scholarly journals Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes

Polymers ◽  
2019 ◽  
Vol 11 (12) ◽  
pp. 1962 ◽  
Author(s):  
Pablo M. Blanco ◽  
Sergio Madurga ◽  
Claudio F. Narambuena ◽  
Francesc Mas ◽  
Josep L. Garcés
Keyword(s):  
Mechanical Properties ◽  
Electrostatic Interactions ◽  
Ph Value ◽  
Persistence Length ◽  
Excluded Volume ◽  
Average Charge ◽  
Zero Force ◽  
Charge Regulation ◽  
Ph Values

This work addresses the role of charge regulation (CR) and the associated fluctuations in the conformational and mechanical properties of weak polyelectrolytes. Due to CR, changes in the pH-value modifies the average macromolecular charge and conformational equilibria. A second effect is that, for a given average charge per site, fluctuations can alter the intensity of the interactions by means of correlation between binding sites. We investigate both effects by means of Monte Carlo simulations at constant pH-value, so that the charge is a fluctuating quantity. Once the average charge per site is available, we turn off the fluctuations by assigning the same average charge to every site. A constant charge MC simulation is then performed. We make use of a model which accounts for the main fundamental aspects of a linear flexible polyelectrolyte that is, proton binding, angle internal rotation, bond stretching and bending. Steric excluded volume and differentiated treatment for short-range and long-range interactions are also included. This model can be regarded as a kind of “minimal” in the sense that it contains a minimum number of parameters but still preserving the atomistic detail. It is shown that, if fluctuations are activated, gauche state bond probabilities increase and the persistence length decreases, so that the polymer becomes more folded. Macromolecular stretching is also analyzed in presence of CR (the charge depends on the applied force) and without CR (the charge is fixed to the value at zero force). The analysis of the low force scaling behavior concludes that Pincus exponent becomes pH-dependent. Both, with and without CR, a transition from 1/2 at high pH-values (phantom chain) to 3/5 at low pH-values (Pincus regime) is observed. Finally, the intermediate force stretching regime is investigated. It is found that CR induces a moderate influence in the force-extension curves and persistence length (which in this force regime becomes force-dependent). It is thus concluded that the effect of CR on the stretching curves is mainly due to the changes in the average charge at zero force. It is also found that, for the cases studied, the effect of steric excluded volume is almost irrelevant compared to electrostatic interactions.

scholarly journals Role of Charge Regulation and Fluctuations in the Conformational and Mechanical Properties of Weak Flexible Polyelectrolytes

2019 ◽  
Author(s):  
Pablo M. Blanco ◽  
Sergio Madurga ◽  
Claudio F. Narambuena ◽  
Francesc Mas ◽  
Josep L. Garcés
Keyword(s):  
Mechanical Properties ◽  
Electrostatic Interactions ◽  
Ph Value ◽  
Persistence Length ◽  
Excluded Volume ◽  
Average Charge ◽  
Zero Force ◽  
Charge Regulation ◽  
Ph Values

This work addresses the role of charge regulation (CR) and the associated fluctuations in the conformational and mechanical properties of weak polyelectrolytes. Due to CR, changes in the pH-value modifies the average macromolecular charge and conformational equilibria. A second effect is that, for a given average charge per site, fluctuations can alter the intensity of the interactions by means of correlation between binding sites. We investigate both effects by means of Monte Carlo simulations at constant pH-value, so that the charge is a fluctuating quantity. Once the average charge per site is available, we turn off the fluctuations by assigning the same average charge to every site. A constant charge MC simulation is then performed. We make use of a model which accounts for the main fundamental aspects of a linear flexible polyelectrolyte i.e. proton binding, angle internal rotation, bond stretching and bending. Steric excluded volume and differentiated treatment for short-range and long-range interactions are also included in the model. It can be regarded as a kind of "minimal'' model in the sense that contains a minimum number of parameters but still preserving the atomistic detail. It is shown that, if fluctuations are activated, gauche state bond probabilities increase, and the persistence length decreases, so that the polymer becomes more folded. Macromolecular stretching is also analyzed in presence of CR (the charge depends on the applied force) and without CR (the charge is fixed to the value at zero force). The analysis of the low force scaling behavior concludes that Pincus exponent becomes pH-dependent. Both with and without CR, a transition from 1/2 at high pH-values (phantom chain) to 3/5 to low pH-values (Pincus regime), is observed. Finally, the intermediate force stretching regime is investigated. It is found that CR induces a moderate influence in the force-extension curves and persistence length (which in this force regime becomes force-dependent). It is thus concluded that the effect of CR on the stretching curves is mainly due to changes in the average charge at zero force. It is also found that, for the cases studied, the effect of steric excluded volume is almost irrelevant compared to electrostatic interactions.

The Role of Alkalis in Hydraulic Mixtures

2019 ◽  
Vol 955 ◽  
pp. 62-67
Author(s):  
Lukáš Procházka ◽  
Jana Boháčová
Keyword(s):  
Mechanical Properties ◽  
Blast Furnace ◽  
Blast Furnace Slag ◽  
Alkali Silica Reaction ◽  
Type Ii ◽  
Hydration Products ◽  
Experimental Part ◽  
Ph Values ◽  
Furnace Slag

Alkali substances are present in cements used as a binder in concrete only in a minimum content. The most known process that alkali causes is the alkali-silica reaction. In this reaction, the alkali contained in the cement or supplied from the outside with an inappropriately selected aggregate containing amorphous SiO2. This reaction results in the development of hydration products, resulting in an increase in the volume of the original components, which can cause a breakage of the concrete structure and subsequent disintegration. The range of alkali-silica reaction can be reduced by the use of a suitable aggregate or the use of Type II admixtures which are characterized by pozzolanic or latently hydraulic activity. These admixtures react with alkali and then no longer react with the amorphous SiO2 contained in the aggregate. Alkalis also affect other properties of concrete such as basic physical-mechanical properties, frost resistance and pH.In the experimental part the pH values were compared between mixtures of Portland cement and alkaline activated blast furnace slag using slag aggregate from the heap Koněv.

Protein Adsorption at Charged Surfaces: The Role of Electrostatic Interactions and Interfacial Charge Regulation

Langmuir ◽  
2011 ◽  
Vol 27 (6) ◽  
pp. 2634-2643 ◽  
Author(s):  
Rune A. Hartvig ◽  
Marco van de Weert ◽  
Jesper Østergaard ◽  
Lene Jorgensen ◽  
Henrik Jensen
Keyword(s):  
Protein Adsorption ◽  
Electrostatic Interactions ◽  
Charge Regulation ◽  
Charged Surfaces ◽  
Interfacial Charge

scholarly journals Mechanical Behavior and Constitutive Model for Loess Samples under Simulated Acid Rain Conditions

2021 ◽  
Author(s):  
xia ye ◽  
Enlong Liu ◽  
Baofeng Di ◽  
yayang yu
Keyword(s):  
Mechanical Properties ◽  
Acid Rain ◽  
Mechanical Model ◽  
Ph Value ◽  
Simulated Acid Rain ◽  
Test Results ◽  
Hardening Model ◽  
Ph Values ◽  
Scanning Electron ◽  
Peak Value

Abstract In this paper, the sulfuric acid solution is diluted to pH 5.0, 4.0 and 3.0 to simulate the acid rain condition, and the triaxial compressional tests and scanning electron microscope are carried out to study the mechanical properties and evolution of the microstructure of the saturated loess samples. The results demonstrate that acid rain increases the porosity of loess samples, and the pore distribution is not uniform, so that the mechanical properties of loess samples change. With the decrease of pH value, the peak value of the deviatoric stress and the volumetric contraction of loess samples decreases, which causes the strength of soil to decrease. Furthermore, the framework of the chemical-mechanical model for loess under the action of acid rain is established, in which the loess is considered as porous medium material, and the variable of acid rain at different pH values through the degree of chemical reaction is taken into account in the double-hardening model, and the model is also verified by the triaxial test results finally.

scholarly journals Revisiting the fundamentals of p-nitrophenol analysis for its application in the quantification of lipases activity. A graphical update.

Uniciencia ◽  
2020 ◽  
Vol 34 (2) ◽  
pp. 31-43
Author(s):  
Randall Syedd-León ◽  
Manuel Sandoval-Barrantes ◽  
Humberto Trimiño-Vásquez ◽  
Luis Roberto Villegas-Peñaranda ◽  
Gerardo Rodríguez-Rodríguez
Keyword(s):  
Lipase Activity ◽  
Ph Value ◽  
Protonated Form ◽  
Spectrophotometric Analysis ◽  
Spectrophotometric Methods ◽  
Ph Values ◽  
Reaction Media ◽  
Activity Quantification

p-Nitrophenol (pNP) is a widely used compound for analytical determinations of several esterases (EC. 3.1.1.X), including lipases (E.C. 3.1.1.3). Most enzymatic measurements employ pNP derivatives such as esters, which are broken down by enzymatic hydrolysis, releasing pNP that is quantified by its absorbance at 410 nm. Although this type of methods was developed a few decades ago, the spectrophotometric analysis of pNP requires analytical measurements of pH and temperature to achieve reliable determinations. The aim of this paper is to offer a graphical update of how pH and temperature affect the p-nitrophenol absorbance at different wavelengths in lipase emulsified media, due to its relevance for the quantitative determination of lipase activity using spectrophotometric methods. To highlight the importance of each variable involved in this analysis, we dissolved pNP in emulsified media (for lipase activity quantification) at several pH values from 4.00 to 11.00, and measured its absorbance in a range of 270 nm – 500 nm and at several temperatures from 25°C to 50°C. The absorption patterns of pNP under the established conditions were graphed in 3D plots. The constructed 3D plots showed that, regardless of the temperature, below pH 6.00, pNP predominantly absorbs at 317 nm, due to the greater abundance of its protonated form, which is completely predominant at pH 3.50 and below. On the other hand, at pH 10.0 and above, the major absorption occurs at about 401 nm, confirming that the equilibrium is completely shifted to the pNP anionic form. These results also indicate that close to neutral pH value pNP, it displays a temperature dependence effect, increasing absorbance to 410 nm at higher temperatures. Due to many analytical determinations of enzymatic activities, the release of pNP is carried around pH 7.00. It is necessary to consider the determinant role of both pH and temperature over these measurements, how these variables must be strictly controlled, and how the calibration curves and blanks should take the reaction media pH and temperature into account.

The Role of Acetate in Denitrification and Biological Phosphate Removal in Modified Bardenpho Systems

1989 ◽  
Vol 21 (4-5) ◽  
pp. 375-385 ◽  
Author(s):  
C. T. Winter
Keyword(s):  
Sodium Acetate ◽  
Ph Value ◽  
Phosphate Removal ◽  
Organic Substances ◽  
Phosphate Release ◽  
Ph Values ◽  
Experimental Systems ◽  
Removal Capacity ◽  
Equivalent Sequence

The importance of easily biodegradable organic substances such as acetate and propionate in biological phosphate removal has been recognised by many researchers. Laboratory-scale studies on the performance of three-stage modified Bardenpho nutrient removal systems, fed with settled sewage supplemented with 0, 50, 100 and 200 mg/l sodium acetate respectively are described. Particular attention is given to the effects of these additions on biological phosphate release and uptake and also to the fate of parameters such as pH, calcium, potassium, ammonia and nitrate. Additional phosphate of 10 mg/l (as P) was initially introduced into the feed in order to burden the experimental systems beyond their normal phosphate removal capacity. This was increased to 20 mg/l and eventually to 40 mg/l of phosphate (as P). Increasing concentrations of sodium acetate resulted in distinct increases in pH values, increase in phosphate release in the anaerobic zones and significantly improved overall phosphate removal in the experimental units. The correlation of phosphate removal on acetate concentration was found to be 0.9886. In some instances the unit receiving 200 mg/l acetate removed up to an average of 30 mg/l of phosphate (as P), constituting an improvement of up to 200% compared with the unit receiving no acetate. The alternating release and uptake of phosphate was accompanied by an equivalent sequence for potassium and magnesium. The high pH value plus the disappearance of phosphate, ammonia and magnesium places doubt on a purely biological phosphate removal but could point at the crystallization of ammonium magnesium phosphate.

scholarly journals Improving the Cellular Uptake of Biomimetic Magnetic Nanoparticles

Nanomaterials ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 766
Author(s):  
Federica Vurro ◽  
Ylenia Jabalera ◽  
Silvia Mannucci ◽  
Giulia Glorani ◽  
Alberto Sola-Leyva ◽  
...  
Keyword(s):  
Magnetic Nanoparticles ◽  
Electrostatic Interactions ◽  
Ph Value ◽  
Cell Uptake ◽  
The Novel ◽  
Tat Peptide ◽  
Ph Values ◽  
Cell Internalization ◽  
Drug Nanocarriers

Magnetococcus marinus magnetosome-associated protein MamC, expressed as recombinant, has been proven to mediate the formation of novel biomimetic magnetic nanoparticles (BMNPs) that are successful drug nanocarriers for targeted chemotherapy and hyperthermia agents. These BMNPs present several advantages over inorganic magnetic nanoparticles, such as larger sizes that allow the former to have larger magnetic moment per particle, and an isoelectric point at acidic pH values, which allows both the stable functionalization of BMNPs at physiological pH value and the molecule release at acidic (tumor) environments, simply based on electrostatic interactions. However, difficulties for BMNPs cell internalization still hold back the efficiency of these nanoparticles as drug nanocarriers and hyperthermia agents. In the present study we explore the enhanced BMNPs internalization following upon their encapsulation by poly (lactic-co-glycolic) acid (PLGA), a Food and Drug Administration (FDA) approved molecule. Internalization is further optimized by the functionalization of the nanoformulation with the cell-penetrating TAT peptide (TATp). Our results evidence that cells treated with the nanoformulation [TAT-PLGA(BMNPs)] show up to 80% more iron internalized (after 72 h) compared to that of cells treated with BMNPs (40%), without any significant decrease in cell viability. This nanoformulation showing optimal internalization is further characterized. In particular, the present manuscript demonstrates that neither its magnetic properties nor its performance as a hyperthermia agent are significantly altered due to the encapsulation. In vitro experiments demonstrate that, following upon the application of an alternating magnetic field on U87MG cells treated with BMNPs and TAT-PLGA(BMNPs), the cytotoxic effect of BMNPs was not affected by the TAT-PLGA enveloping. Based on that, difficulties shown in previous studies related to poor cell uptake of BMNPs can be overcome by the novel nanoassembly described here.

scholarly journals Characterizing the impact of MnO2 addition on the efficiency of Fe0/H2O systems

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Viet Cao ◽  
Ghinwa Alyoussef ◽  
Nadège Gatcha-Bandjun ◽  
Willis Gwenzi ◽  
Chicgoua Noubactep
Keyword(s):  
Ph Value ◽  
Iron Corrosion ◽  
Dissolved Iron ◽  
Ph Values ◽  
Solid Iron ◽  
Initial Ph ◽  
Fixation Capacity ◽  
Co Precipitation ◽  
The Impact

AbstractThe role of manganese dioxide (MnO2) in the process of water treatment using metallic iron (Fe0/H2O) was investigated in quiescent batch experiments for t ≤ 60 d. MnO2 was used as an agent to control the availability of solid iron corrosion products (FeCPs) while methylene blue (MB) was an indicator of reactivity. The investigated systems were: (1) Fe0, (2) MnO2, (3) sand, (4) Fe0/sand, (5) Fe0/MnO2, and (6) Fe0/sand/MnO2. The experiments were performed in test tubes each containing 22.0 mL of MB (10 mg L−1) and the solid aggregates. The initial pH value was 8.2. Each system was characterized for the final concentration of H+, Fe, and MB. Results show no detectable level of dissolved iron after 47 days. Final pH values varied from 7.4 to 9.8. The MB discoloration efficiency varies from 40 to 80% as the MnO2 loading increases from 2.3 to 45 g L−1. MB discoloration is only quantitative when the operational fixation capacity of MnO2 for Fe2+ was exhausted. This corresponds to the event where adsorption and co-precipitation with FeCPs is intensive. Adsorption and co-precipitation are thus the fundamental mechanisms of decontamination in Fe0/H2O systems. Hybrid Fe0/MnO2 systems are potential candidates for the design of more sustainable Fe0 filters.

scholarly journals The role of pH values in porcine reproductive tracts of male and female individuals

2008 ◽  
Vol 24 (3-4) ◽  
pp. 101-108 ◽  
Author(s):  
T. Smiljakovic ◽  
S. Josipovic ◽  
O. Kosovac ◽  
N. Delic ◽  
S. Aleksic ◽  
...  
Keyword(s):  
Reproductive Tract ◽  
Ph Value ◽  
Rete Testis ◽  
Female Reproductive Tract ◽  
Ductus Deferens ◽  
Male And Female ◽  
Ph Values ◽  
Small Peak

For a long time, in practice, and science, has been known that pH values of sperm and vagina are important for successful fertilization. In this investigation this fact was confirmed, and the goal was to investigate the role of pH values through whole reproductive tract of male and female individuals: testis, rete testis, epididymis, ductus deferens, Cowper's gland, vesicula seminalis, prostata, corpus cavernosus, corpus spongiosus, epitel tissue of penis tube, sperm, vagina, uterus, horn of uterus, oviduct, fimbrie ovarica, ovarium, follicular fluid. Measurement was performed in reproductive active males as well as before and after ovulation in females. Porcine reproductive tracts (per 15 female and male individuals) were collected from institute's slaughterhouse, immediately post mortem dissected, homogenised and pH values were measured (according to method Rede&Rahelic (1969)). Ovarium and follicular liquid have the highest pH values (7,4) in females, but a small peak in preovulatory oviduct is also present and corresponded to pH of sperm of reproductive fully active male individuals (pH=app.7,2). After fertilization pH in surrounding of zygot (through depolarisation of its membrane) in oviduct, and zygot which then has external decreased pH value moves to less pH values regions by the same principle, that means to uterus, (pH between 7,2 (horn) and 7,07(cervix)) in postovulatory female reproductive tract, where nidation of blastocyst occurs. This investigation could help to elucidate knowledge about reproductive physiology in vivo, giving importance to role of pH values along reproductive tract of male and female individuals.

pH-Effect on Sinterability, Mechanical Properties and Cytotoxicity of Hydroxyapatite-Based Bone Grafts

2013 ◽  
Vol 319 ◽  
pp. 134-139
Author(s):  
Mehtap Demirel ◽  
Bunyamin Aksakal ◽  
Nese Basak
Keyword(s):  
Mechanical Properties ◽  
Ph Value ◽  
Ph Effect ◽  
Sol Gel ◽  
Bone Grafts ◽  
Quantitative Phase Analysis ◽  
Osteoblast Cells ◽  
Ph Values ◽  
Hardness Tests ◽  
Before And After

Hydroxyapatite (HA) based bone grafts were synthesized by sol-gel method at various pH values 5, 7, 9 and 12, respectively. In order to ascertain the influence of the obtained bone grafts on the morphology, sinterability and mechanical properties, each composition was sintered at 11500C, and quantitative phase analysis was characterized by XRD and FTIR. The microstructures were studied via SEM-EDX and the validation of mechanical properties was evaluated by compression and Vickers hardness tests. The density of HA synthesis samples with different pH values before and after sintering were measured. Besides, the cytotoxicity analysis were conducted for all grafts having various pH values. The experimental results revealed that the density and mechanical strenght of HA based bone grafts were increased with increasing pH value. The highest hardness and strength were obtained for the samples having pH=12. Furthermore, the samples with pH=12 exhibited the best densification and properties when compared to the samples at pH of 5, 7 and 9. The cytotoxicity tests also indicated that the pH=7-12 value showed no toxicity to osteoblast cells at 0,1 and 0,3 µM concentration, whereas HA synthesis sample at pH=5 value with 0,3 µM concentration induced significantly and reduced cell viability.

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