scholarly journals Stability of Gamma-valerolactone Under Pulping Conditions as a Basis for Process Optimization and Chemical Recovery

Author(s):  
Marianna Granatier ◽  
Inge Schlapp-Hackl ◽  
Huy Quang Lê ◽  
Kaarlo Nieminen ◽  
Herbert Sixta

Abstract This study investigates the extent of the g-valerolactone (GVL) hydrolysis forming an equilibrium with 4-hydroxyvaleric acid (4-HVA) in aqueous solutions over a wide pH range. The hydrolysis of pure 50 wt% GVL to 4-HVA (3.5 mol%) was observed only at elevated temperatures. The addition of sulfuric acid (0.2×10-5 wt% to 6 wt%) at elevated temperatures (150 – 180°C) and reaction times between 30-180 min caused the formation of 4 mol% 4-HVA but with decreasing acidity, the 4-HVA remained constant at about 3 mol%. The hydrolysis reactions in alkaline conditions were conducted at constant time (30 min) and temperature (180 °C) with variation of the NaOH concentration (0.2×10-6 wt% to 7 wt%). The addition of less than 0.2 wt % of NaOH resulted in the formation of less than 4 mol% of sodium 4-hydroxyvalerate. A maximum amount of 21 mol% of 4-HVA was observed in a 7 wt% NaOH solution. The stability after synthesis was determined by NMR analysis. To verify the GVL stability results obtained under practical conditions, Betula pendula sawdust was fractionated in 50% GVL with and without addition of H2SO4 or NaOH at 180°C and 120 min, and spent liquor was analyzed. The spent liquor contained 5.6 mol% and 6.0 mol% of 4-HVA in a highly acidic (20 kg H2SO4/t wood) and alkaline (192 kg NaOH/ t wood) environment, respectively.

Cellulose ◽  
2021 ◽  
Author(s):  
Marianna Granatier ◽  
Inge Schlapp-Hackl ◽  
Huy Quang Lê ◽  
Kaarlo Nieminen ◽  
Leena Pitkänen ◽  
...  

AbstractThis study focuses on the investigation of the extent of the γ-valerolactone (GVL) hydrolysis forming an equilibrium with 4-hydroxyvaleric acid (4-HVA) in aqueous solutions over a wide pH range. The hydrolysis of a 50 wt% GVL solution to 4-HVA (3.5 mol%) was observed only at elevated temperatures. The addition of sulfuric acid (0.2 × 10–5 wt% to 6 wt%) at elevated temperatures (150–180 °C) and reaction times between 30 and 180 min caused the formation of 4 mol% 4-HVA. However, with decreasing acidity, the 4-HVA remained constant at about 3 mol%. The hydrolysis reactions in alkaline conditions were conducted at a constant time (30 min) and temperature (180 °C) with the variation of the NaOH concentration (0.2 × 10–6 wt% to 7 wt%). The addition of less than 0.2 wt% of NaOH resulted in the formation of less than 4 mol% of sodium 4-hydroxyvalerate. A maximum amount of 21 mol% of 4-HVA was observed in a 7 wt% NaOH solution. The degree of decomposition after treatment was determined by NMR analysis. To verify the GVL stability under practical conditions, Betula pendula sawdust was fractionated in 50 wt% GVL with and without the addition of H2SO4 or NaOH at 180 °C and a treatment time of 120 min. The spent liquor was analyzed and a 4-HVA content of 5.6 mol% in a high acidic (20 kg H2SO4/t wood) and 6.0 mol% in an alkaline (192 kg NaOH/t wood) environment have been determined.


2020 ◽  
Author(s):  
Juliana C. Ferreira ◽  
Wael M. Rabeh

Abstract Severe acute respiratory syndrome-coronavirus 2 (SARS-CoV-2) is responsible for the novel coronavirus disease 2019 (COVID-19). An appealing antiviral drug target is the coronavirus 3C-like protease (3CLpro) that is responsible for the processing of the viral polyproteins and liberation of functional proteins essential for the maturation and infectivity of the virus. In this study, multiple thermal analytical techniques have been implemented to acquire the thermodynamic parameters of 3CLpro at different buffer conditions. 3CLpro exhibited relatively high thermodynamic stabilities over a wide pH range; however, the protease was found to be less stable in the presence of salts. Divalent metal cations reduced the thermodynamic stability of 3CLpro more than monovalent cations; however, altering the ionic strength of the buffer solution did not alter the stability of 3CLpro. Furthermore, the most stable thermal kinetic stability of 3CLpro was recorded at pH 7.5, with the highest enthalpy of activation calculated from the slope of Eyring plot. The biochemical and biophysical properties of 3CLpro explored here will improve the solubility and stability of 3CLpro for optimum conditions for the setup of an enzymatic assay for the screening of inhibitors to be used as lead candidates in the drug discovery and antiviral design for therapeutics against COVID-19.


2001 ◽  
Vol 89 (6) ◽  
Author(s):  
K. Vercammen ◽  
M.A. Glaus ◽  
Luc R. Van Loon

The complexation of Th(IV) and Eu(III) by α-isosaccharinic acid (ISA) has been studied in the pH range from 10.7 to 13.3 by batch sorption experiments, and the influence of Ca on the complexation was investigated. Sixteen data sets – each determined at variable ISA concentrations – are used to determine the stoichiometry of the complexation reactions and the stability constants. Based on best-fit analysis of the sorption data, it is postulated that 1:1 Th:ISA complexes are formed in the absence of Ca according to the complexation reaction: Th+ISA↔(ThISA)


The six-carbon intermediate of the ribulose 1,5-bisphosphate (RuBP) carboxylase reaction, 2'-carboxy-3-keto-D-arabinitol 1,5-bisphosphate (CKABP), was prepared enzymatically by quenching the reaction with acid after a short time ( ca 12 ms). Over a wide pH range (4-11), GKABP undergoes a slow ( t 1/2 = 1 h), pH-independent decarboxylation. No detectable decomposition of CKABP occurs over a six-week period at — 80 °C. The decarboxylation of CKABP is acid-catalysed and is also catalysed by deactivated enzyme lacking the activator carbamate-divalent metal ion complex. Decarboxylation is accompanied by β-elimination of the C-1 phosphate from the 2,3-enediolate. Under alkaline conditions (pH >11) CKABP undergoes hydrolysis. Non-enzymatic hydrolysis of the intermediate is also accompanied by β-elimination of the C-1 phosphate (presumably from the aci-acid of the upper glycerate 3-phosphate) and the formation of pyruvate. Fully activated enzyme catalyses the complete hydrolysis of CKABP to glycerate 3-phosphate, although enzymic hydrolysis of CKABP is limited by an event not on the direct path of carboxylation. Carbon-13 NMR analysis of [2',3- 13 C]CKABP indicates that it exists in solution predominantly (> 85%) as the C-3 ketone. In contrast, borohydride trapping of CKABP formed from [3- 18 O]RuBP indicates that the intermediate exists on the enzyme predominantly (> 94%) as the hydrated C-3 gem-diol. In solution, the hydration of the C-3 ketone of CKABP proceeds slowly ( k = 2.5 x 10 -3 s -1 ). The enzymatic hydration of CKABP must proceed at least as fast as k cat ( ca. 5 s -1 ) or at least 2000 times faster than the hydration of CKABP in solution.


2020 ◽  
Vol 4 (1) ◽  
pp. 12-17
Author(s):  
Fábio Barbosa ◽  
Leonardo Pezzi ◽  
Julia Sorrentino ◽  
Martin Steppe ◽  
Nadia Volpato ◽  
...  

Stability studies correspond to a set of tests designed to assess changes in the quality of a given drug over time and under the influence of a number of factors. Among these factors, pH plays an important role, due to the catalytic effect that hydronium and hydroxide ions can play in several reactions. In the present study, the degradation kinetics of nitazoxanide was evaluated over a wide pH range, and the main degradation product generated was identified by LC-MS/MS. Nitazoxanide showed first-order degradation kinetics in the pH range of 0.01 to 10.0 showing greater stability between pH 1.0 and 4.0. The degradation rate constant calculated for these pH was 0.0885 x 10-2 min-1 and 0.0689 x 10-2 min-1, respectively. The highest degradation rate constant value was observed at pH 10.0 (0.7418 x 10-2 min-1) followed by pH 0.01 (0.5882 x 10-2 min-1). A major degradation product (DP-1) was observed in all conditions tested. Through LC-MS/MS analysis, DP-1 was identified as a product of nitazoxanide deacetylation. The effect of pH on the stability of nitazoxanide and the kinetic data obtained contribute to a better understanding of the intrinsic stability characteristics of nitazoxanide.


Marine Drugs ◽  
2019 ◽  
Vol 17 (1) ◽  
pp. 55 ◽  
Author(s):  
Francisca de la Coba ◽  
José Aguilera ◽  
Nathalie Korbee ◽  
María de Gálvez ◽  
Enrique Herrera-Ceballos ◽  
...  

The safety and stability of synthetic UV-filters and the procedures for evaluating the photoprotective capability of commercial sunscreens are under continuous review. The influence of pH and temperature stressors on the stability of certain Mycosporine-like amino acids (MAAs) isolated at high purity levels was examined. MAAs were highly stable at room temperature during 24 h at pH 4.5–8.5. At 50 °C, MAAs showed instability at pH 10.5 while at 85 °C, progressive disappearances were observed for MAAs through the studied pH range. In alkaline conditions, their degradation was much faster. Mycosporine-serinol and porphyra-334 (+shinorine) were the most stable MAAs under the conditions tested. They were included in four cosmetically stable topical sunscreens, of which the Sun Protection Factor (SPF) and other Biological Effective Protection Factors (BEPFs) were calculated. The formulation containing these MAAs showed similar SPF and UVB-BEPFs values as those of the reference sunscreen, composed of synthetic UV absorbing filters in similar percentages, while UVA-BEPFs values were slightly lower. Current in vitro data strongly suggest that MAAs, as natural and safe UV-absorbing and antioxidant compounds, have high potential for protection against the diverse harmful effects of solar UV radiation. In addition, novel complementary in vitro tests for evaluation of commercial sunscreens efficacy are proposed.


Author(s):  
YU-HONG TSE ◽  
PAVEL JANDA ◽  
HERMAN LAM ◽  
JIUJUN ZHANG ◽  
WILLIAM J. PIETRO ◽  
...  

The monomeric and polymeric tetra-aminophthalocyane to, cobalt(II) species adsorbed onto graphite electrodes are active in electrocatalytic oxygen reduction. While the monomeric species is unstable, the polymerized species is an effective and stable reduction catalyst over a wide pH range. Both the two-electron reduction of oxygen to hydrogen peroxide and the four-electron reduction of oxygen to water are characterized by cyclic voltammetry, rotating disc and rotating ring-disc studies with appropriate theoretical analysis. Some mechanistic information is obtained. This is the first cobalt phthalocyanine species to provide a four-electron reduction pathway which exists over a wide pH range and is stable. The stability is associated with the polymerization since the monomeric species is not stable.


2016 ◽  
Vol 8 (28) ◽  
pp. 5684-5689 ◽  
Author(s):  
Na Xu ◽  
Quan Zhu ◽  
Xiang-Yue Kong ◽  
Lei Meng

A sensitive fluorescence probe of polyethyleneimine protected silver nanoclusters (AgNCs@PEI) was proposed for the detection of trace level of Cr(vi) in both acidic and alkaline conditions.


2021 ◽  
Author(s):  
Jinjin Cao ◽  
Fang Lv ◽  
Ting Liu ◽  
Luchen Niu ◽  
Bocong Han ◽  
...  

Abstract In this work, reasons for the spectral difference between two isoflavones, Formononetin (F) and ononin (FG), are explained in the viewpoint of molecular structure through a comparison study of the fluorescence features of the two. The fluorescence enhancement of FG in hot alkaline condition is reported for the first time. For F, there was almost no fluorescence under acidic conditions, but when pH>5, its fluorescence began to increase with increasing pH due to the proton ionization of 7-OH. In the range of pH 9.3-12.0, the anion form of F produced a fairly strong and stable fluorescence with maximum excitation wavelength (λex) of 334 nm and emission wavelength (λem) of 464 nm, its fluorescence quantum yield (Yf) was measured to be 0.042. And for FG, its aqueous solution fluoresced weakly in a wide pH range until it was placed under hot alkaline conditions, which was presumed to the cleavage reaction of the γ-pyrone ring in FG by observing a significant fluorescence at λex / λem =288 / 388nm, and Yf was determined to be 0.020. The fluorescence sensitization methods of F and FG both exhibit low limits of detection (2.60 ng·mL-1, 9.30 ng·mL-1) and wide linear ranges (0.0117-1.86 μg·mL-1, 0.0146-2.92μg·mL-1). Although the structural relationship between F and FG is glycoside and aglycone, FG cannot be translated to F by glucoside hydrolysis under hot alkaline condition, the fluorescence enhancement mechanisms of the two are essentially different. The fluorescence difference between the two under different experimental conditions lays the foundation for future fluorescence quantitative analysis.


2021 ◽  
Author(s):  
Mandeep Khan ◽  
Mohammed Qamruzzaman ◽  
Dhirendra Chandra Roy ◽  
Ravi Raman

Abstract Acid jobs with conventional acid systems like hydrochloric acid in high temperature conditions is challenging on various fronts. Enhanced reactivity of strong acids results in poor penetration and severe face dissolution. Also, it aggravates the issue of corrosion of downhole equipment and may also result in sludge formation/asphaltene deposition. Worldwide, chelating agents has emerged as a standalone stimulation fluid for high temperature acidizing. Their unique attributes and properties have been proved very useful for acid jobs at elevated temperatures. However, the chelating agents-based formulations need to be carefully evaluated on various acidization parameters for a fruitful stimulation. Mumbai Offshore field has been encountering the above-mentioned problems in acidizing of its high temperature (>275°F) limestone reservoirs. The paper presents innovative solutions devised for high temperature matrix acidizing. Two chelating agents viz., EDTA (Ethylenediaminetetraceticacid) and GLDA (L-Glutamic Acid N, N-diacetic acid) were explored and evaluated with meticulous laboratory studies. The performance of the chelating agent-based stimulation fluid was compared with acetic acid. Slurry tests were performed to quantify the dissolving power of each acid. Consequently, core flooding tests were carried out to to find the optimum pH of the chelating agents from stimulation point of view. Core flooding studies were performed at anticipated injection rates on representative core samples from a payzone A, with BHT 275-290° F, from Mumbai Offshore. pH optimized formulations were tested against N-80 metallurgy coupons at reservoir temperature for corrosion potential estimation. Also, sludge, asphaltene and emulsion formation tendencies were analyzed with representative oil samples. The results convey that both EDTA and GLDA were able to mitigate the challenges encountered at elevated temperatures. EDTA and GLDA were found to stimulate the cores with wormholes formed at wide pH range with no face dissolution observed. Chelating agents enjoyed good dissolving power with negligible corrosion rates, absence of sludge and asphaltene deposition, compatibility with formation fluid and excellent iron control properties.


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