STUDIES ON LIGNIN AND RELATED COMPOUNDS.: VIII. A KINETIC STUDY OF THE ACTION OF SULPHUROUS ACID ON LIGNIN AND RELATED COMPOUNDS

1931 ◽  
Vol 5 (1) ◽  
pp. 1-47 ◽  
Author(s):  
Charles A. Sankey ◽  
Harold Hibbert

Electrical conductivity measurements have been made over the temperature range 18–145 °C. of reaction mixtures of sulphurous acid and a large number of type compounds, and data obtained on the stability of the resulting sulphonic acids and the mobility of the equilibria involved. The compounds investigated include saturated and unsaturated aldehydes; saturated, unsaturated and cyclic ketones; phenols; substances in which an ethylene linkage is the only reactive group; furane derivatives; and substances containing pyrone rings.The results are discussed from the standpoints of structure and reaction mechanism. The sulphonic acids of nuclear aldehydes, saturated ketones and cylic ketones are typically unstable. With compounds containing an ethylene linkage conjugated with a carbonyl group, addition normally takes place in the 1:4 positions and is followed by hydrogen migration. Where an ethylene linkage is the only reactive group present, addition proceeds only very slowly and at high temperatures. The difficulty of effecting a reaction between sulphurous acid and phenols in their tautomeric alicyclic forms is indicated by the non-reactivity of resorcinol, and the formation of only a small percentage of an extremely unstable derivative by phloroglucinol. Furfuryl alcohol and glucal are shown to form oxonium derivatives which serve as intermediates for the entry of the sulphonic acid group into the ring system.Conductivity-temperature curves for lignosulphonic acids from various sources indicate that the products are sulphonic acids of the —C = C—type. Other evidence points to an oxonium addition product with a ring oxygen as being a probable intermediate in the formation of the final and more stable lignosulphonic acid. The relation of such a mechanism to the experimental conditions employed in the commercial process of the manufacture of sulphite pulp is indicated.The formation of lignosulphonic acids through tautomerization of a phenolic nucleus is highly improbable. Also for such formation a carbonyl group does not necessarily have to be present. Strong additional evidence is presented for the presence of a heterocyclic ring containing oxygen and for an ethylene linkage in the lignin molecule. The latter is indicated to be in the same ring system as the oxygen atom.

1965 ◽  
Vol 25 (1) ◽  
pp. 137-144 ◽  
Author(s):  
R. E. Kane

Previous investigations have shown that the mitotic apparatus (MA) can be isolated from dividing sea urchin eggs in water buffered at pH 5.6 and that the addition of 1 M hexanediol to the solution raises the usable pH to 6.4. Long chain glycols appeared to be much more effective than related compounds in increasing the stability of the MA, and the aim of the investigations reported here was to determine the basis of this specificity. These experiments show that this impression of specificity is misleading and that under suitable experimental conditions a variety of compounds can be substituted for the glycols. A number of alcohols will duplicate the action of the glycols in stabilizing the MA at pH 6.4, but they must be used at a similar per cent concentration rather than at a similar molar concentration. Increases in the concentration of alcohol or glycol allow isolation at more alkaline pH values, and a pH-concentration relation for the stability of the MA, covering the range from pH 5.6–8, has been determined. These results indicate that the action of these compounds in stabilizing the mitotic apparatus is non-specific and is similar to their effects on the solubility of proteins. The isolation and stabilization of the mitotic apparatus can thus be viewed as a function of the solubility properties of its constituent proteins, opening a variety of new experimental approaches to this problem.


2019 ◽  
Vol 26 (5) ◽  
pp. 339-347 ◽  
Author(s):  
Dilani G. Gamage ◽  
Ajith Gunaratne ◽  
Gopal R. Periyannan ◽  
Timothy G. Russell

Background: The dipeptide composition-based Instability Index (II) is one of the protein primary structure-dependent methods available for in vivo protein stability predictions. As per this method, proteins with II value below 40 are stable proteins. Intracellular protein stability principles guided the original development of the II method. However, the use of the II method for in vitro protein stability predictions raises questions about the validity of applying the II method under experimental conditions that are different from the in vivo setting. Objective: The aim of this study is to experimentally test the validity of the use of II as an in vitro protein stability predictor. Methods: A representative protein CCM (CCM - Caulobacter crescentus metalloprotein) that rapidly degrades under in vitro conditions was used to probe the dipeptide sequence-dependent degradation properties of CCM by generating CCM mutants to represent stable and unstable II values. A comparative degradation analysis was carried out under in vitro conditions using wildtype CCM, CCM mutants and two other candidate proteins: metallo-β-lactamase L1 and α -S1- casein representing stable, borderline stable/unstable, and unstable proteins as per the II predictions. The effect of temperature and a protein stabilizing agent on CCM degradation was also tested. Results: Data support the dipeptide composition-dependent protein stability/instability in wt-CCM and mutants as predicted by the II method under in vitro conditions. However, the II failed to accurately represent the stability of other tested proteins. Data indicate the influence of protein environmental factors on the autoproteolysis of proteins. Conclusion: Broader application of the II method for the prediction of protein stability under in vitro conditions is questionable as the stability of the protein may be dependent not only on the intrinsic nature of the protein but also on the conditions of the protein milieu.


Synthesis ◽  
2019 ◽  
Vol 51 (17) ◽  
pp. 3356-3368
Author(s):  
Piotr Pomarański ◽  
Zbigniew Czarnocki

The synthesis of novel l-prolinal dithioacetal and its application as an organocatalyst for the direct Michael addition of cyclic ketones and acetophenone derivatives to trans-β-nitrostyrene and related compounds is described. The prolinal dithioacetal acts as effective catalyst in the case of cyclic ketones of different ring size, in particular five- and six-membered examples, as well as larger and smaller ring systems. High enantioselectivity and diastereoselectivity is observed for different substrates and trans-β-nitrostyrenes. Also, the first asymmetric syntheses of selected 2-methyl-4-nitro-1,3-diphenylbutan-1-one derivatives by application of the obtained organocatalyst is presented.


Catalysts ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 510
Author(s):  
Majeda Khraisheh ◽  
Fares. Almomani ◽  
Gavin Walker

The separation of C3H4/C3H6 is one of the most energy intensive and challenging operations, requiring up to 100 theoretical stages, in traditional cryogenic distillation. In this investigation, the potential application of two MOFs (SIFSIX-3-Ni and NbOFFIVE-1-Ni) was tested by studying the adsorption–desorption behaviors at a range of operational temperatures (300–360 K) and pressures (1–100 kPa). Dynamic adsorption breakthrough tests were conducted and the stability and regeneration ability of the MOFs were established after eight consecutive cycles. In order to establish the engineering key parameters, the experimental data were fitted to four isotherm models (Langmuir, Freundlich, Sips and Toth) in addition to the estimation of the thermodynamic properties such as the isosteric heats of adsorption. The selectivity of the separation was tested by applying ideal adsorbed solution theory (IAST). The results revealed that SIFSIX-3-Ni is an effective adsorbent for the separation of 10/90 v/v C3H4/C3H6 under the range of experimental conditions used in this study. The maximum adsorption reported for the same combination was 3.2 mmolg−1. Breakthrough curves confirmed the suitability of this material for the separation with a 10-min gab before the lighter C3H4 is eluted from the column. The separated C3H6 was obtained with a 99.98% purity.


2021 ◽  
Vol 23 (1) ◽  
Author(s):  
Kevin Kuhlmann ◽  
Melanie Cieselski ◽  
Julia Schumann

Abstract Background In the present study, two distinct PCR methods were used for the quantification of genetic material and their results were compared: real-time-PCR (qPCR; relative quantification) and droplet digital PCR (ddPCR; absolute quantification). The comparison of the qPCR and the ddPCR was based on a stimulation approach of microvascular endothelial cells in which the effect of a pro-inflammatory milieu on the expression of vasoactive receptors was investigated. Results There was consistency in directions of effects for the majority of genes tested. With regard to the indicated dimension of the effects, the overall picture was more differentiated. It was striking that deviations were more pronounced if the measured values were on the extreme edges of the dynamic range of the test procedures. Conclusions To obtain valid and reliable results, dilution series are recommended, which should be carried out initially. In case of ddPCR the number of copies per µl should be adjusted to the low three-digit range. With regard to qPCR it is essential that the stability and reliability of the reference genes used is guaranteed. Here, ddPCR offers the advantage that housekeeping genes are not required. Furthermore, an absolute quantification of the sample can be easily performed by means of ddPCR. Before using ddPCR, however, care should be taken to optimize the experimental conditions. Strict indications for this methodology should also be made with regard to economic and timing factors.


Nanoscale ◽  
2020 ◽  
Vol 12 (2) ◽  
pp. 658-668 ◽  
Author(s):  
Rafael del Caño ◽  
Jose M. Gisbert-González ◽  
Jose González-Rodríguez ◽  
Guadalupe Sánchez-Obrero ◽  
Rafael Madueño ◽  
...  

The highly packed cetyltrimethylammonium bromide bilayer on the surface of gold nanorods synthesized by the seed-mediated procedure hampers the complete ligand exchange under experimental conditions that preserves the stability of the dispersions.


2014 ◽  
Vol 13 (1) ◽  
Author(s):  
Dariusz Wyrzykowski ◽  
Joanna Pranczk ◽  
Dagmara Jacewicz ◽  
Aleksandra Tesmar ◽  
Bogusław Pilarski ◽  
...  

AbstractA potentiometric titration method (PT) and a stopped-flow kinetic technique monitored by a UV−Vis spectroscopy have been used to characterize the stability of series of Co(II)- and Ni(II)-thiodiacetato complexes, M(TDA), in the presence of 1,10-phenanthroline (phen) or 2,2’-bipyridine (bipy) in aqueous solutions. The stability constants of the binary (1:1), ternary (1:1:1) as well as the resulting hydroxo complexes were evaluated and compared to the corresponding oxydiacetate complexes. Based on the species distribution as a function of pH the relative predominance of the species in the system over a pH range was discussed. Furthermore, the kinetic measurements of the substitution reactions of the aqua ligands to phen or bipy in the coordination sphere of the binary complexes M(TDA) were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (0.2–0.5 mM). The kinetic stability of the M(TDA) complexes was discussed in relation to the experimental conditions and the kind of the auxiliary ligands (phen/bipy). Moreover, the influence of the type of primary ligand (thiodiacetate/oxydiacetate) on the substitution rate of the auxiliary ligands was also compared.


Genes ◽  
2021 ◽  
Vol 12 (7) ◽  
pp. 960
Author(s):  
Meagan Archer ◽  
Jianping Xu

Aspergillus is a genus of filamentous fungi with vast geographic and ecological distributions. Species within this genus are clinically, agriculturally and biotechnologically relevant, leading to increasing interest in elucidating gene expression dynamics of key metabolic and physiological processes. Reverse-transcription quantitative Polymerase Chain Reaction (RT-qPCR) is a sensitive and specific method of quantifying gene expression. A crucial step for comparing RT-qPCR results between strains and experimental conditions is normalisation to experimentally validated reference gene(s). In this review, we provide a critical analysis of current reference gene selection and validation practices for RT-qPCR gene expression analyses of Aspergillus. Of 90 primary research articles obtained through our PubMed query, 17 experimentally validated the reference gene(s) used. Twenty reference genes were used across the 90 studies, with beta-tubulin being the most used reference gene, followed by actin, 18S rRNA and glyceraldehyde 3-phosphate dehydrogenase. Sixteen of the 90 studies used multiple reference genes for normalisation. Failing to experimentally validate the stability of reference genes can lead to conflicting results, as was the case for four studies. Overall, our review highlights the need to experimentally validate reference genes in RT-qPCR studies of Aspergillus.


2010 ◽  
Vol 146-147 ◽  
pp. 460-465 ◽  
Author(s):  
Sheng Hui Guo ◽  
Dong Bo Li ◽  
Li Jun Liu ◽  
Jin Hui Peng ◽  
Li Bo Zhang ◽  
...  

The stability is one most important product performance index, which can directly determine the quality of the partially stabilized zirconia (PSZ), and the stability of PSZ is always fluctuating in the commercial process, so how to accurately, quickly and easily predict the stability of PSZ in the preparation process is very important. In the present paper, a new mathematical model to predict the stability of PSZ was proposed, based on statistical theory (SLT) and support vector machine (SVM) theory, which relates the stability of PSZ and the influence factors, such as the holding temperature, rising rate of temperature, holding time, decreasing rate of temperature and hardening temperature. Typical data collected from commercial process were collected for the training samples and test samples. Then testing and analyzing was done. The results showed that the max relative error was 1.80%, the least relative error was 0%, and the average relative error was 0.58%. It is accurate and reliable to predict the stability of PSZ by SVM model. Besides, multiple influence factors can be comprehensively considered in the SVM model, thus a new highly effective method for predicting the stability of PSZ is provided for commercial application.


1963 ◽  
Vol 41 (1) ◽  
pp. 18-20 ◽  
Author(s):  
Vladimir Palaty

The stability constant of the sodium chelate of EDTA was determined by means of a sodium-sensitive glass electrode. It appears that a hydrogen chelate of the formula NaHY2− is formed in the neutral solution of EDTA, but is very unstable. The stability constants, pKNaY = −2.61 and pKNaHY = 0.03, are comparable to the value obtained by Schwarzenbach and Ackermann under different experimental conditions by a less sensitive method.


Sign in / Sign up

Export Citation Format

Share Document