Hydrolysis Conditions Research Articles

Optimization of Sorghum Starch (Sorghum bicolor L.) Partial Hydrolysis using Microwave-Assisted Acetic Acid Catalyst

Hydrolysis process is relatively slow, requiring the use of catalyst and microwave assistance to accelerate the reaction. There fore, this study aimed to determine the optimum conditions for partial hydrolysis of sorghum starch (Sorghum bicolor L.) using acetic acid as a microwave-assisted catalyst to produce maltodextrin. The experiment was carried out in several stages, namely gelatinization, liquefaction, and drying, while Response Surface Method (RSM) was used for variable design and data analysis. Hydrolysis process was carried out with three independent variables, including acetic acid concentration (9%, 12%, and 15%), microwave power (300 watts, 400 watts, and 500 watts), and liquefaction time (35 minutes, 45 minutes, and 55 minutes). The results showed that the highest DE (Dextrose Equivalent) value of maltodextrin was found at 17.04% acid concentration, 400 watts microwave power, and 45 minutes liquefaction time, valued at 18.921 ± 0.099. The optimum dextrose equivalent of 17.763 would be achieved at 16.879% acetic acid concentration, 390.233 watts of microwave power, and 47.055 minutes of liquefaction time. This study introduces the innovation of using acetic acid as a catalyst and microwave assistance during the gelatinization stage.

Bioactive Peptide Profiling in Collagen Hydrolysates: Comparative Analysis Using Targeted and Untargeted Liquid Chromatography-Tandem Mass Spectrometry Quantification.

The investigation of collagen hydrolysates (CHs) is essential due to their widespread use in health, cosmetic, and therapeutic industries, attributing to the presence of bioactive dipeptides (DPs) and tripeptides (TPs). This study developed a novel targeted liquid chromatography-tandem mass spectrometry (LC-MS/MS) method with propyl chloroformate (PCF) derivatization to measure three bioactive peptides-Hydroxyprolyl-glycine (Hyp-Gly), Glycyl-prolyl-hydroxyproline (Gly-Pro-Hyp), and Prolyl-hydroxyproline (Pro-Hyp)-in CHs, with strong correlation coefficients (0.992, 1.000, and 0.995, respectively) and low limits of detection (LODs) of 1.40, 0.14, and 1.16 µM, respectively. Untargeted data-dependent acquisition (DDA) analyses measured peptide size distribution, while amino acid analysis assessed nutritional content. The analysis of ten commercial CHs revealed similar amino acid profiles but varied peptide lengths, indicating diverse hydrolysis conditions. Products with higher proportions of smaller peptides showed elevated levels of the targeted bioactive peptides, suggesting that a smaller peptide size may increase bioactivity. These findings can inform the optimization of CH supplements, providing consumers with detailed peptide content for more informed choices. Data are available via ProteomeXchange with the identifier PXD051699.

Turning discarded blue shark (Prionace glauca) skin into a valuable nutraceutical resource: An enzymatic collagen hydrolysate

Marine-derived collagen, particularly from blue shark (Prionace glauca) skin, represents a sustainable resource for the nutraceutical industry, yet its effective utilization remains underexplored. This study aims to optimise the enzymatic hydrolysis of blue shark skin collagen using alcalase and bromelain to enhance the bioactive properties of the resultant hydrolysates. We employed a multifactorial experimental design to determine the optimal hydrolysis conditions, assessing factors including enzyme concentration, pH, and temperature. The alcalase-treated hydrolysates demonstrated superior antioxidant and anti-inflammatory activities compared to those treated with bromelain, with increased solubilised proteins and a higher degree of hydrolysis. Notably, peptide profiles indicated that alcalase hydrolysates favoured the production of smaller peptides, suggesting enhanced bioavailability and digestive stability. In vitro gastrointestinal simulations demonstrated the functional stability of these peptides, indicating that while they undergo structural changes during digestion, their potential for gastrointestinal health remains significant. Our findings highlight the feasibility of converting blue shark skin, a commonly discarded by-product, into valuable nutraceutical ingredients, thus contributing to marine sustainability and waste reduction This research advances the biotechnological application of marine collagen and opens avenues for developing functional foods and pharmaceuticals.

Identification and Characterization of Rotigotine Degradation Products by HPLC Coupled DAD and CAD Detectors and HRMS Through Q-Orbitrap and Electrospray Ionization

Rotigotine (RTG) is a dopamine agonist used in the treatment of Parkinson's disease. As it is susceptible to oxidation, stability studies must be carefully designed for the identification and characterization of all possible degradation products. Here, RTG degradation was evaluated according to the International Conference on Harmonization guidelines under various stress conditions, including acidic and basic hydrolysis, oxidative, metallic, photolytic, and thermal conditions. Additionally, more severe stress conditions were applied to induce RTG degradation. Significant degradation was only observed under oxidative and photolytic conditions. The samples were analyzed by high performance liquid chromatography coupled to photodiode array detectors, charged aerosol, and high-resolution mass spectrometry. Chromatographic analyses revealed the presence of eight substances related to RTG, four of which were already described and were qualified impurities (impurities B, C, K and E) and four new degradation products (DP-1 – DP-4), whose structures were characterized by high-resolution mass spectrometry through Q-Orbitrap and electrospray ionization. In the stress testing of the active pharmaceutical ingredient in solid form, significant RTG degradation was observed in the presence of the oxidative matrix. The results corroborate the literature that confirm the high susceptibility of RTG to oxidation and the importance of using different detectors to detect degradation products in forced degradation studies.

Efficient acid hydrolysis for compound-specific δ15N analysis of amino acids for determining trophic positions

Compound-specific isotope analysis of nitrogen in amino acids (CSIA-AA, δ15NAA) has gained increasing popularity for elucidating energy flow within food chains and determining the trophic positions of various organisms. However, there is a lack of research on the impact of hydrolysis conditions, such as HCl concentration and hydrolysis time, on δ15NAA analysis in biota samples. In this study, we investigated two HCl concentrations (6 M and 12 M) and four hydrolysis times (2 h, 6 h, 12 h, and 24 h) for hydrolyzing and derivatizing AAs in reference materials (Tuna) and biological samples of little egret (n = 4), night heron (n = 4), sharpbelly (n = 4) and Algae (n = 1) using the n-pivaloyl-iso-propyl (NPIP) ester approach. A Dowex cation exchange resin was used to purify amino acids before derivatization. We then determined δ15NAA values using gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). The results revealed no significant differences (p > 0.05) in δ15NAA values among samples treated with different HCl concentrations or hydrolysis times, particularly for δ15NGlx (range: 21.0–23.5‰) and δ15NPhe (range: 4.3–5.4‰) in Tuna (12 M). Trophic positions (TPs) calculated based on δ15NAA at 2 h (little egret: 2.9 ± 0.1, night heron: 2.8 ± 0.1, sharpbelly: 2.0 ± 0.1 and Algae: 1.3 ± 0.2) were consistent with those at 24 h (3.1 ± 0.1, 2.8 ± 0.1, 2.2 ± 0.1 and 1.1 ± 0.1, respectively), suggesting that a 2-h hydrolysis time and a 6 M HCl concentration are efficient pretreatment conditions for determining δ15NAA and estimating TP. Compared to the currently used hydrolysis conditions (24 h, 6 M), the proposed conditions (2 h, 6 M) accelerated the δ15NAA assay, making it faster, more convenient, and more efficient. Further research is needed to simplify the operational processes and reduce the time costs, enabling more efficient applications of CSIA-AA.

Lemon basil seed-derived peptide: Hydrolysis, purification, and its role as a pancreatic lipase inhibitor that reduces adipogenesis by downregulating SREBP-1c and PPAR-γ in 3T3-L1 adipocytes.

The purpose of this study is to assess the bioactive peptides derived from the defatted lemon basil seeds hydrolysate (DLSH) for their ability to inhibit pancreatic lipase, decrease intracellular lipid accumulation, and reduce adipogenesis. Response surface methodology (RSM) was employed to optimize trypsin hydrolysis conditions for maximizing lipase inhibitory activity (LI). A hydrolysis time of 387.06 min, a temperature of 49.03°C, and an enzyme concentration of 1.61% w/v, resulted in the highest LI with an IC50 of 368.07 μg/mL. The ultrafiltration of the protein hydrolysate revealed that the fraction below 0.65kDa exhibited the greatest LI potential. Further purification via RP-HPLC identified the Gly-Arg-Ser-Pro-Asp-Thr-His-Ser-Gly (GRSPDTHSG) peptide in the HPLC fraction F1 using mass spectrometry. The peptide was synthesized and demonstrated LI with an IC50 of 0.255 mM through a non-competitive mechanism, with a constant (Ki) of 0.61 mM. Docking studies revealed its binding site with the pancreatic lipase-colipase complex. Additionally, GRSPDTHSG inhibited lipid accumulation in 3T3-L1 cells in a dose-dependent manner without cytotoxic effects. Western blot analysis indicated downregulation of PPAR-γ and SREBP-1c levels under GRSPDTHSG treatment, while an increase in AMPK-α phosphorylation was observed, suggesting a role in regulating cellular lipid metabolism. Overall, GRSPDTHSG demonstrates potential in attenuating lipid absorption and adipogenesis, suggesting a prospective application in functional foods and nutraceuticals.

Preparation of xylooligosaccharides from rice husks and their structural characterization, antioxidant activity, and probiotic properties

Rice husks are rich in xylan, which can be hydrolyzed by xylanase to form xylooligosaccharides (XOS). XOS are a functional oligosaccharide such as improving gut microbiota and antioxidant properties. In this study, the structure and functional characteristics of XOS were studied. The optimal xylanase hydrolysis conditions through response surface methodology (RSM) were: xylanase dosage of 3000 U/g, hydrolysis time of 3 h, hydrolysis temperature of 50 °C. Under this condition, the yield of XOS was 150.9 mg/g. The TG-DTG curve showed that XOS began to decompose at around 200 °C. When the concentration of XOS reached 1.0 g/L, the clearance rate of DPPH reached 65.76 %, and the scavenging rate of OH reached 62.10 %, while the clearance rate of ABTS free radicals reached 97.70 %, which was equivalent to the clearance rate of VC. XOS had a proliferative effect on four probiotics: Lactobacillus plantarum, Lactobacillus brucelli, Lactobacillus acidophilus, and Lactobacillus rhamnosus. However, the further experiments are needed to explore the improvement effect of XOS on human gut microbiota, laying a foundation for the effective utilization of XOS. XOS have a wide range of sources, low price, and broad development prospects. The reasonable utilization of XOS can bring greater economic benefits.

The study of galactomannans with different molecular weights and their ability to form microparticles suitable for pulmonary delivery

The influence of locust bean gum (LBG) galactomannans (GMs) molecular weight (Mw) to assemble microparticulate systems was evaluated, and carriers for deep lung delivery were developed. A commercial batch of LBG with a mannose/galactose (M/G) ratio of 2.4 (batch 1) was used to study the influence of different microwave partial acid hydrolysis conditions on carbohydrate composition, glycosidic linkages, and aqueous solutions viscosity. The microwave treatment did not affect the composition, presenting 4-Man (36–42 %), 4,6-Man (27–35 %), and T-Gal (24–25 %) as the main glycosidic linkages. Depolymerization led to a viscosity reduction (≤0.005 Pa·s) with no major impact on polysaccharide debranching. The structural composition of the LBG galactomannans were further elucidated with sequence-specific proteins using carbohydrate microarray technologies. A second batch of LBG (M/G 3.3) was used to study the impact of GMs with different Mw on microparticle assembling, characteristics, and insulin release kinetics. The low-Mw GMs microparticles led to a faster release (20 min) than the higher-Mw (40 min) ones, impacting the release kinetics. All microparticles exhibited a safety profile to cells of the respiratory tract. However, only the higher-Mw GMs allowed the assembly of microparticles with sizes suitable for this type of administration.

Optimization of Ultrasound-enhanced Subcritical Water Hydrolysis of Oil Palm Empty Fruit Bunch for the Production of Fermentable Sugar

To enhance the hydrolysis to produce fermentable sugar, oil palm empty fruit bunch (OPEFB) has undergone ultrasonication pretreatment prior to subjection to subcritical water hydrolysis. This work aims to optimize the effect of temperature, reaction time, and the concentration of sodium dodecyl sulfate (SDS) as the surfactant, with the primary aim of maximizing sugar production in the subcritical water hydrolysis process applied to oil palm empty fruit bunch (OPEFB). The pretreatment process conditions were optimized using response surface methodology of the central composite design (RSM–CCD). The experimental design includes three factors and levels, with a range of 180–220 °C temperature (X1), 60–80 minutes process time (X2), and 1–5% w/w SDS concentration (X3), an α value of 1.68, and reducing sugar concentration (g/L) as response (Y1). The optimum condition for subcritical water hydrolysis of OPEFB was obtained at 208 °C, 78 minutes, and 2.6% w/w SDS concentration with an expected yield of 6.09 g/L. As a result, reducing sugar produced by enzymatic hydrolysis increased by 324.7% compared to raw OPEFB, with sugar yield of 45.64% after 36 hours. Along these, changes in crystallinity, chemical composition, lignocellulosic functional groups, and morphology were analyzed to determine the impact of the pre-treatment on OPEFB.

Recovery of Ellagic Acid from Pomegranate Peels with the Aid of Ultrasound-Assisted Alkaline Hydrolysis.

The pomegranate processing industry generates worldwide enormous amounts of by-products, such as pomegranate peels (PPs), which constitute a rich source of phenolic compounds. In this view, PPs could be exploited as a sustainable source of ellagic acid, which is a compound that possesses various biological actions. The present study aimed at the liberation of ellagic acid from its bound forms via ultrasound-assisted alkaline hydrolysis, which was optimized using response surface methodology. The effects of duration of sonication, solvent:solid ratio, and NaOH concentration on total phenol content (TPC), antioxidant activity, and punicalagin and ellagic acid content were investigated. Using the optimum hydrolysis conditions (i.e., 32 min, 1:48 v/w, 1.5 mol/L NaOH), the experimental responses were found to be TCP: 4230 ± 190 mg GAE/100 g dry PPs; AABTS: 32,398 ± 1817 µmol Trolox/100 g dry PPs; ACUPRAC: 29,816 ± 1955 µmol Trolox/100 g dry PPs; 59 ± 3 mg punicalagin/100 g dry PPs; and 1457 ± 71 mg ellagic acid/100 g dry PPs. LC-QTOF-MS and GC-MS analysis of the obtained PP extract revealed the presence of various phenolic compounds (e.g., ellagic acid), organic acids (e.g., citric acid), sugars (e.g., fructose) and amino acids (e.g., glycine). The proposed methodology could be of use for food, pharmaceutical, and cosmetics applications, thus reinforcing local economies.

Hydrolytic degradation behaviors of polylactides/poly(propylene carbonate blends: Monolayers and bulk films

The study investigates the hydrolytic degradation behaviors of blends comprising polylactides (PLA) and poly(propylene carbonate) (PPC) in the form of monolayers and bulk films. PLA is a biodegradable polymer widely used in various applications, while PPC offers unique properties, making it a promising candidate for blend formulations. The research explores the degradation kinetics and mechanical properties under controlled hydrolysis conditions. The finding focuses on the compatibility of PLA and PPC, their degradation mechanisms, and the impact of blend composition on degradation rates. Understanding the hydrolytic behavior of these blends is crucial for designing eco-friendly materials with tailored degradation profiles for diverse applications.

A comprehensive study on the identification and characterization of degradation products of lipoglycopeptide Dalbavancin using LC and LC-HRMS/MS.

Dalbavancin is the second-generation approved semisynthetic lipoglycopeptide by the United States Food and Drug Administration (USFDA) for the treatment of acute bacterial skin and skin-structure infections. Unlike other lipoglycopeptides, the stability behavior of Dalbavancin was least explored, which is a prerequisite. The current study endeavors to elucidate the oxidative and hydrolytic stability behavior of Dalbavancin by exposing the drug to oxidative, acidic, and basic stress conditions. A simple liquid chromatography (LC) method was developed, where significant resolution between Dalbavancin, its homologs, and the generated degradation products was achieved. Seven degradation products were identified under acidic, basic, and oxidative stress conditions. Using liquid chromatography and high-resolution mass spectrometry (LC-HRMS), MS/MS studies, the generated degradation products were identified and characterized. Formation of isomeric degradation products was identified especially upon exposure to basic stress conditions. The mechanistic fragmentation pathway for the seven degradation products was established, and the chemical structure for the identified degradation products was elucidated. The results strongly suggest that Dalbavancin is highly susceptible to degradation under oxidative and hydrolytic stress conditions. This study provides insights into the hydrolytic and oxidative stability of Dalbavancin, which can be employed during drug development and discovery in synthesizing relatively stable analogs.

Effect of enzymatic hydrolysis with Alcalase or Protamex on technological and antioxidant properties of whey protein hydrolysates

The aim of this study was to evaluate the effect of the enzymatic hydrolysis, performed using Alcalase and Protamex enzymes, on the technological functionalities and the antioxidant capacity of whey protein hydrolysates (WPHs) to identify the conditions allowing to obtain target functionality/ies. Samples were characterized for hydrolysis degree (DH), molecular weight distribution, structural properties, and food-related functionalities. Free sulfhydryl groups and surface hydrophobicity significantly decreased with the increase in DH, regardless of the used enzyme. The foaming and antioxidant properties of Alcalase WPHs were higher as compared to those of WPI, reaching the maximum value at DH = 18–20 %, while higher DH resulted in impaired functionality. Gelling properties were guaranteed when WPI was hydrolysed by Protamex at DH < 15 % while foaming and antioxidant abilities were fostered at 15 < DH < 21 %. These results were well correlated with MW distribution and were rationalized into a road map which represents a useful tool in the selection of proper hydrolysis conditions (time, DH, enzyme type) to obtain WPHs with tailored functionalities. Research outcomes highlighted the possibility to drive protein hydrolysis to optimize the desired functionality/ies.

Determination of Flavonoids and Phenolic Acids in the Liver of Wistar Rats after a Dietary Enrichment with Corinthian Currant (Vitis vinifera L., var. Apyrena): A Liquid Chromatography-Tandem Mass Spectrometry Study.

Corinthian currants are dried fruits produced from Vitis vinifera L. var. Apyrena grape. This study investigated the distribution of phenolic compounds in male Wistar rat livers following two distinct Corinthian currant long-term dietary intake protocols (3 and 10% w/w). Method optimization, comparing fresh and lyophilized tissues, achieved satisfactory recoveries (>70%) for most analytes. Enzymatic hydrolysis conditions (37 °C, pH 5.0) minimally affected phenolics, but enzyme addition showed diverse effects. Hydrolyzed lyophilized liver tissue from rats consuming Corinthian currants (3 and 10% w/w) exhibited elevated levels of isorhamnetin (20.62 ± 2.27 ng/g tissue and 33.80 ± 1.38 ng/g tissue, respectively), along with similar effects for kaempferol, quercetin, and chrysin after prolonged Corinthian currant intake. This suggests their presence as phase II metabolites in the fasting-state liver. This study is the first to explore phenolic accumulation in rat liver, simulating real conditions of dried fruit consumption, as seen herein with Corinthian currant.

Integrated biorefinery approach for utilization of wood waste into levulinic acid and 2-Phenylethanol production under mild treatment conditions

In a bid to explore the on-site biorefinery approach for conversion of forestry residues, lignocellulosic biomass into value-added products was studied. The bark white pine wood was subjected to the microwave technique of fast and slow hydrolysis under varying acid and biomass concentrations to produce levulinic acid (LA). The HCl (2% v/v) and plant biomass (1% w/v) were identified as the optimum conditions for fast wood hydrolysis (270 ºC for 12 sec), which led to maximum LA yield of 446.68 g/kgPB. The proposed sustainable approach is mild, quick, and utilized a very low concentration of the HCl for the production of LA. The hydrolysate was used as a medium for Kluyveromyces marxianus growth to produce 2-phenylethanol (2-PE). K. marxianus used 74–95% of furfural from hydrolysate as a co-substrate to grow. The proposed model of the integrated biorefinery is an affordable on-site approach of using forest waste into localized solutions to produce LA and 2-PE.

Immobilization of Cutinase from Fussarium oxysporum into Sea Sand Matrix for Catalytic Degradation of Polyethylene Terephthalate (PET)

Cutinase is an enzyme that can be used as a catalyst in the hydrolysis reaction of polyethylene terephthalate (PET) waste into terephthalic acid and ethylene glycol. Generally, cutinase has low stability in its free form. Therefore, to increase cutinase stability, cutinase needs to be immobilized. In this study, cutinase was immobilized into a sea sand matrix by adsorption technique. The purpose of this study was to determine the optimum conditions of PET hydrolysis (pH, temperature, and incubation time), and to study the ability of immobilized cutinase for catalytic degradation of PET. The results show that immobilized cutinase has optimum conditions at pH 8, temperature of 50 °C, and incubation time of 24 hrs. Moreover, the immobilized cutinase can be used for up to three cycles with a residual activity percentage of 66.2% and an activity value of 23.224 nmol. g-1. min-1. The total enzyme activity of immobilized cutinase after being used in three cycles was 89.99 nmol. g-1. min-1 or 28.6% of its free enzyme activity.

Enhancing Cutin Extraction Efficiency from Industrially Derived Tomato Processing Residues by High-Pressure Homogenization.

This study primarily aimed to enhance the extraction of cutin from industrial tomato peel residues. Initially, the conventional extraction process was optimized using response surface methodology (RSM). Subsequently, high-pressure homogenization (HPH) was introduced to improve extraction efficiency and sustainability. The optimization process focused on determining the optimal conditions for conventional extraction via chemical hydrolysis, including temperature (100-130 °C), time (15-120 min), and NaOH concentration (1-3%). The optimized conditions, determined as 130 °C, 120 min, and 3% NaOH solution, yielded a maximum cutin extraction of 32.5%. Furthermore, the results indicated that applying HPH pre-treatment to tomato peels before alkaline hydrolysis significantly increased the cutin extraction yield, reaching 46.1%. This represents an approximately 42% increase compared to the conventional process. Importantly, HPH pre-treatment enabled cutin extraction under milder conditions using a 2% NaOH solution, reducing NaOH usage by 33%, while still achieving a substantial cutin yield of 45.6%. FT-IR analysis confirmed that cutin obtained via both conventional and HPH-assisted extraction exhibited similar chemical structures, indicating that the main chemical groups and structure of cutin remained unaltered by HPH treatment. Furthermore, cutin extracts from both conventional and HPH-assisted extraction demonstrated thermal stability up to approximately 200 °C, with less than 5% weight loss according to TGA analysis. These findings underscore the potential of HPH technology to significantly enhance cutin extraction yield from tomato peel residues while utilizing milder chemical hydrolysis conditions, thereby promoting a more sustainable and efficient cutin extraction process.

Acid-hydrolyzed phenolic extract of parsley (Petroselinum crispum L.) leaves inhibits lipid oxidation in soybean oil-in-water emulsions

The antioxidant activity of the natural phenolic extracts is limited in particular food systems due to the existence of phenolic compounds in glycoside form. Acid hydrolysis post-treatment could be a tool to convert the glycosidic polyphenols in the extracts to aglycones. Therefore, this research investigated the effects of an acid hydrolysis post-treatment on the composition and antioxidant activity of parsley extracts obtained by an ultrasound-assisted extraction method to delay lipid oxidation in a real food system (i.e., soybean oil-in-water emulsion). Acid hydrolysis conditions were varied to maximize total phenolic content (TPC) and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity. When extracts were exposed to 0.6 M HCl for 2 h at 80 ℃, TPC was 716.92 ± 24.43 µmol gallic acid equivalent (GAE)/L, and DPPH radical scavenging activity was 66.89 ± 1.63 %. Not only did acid hydrolysis increase the concentrations of individual polyphenols, but it also resulted in the release of new phenolics such as myricetin and gallic acid. The extract's metal chelating and ferric-reducing activity increased significantly after acid hydrolysis. In soybean oil-in-water emulsion containing a TPC of 400 µmol GAE/L, the acid-hydrolyzed extract had an 11-day lag phase for headspace hexanal compared to the 6-day lag phase of unhydrolyzed extract. The findings indicated that the conversion of glycosidic polyphenols to aglycones in phenolic extracts can help extend the shelf-life of emulsion-based foods.

Environmentally safe chemometric evaluation and data analysis for the kinetic investigation of mirabegron stability

The physicochemical characteristics of different pharmaceuticals may change with transportation, storage, and usage which directly affect their efficacy, quality, and other features. It is crucial to investigate the kinetic action of pharmaceutical compounds to produce predictive data that aid in the computation of their shelf lives. Several conventional analytical methods introduce unwanted dangerous risks, like employing unsafe solvents, that harm both the analyst and the environment. This created the motive for analysts to apply green approaches that consider using safe chemicals and producing as little waste as possible. In this study, powerful green assessment methods were investigated to study the kinetic process of Mirabegron (MIR) in different hydrolytic conditions giving its main degradation product. First, the optimal solvent was identified for the given kinetic procedures with the aid of Principal Component Analysis. Then two advanced chemometric methods were applied to estimate the kinetic parameters of the MIR degradation process namely: Multivariate Curve Resolution-Alternating Least Squares and Artificial Neural Networks. By data manipulation, both algorithms could provide an explanation of the MIR kinetic process in different hydrolytic conditions. Moreover, modified National Environmental Methods Index (NEMI), eco-scale, Hexagon algorithm, Complementary Green Analytical Procedure Index (Complex GAPI), and analytical greenness metric for sample preparation (AGREEprep) were adopted to ensure the greenness of the proposed study. Eventually, the presented investigation could successfully present an eco-friendly chemometric approach for monitoring the different kinetic processes of pharmaceutical compounds with minimum effort and solvent consumption and maximum time saving and analyst safety compared to other traditional methods.

Crystallographic phase stability of nanocrystalline polymorphs TiO2 by tailoring hydrolysis pH

Nanocrystal TiO2 of high crystallinity (88.72 %) polymorphs have been synthesized by a unique simple route. At a low temperature under a measurable condition with differentiated hydrolysis pH of the reaction. Here titanium isopropoxide (TTIP) is used as a precursor, isopropyl alcohol (IP) is a peptizing agent and hydrolysis medium with variable pH (2.0, 2.5, 3.5, 4.5, 5.5, 7.0, 8.5, 9.5) acts as a promoter or catalyst of the reaction. We observed in the whole powder pattern fitting (WPPF) method, TiO2 consisting of 65.0 % anatase, 68.0 % brookite and 45.0 % rutile phase in weight fraction by tailoring different hydrolysis conditions with predominant crystal plane (101), (111), (110) for the individual polymorph anatase, brookite and rutile. The crystal lattice parameters, crystal structure, volume of the crystal lattice, crystal strain, asymmetry, d-spacing and average crystallite size were also studied for the polymorph. The percent of crystallinity dominating around 54.0 to 89.0 % of the titanium and oxygen atoms are arranged regularly and periodically observed for change in the molar ratio (r) tailoring the polymorph phase stability. TiO2 polymorph followed the blue shift at 319.00 to 336.00 nm and had good stability for the decreasing particle size (11.03 nm). This phenomenon has been revealed by transmission electron microscopy (TEM) into the polymorphs. Selected area electron diffraction (SAED) and nanobeam diffraction (NBD) showed the nanocrystal anatase with the prominent miller indices (101) and interplanar distance of 0.35 nm that was revealed by HR-TEM at the lowest pH. Nano anatase is ultrafine which was confirmed by EDS.