sulfates/chemistry , Metals, Heavy/chemistry , Adsorption , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/metabolism , Silicon Compounds/chemistry , Magnesium Compounds/chemistry , Acids/chemistry , Oxidation-Reduction , Biodegradation, Environmental , Hydrogen-Ion Concentration
14.
PLoS One ; 19(4): e0301923, 2024.
Article in English | MEDLINE | ID: mdl-38652724

ABSTRACT

The chemical and pore structures of coal play a crucial role in determining the content of free gas in coal reservoirs. This study focuses on investigating the impact of acidification transformation on the micro-physical and chemical structure characteristics of coal samples collected from Wenjiaba No. 1 Mine in Guizhou. The research involves a semi-quantitative analysis of the chemical structure parameters and crystal structure of coal samples before and after acidification using Fourier Transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) experiments. Additionally, the evolution characteristics of the pore structure are characterized through high-pressure mercury injection (HP-MIP), low-temperature nitrogen adsorption (LT-N2A), and scanning electron microscopy (SEM). The experimental findings reveal that the acid solution modifies the structural features of coal samples, weakening certain vibrational structures and altering the chemical composition. Specifically, the asymmetric vibration structure of aliphatic CH2, the asymmetric vibration of aliphatic CH3, and the symmetric vibration of CH2 are affected. This leads to a decrease in the contents of -OH and -NH functional groups while increasing aromatic structures. The crystal structure of coal samples primarily dissolves transversely after acidification, affecting intergranular spacing and average height. Acid treatment corrodes mineral particles within coal sample cracks, augmenting porosity, average pore diameter, and the ratio of macro-pores to transitional pores. Moreover, acidification increases fracture width and texture, enhancing the connectivity of the fracture structure in coal samples. These findings provide theoretical insights for optimizing coalbed methane (CBM) extraction and gas control strategies.


Subject(s)
Coal , X-Ray Diffraction , Coal/analysis , Porosity , Spectroscopy, Fourier Transform Infrared , Acids/chemistry , Microscopy, Electron, Scanning , Coal Mining
15.
Nature ; 628(8006): 104-109, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38350601

ABSTRACT

The development of bimolecular homolytic substitution (SH2) catalysis has expanded cross-coupling chemistries by enabling the selective combination of any primary radical with any secondary or tertiary radical through a radical sorting mechanism1-8. Biomimetic9,10 SH2 catalysis can be used to merge common feedstock chemicals-such as alcohols, acids and halides-in various permutations for the construction of a single C(sp3)-C(sp3) bond. The ability to sort these two distinct radicals across commercially available alkenes in a three-component manner would enable the simultaneous construction of two C(sp3)-C(sp3) bonds, greatly accelerating access to complex molecules and drug-like chemical space11. However, the simultaneous in situ formation of electrophilic and primary nucleophilic radicals in the presence of unactivated alkenes is problematic, typically leading to statistical radical recombination, hydrogen atom transfer, disproportionation and other deleterious pathways12,13. Here we report the use of bimolecular homolytic substitution catalysis to sort an electrophilic radical and a nucleophilic radical across an unactivated alkene. This reaction involves the in situ formation of three distinct radical species, which are then differentiated by size and electronics, allowing for regioselective formation of the desired dialkylated products. This work accelerates access to pharmaceutically relevant C(sp3)-rich molecules and defines a distinct mechanistic approach for alkene dialkylation.


Subject(s)
Alkenes , Catalysis , Hydrogen , Acids/chemistry , Alcohols/chemistry , Alkenes/chemistry , Biomimetics , Hydrogen/chemistry , Pharmaceutical Preparations/chemical synthesis , Pharmaceutical Preparations/chemistry
16.
J Am Soc Mass Spectrom ; 35(4): 746-755, 2024 Apr 03.
Article in English | MEDLINE | ID: mdl-38422384

ABSTRACT

Hops (Humulus lupulus L.) are essential raw materials for beer brewing, and the major contributors to beer bitterness are isohumulones (iso-α-acids) and humulinones. In recent years, many breweries have focused on the production of hop-forward beer styles by adding hops after or during the cold fermentation stage, which will tend to release humulinones or other hop-derived bitter compounds. In this study, a LC-MS/MS method was developed for quantification of 60 hop-derived bitter compounds in 25 min. Reverse-phase chromatography with an alkaline methanol/acetonitrile (70:30) mobile phase was used for the separation. The quantitative range was 0.053-3912 ng/mL with correlation coefficient r > 0.99, and the LOQ were 0.26 and 0.053 ng/mL for iso-α-acids and humulinones. Precision (RSD < 5.0%) and accuracy (recovery 86.3%-118.1%) were both satisfactory. The abundance of hop-derived bitter compounds in the dry-hopped beer (Double-India Pale Ale) and the nondry-hopped beer (Vienna Lager) were monitored throughout the fermentation and storage stages, and the formation of oxidation and cyclization products showed difference profiles between these two beers. The quantification results reveal how hop-derived bitter compounds change throughout the brewing process, as well as the influence of hops and brewing techniques on beer bitterness.


Subject(s)
Beer , Humulus , Chromatography, Liquid , Beer/analysis , Humulus/chemistry , Liquid Chromatography-Mass Spectrometry , Tandem Mass Spectrometry , Acids/chemistry
17.
Adv Mater ; 36(24): e2400544, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38390909

ABSTRACT

Engineered protein fibers are promising biomaterials with diverse applications due to their tunable protein structure and outstanding mechanical properties. However, it remains challenging at the molecular level to achieve satisfied mechanical properties and environmental tolerance simultaneously, especially under extreme acid conditions. Herein, the construction of artificial fibers comprising chimeric proteins made of rigid amyloid peptide and flexible cationic elastin-like protein (ELP) module is reported. The amyloid peptide readily assembles into highly organized ß-sheet structures that can be further strengthened by the coordination of Cu2+, while the flexible ELP module allows the formation of imine-based crosslinking networks. These double networks synergistically enhance the mechanical properties of the fibers, leading to a high tensile strength and toughness, overwhelming many reported recombinant spidroin fibers. Notably, the coordination of Cu2+ with serine residues could stabilize ß-sheet structures in the fibers under acidic conditions, which makes the fibers robust against acid, thus enabling their successful utilization in gastric perforation suturing. This work highlights the customization of double networks at the molecular level to create tailored high-performance protein fibers for various application scenarios.


Subject(s)
Copper , Imines , Copper/chemistry , Imines/chemistry , Tensile Strength , Elastin/chemistry , Elastin/metabolism , Acids/chemistry , Biocompatible Materials/chemistry
18.
J Sci Food Agric ; 104(9): 5381-5390, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38334323

ABSTRACT

BACKGROUND: Hot trub is a macronutrient- and micronutrient-rich by-product generated in the brewing industry, which is still underrated as a raw material for reprocessing purposes. In this context, this study aimed to investigate the extraction of bitter acids' and xanthohumol from hot trub as well as identify the significance of parameters for the process. The research assessed various extraction parameters, such as pH, ethanol concentration, temperature, and solid-to-liquid ratio, using a Plackett-Burman design. RESULTS: Ethanol concentration and pH were the most significant parameters affecting extraction yield. ß-acids were found to be the principal components of the bitter acids, with a maximum concentration near 16 mg g-1, followed by iso-α-acids and α-acids achieving 6 and 3.6 mg g-1, respectively. The highest yields of bitter acids were observed in the highest ethanol concentration, while pH was relevant to extraction process in treatments with low ethanol ratios. Concerning the xanthohumol extraction, the approach achieved maximum concentration (239 µg g-1) in treatments with ethanol concentration above 30%. Despite their variances, the phytochemicals exhibited comparable extraction patterns, indicating similar interactions with macromolecules. Moreover, the characterization of the solid residues demonstrated that the extraction process did not bring about any alterations to the chemical and total protein profiles. CONCLUSION: Ethanol concentration was found to have the most significant impact on the extraction of bitter acids and xanthohumol, while temperature had no significant effect. The solid remains resulting from the extraction showed potential for use as a protein source. © 2024 Society of Chemical Industry.


Subject(s)
Flavonoids , Propiophenones , Flavonoids/isolation & purification , Flavonoids/analysis , Flavonoids/chemistry , Propiophenones/isolation & purification , Propiophenones/analysis , Propiophenones/chemistry , Acids/chemistry , Plant Extracts/chemistry , Plant Extracts/isolation & purification , Beer/analysis , Hydrogen-Ion Concentration , Humulus/chemistry
19.
Curr Med Chem ; 31(10): 1172-1213, 2024.
Article in English | MEDLINE | ID: mdl-36915986

ABSTRACT

The biological and medicinal chemistry of the oxocarbon acids 2,3- dihydroxycycloprop-2-en-1-one (deltic acid), 3,4-dihydroxycyclobut-3-ene-1,2-dione (squaric acid), 4,5-dihydroxy-4-cyclopentene-1,2,3-trione (croconic acid), 5,6-dihydroxycyclohex- 5-ene-1,2,3,4-tetrone (rhodizonic acid) and their derivatives is reviewed and their key chemical properties and reactions are discussed. Applications of these compounds as potential bioisosteres in biological and medicinal chemistry are examined. Reviewed areas include cell imaging, bioconjugation reactions, antiviral, antibacterial, anticancer, enzyme inhibition, and receptor pharmacology.


Subject(s)
Acids , Chemistry, Pharmaceutical , Acids/chemistry
20.
J Food Sci ; 89(1): 320-329, 2024 Jan.
Article in English | MEDLINE | ID: mdl-38051010

ABSTRACT

The main objective of this work was to characterize the acid-soluble collagen (ASC) and pepsin-soluble collagen (PSC) from the body wall of the sea cucumber scientifically called, Stichopus hermanni. For the extraction of ASC and PSC, the pre-treated sea cucumber body walls were subjected to 0.5 M acetic acid and 5 g L-1 pepsin, respectively. The yield of ASC (7.30% ± 0.30%) was found to be lower than the PSC (23.66% ± 0.15%), despite both ASC and PSC having similar chemical compositions except for the quantity of protein. The collagens produced from ASC and PSC show maximum peaks on ultraviolet-visible spectroscopic profiles at wavelengths of 230 and 235 nm, respectively, with no significant difference in the maximum temperature (Tmax ) of the extracted ASC and PSC. The ASC's coloration was whiter than that of the PSC. As a result, the collagen obtained from the body wall of the sea cucumber showed promise for usage as a substitute for collagen derived from marine sources. PRACTICAL APPLICATION: The two most popular methods of collagen extraction were acid hydrolysis and enzymatic hydrolysis. To determine whether the extracted collagen is a suitable substitute for animal collagen in different industries, it is required to characterize its physicochemical qualities. This study discovered a new application for marine collagen in the food industry: The sea cucumber has collagen with a greater yield in pepsin extraction with good physicochemical qualities.


Subject(s)
Sea Cucumbers , Stichopus , Animals , Stichopus/chemistry , Stichopus/metabolism , Pepsin A/metabolism , Sea Cucumbers/metabolism , Collagen/chemistry , Acids/chemistry
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