scholarly journals d-, l- and d,l-Tryptophan-Based Polyamidoamino Acids: pH-Dependent Structuring and Fluorescent Properties

Polymers ◽  
2019 ◽  
Vol 11 (3) ◽  
pp. 543 ◽  
Author(s):  
Federica Lazzari ◽  
Amedea Manfredi ◽  
Jenny Alongi ◽  
Daniele Marinotto ◽  
Paolo Ferruti ◽  
...  

Chiral polyamidoamino acids were obtained by polyaddition of N,N’-methylenebisacrylamide with d-, d,l- and l-tryptophan (M-d-Trp, M-d,l-Trp and M-l-Trp). l-tryptophan/glycine copolymers, M-G-l-Trp5, M-G-l-Trp10, M-G-l-Trp20 and M-G-l-Trp40, were prepared from l-tryptophan/glycine mixtures. These polymers were amphoteric, with acid-base properties similar to those of the parent amino acids. The l-tryptophan/glycine copolymers with high glycine content were water soluble in the pH range 2-12. M-G-l-Trp40 showed a solubility gap centred at pH 4.5 and all tryptophan homopolymers were soluble only at pH > 7. Dynamic light scattering measurements performed in their solubility ranges, namely 2-11 M-G-l-Trp5, M-G-l-Trp10 and M-G-l-Trp20 and 7-11 for M-G-l-Trp40, M-d-Trp, M-l-Trp and M-d,l-Trp, showed that the size of all samples did not significantly vary with pH. Both M-l-Trp and M-G-l-Trp copolymers showed pH-dependent circular dichroism spectra in the wavelength interval 200–280 nm, revealing structuring. All samples were fluorescent. Their emission spectra were unstructured and, if normalized for their tryptophan content, almost superimposable at the same pH, providing evidence that only tryptophan governed the photoluminescence properties. Changing pH induced in all cases a slight shift of the emission wavelength maximum ascribed to the modification of the microenvironment surrounding the indole ring induced by different protonation degrees.

1982 ◽  
Vol 37 (3) ◽  
pp. 262-265 ◽  
Author(s):  
Jerzy Grzywacz ◽  
Stanisława Taszner

Abstract Absorption and emission spectra of 6,7-dihydroxycoumarin [6,7-DHC] in aqueous solution over a wide pH range are reported. The absorption spectra proved to be strongly sensitive to the pH-value of the solution, whereas the emission spectra change in this range only insignificantly. An interpretation is attempted on the basis of the differences of the acid-base properties of the 6,7-DHC molecule in its ground and excited singlet state. For this purpose the pKa's and pKax's values have been calculated. It has been stated that in the excited state the phototautomer form is very unlikely.


1965 ◽  
Vol 58 (11P2) ◽  
pp. 961-963 ◽  
Author(s):  
M D Milne

Changes in acid-base balance have a profound influence on many aspects of the action of drugs. This is illustrated by data on the absorption of drugs from the stomach and intestine, in changes in distribution of drugs between plasma and cells, and the effect of change in urinary pH. As a general principle, these changes in the pharmacology of weak acids and bases are governed by physicochemical principles, which influence the proportion of the ionized and unionized components according to the pH of the medium and also to the peculiar property of biological membranes which allow the free passage of the lipoid-soluble unionized component and impede transfer of the water-soluble ionized fraction. Lipoid-soluble weak acids are excreted at higher clearances in alkaline urine, and conversely weak bases in acid urine. This is shown to be of practical importance in the treatment of poisoning, in the diagnosis of addiction to drugs and in studies of drug metabolism. In general, the excretion of natural metabolites is less likely to be influenced by urinary pH, as these substances are usually less lipoid-soluble than many widely used drugs. pH-dependent excretion is, however, of practical importance in relation to the urinary content of many indolic metabolites and also in the excretion of pigments derived from the degradation of hæmoglobin. Urobilinogen excretion is certainly pH-dependent, a higher clearance rate occurring in alkaline urine. However, work is necessary to decide whether some of the porphyrins also show this important physiological property.


RSC Advances ◽  
2014 ◽  
Vol 4 (43) ◽  
pp. 22651-22659 ◽  
Author(s):  
Wenchao Ding ◽  
Yong Liu ◽  
Yijing Li ◽  
Qiurong Shi ◽  
Houshen Li ◽  
...  

We present a simple strategy for synthesis of water-soluble, monodisperse, highly fluorescent gold nanoclusters (Au NCs) with sizes of 1.8 nm by co-reduction of glutathione and citrate for 24 h at 50 °C. The fluorescence intensity of the GS/C–Au NCs obtained is pH-dependent and can be reversibly adjusted in the pH range from 4.1 to 8.6.


2019 ◽  
Author(s):  
Jonas Landsgesell ◽  
Oleg Rud ◽  
Pascal Hebbeker ◽  
Raju Lunkad ◽  
Peter Košovan ◽  
...  

We introduce the grand-reaction method for coarse-grained simulations of acid-base equilibria in a system coupled to a reservoir at a given pH and concentration of added salt. It can be viewed as an extension of the constant-pH method and the reaction ensemble, combining explicit simulations of reactions within the system, and grand-canonical exchange of particles with the reservoir. Unlike the previously introduced methods, the grand-reaction method is applicable to acid-base equilibria in the whole pH range because it avoids known artifacts. However, the method is more general, and can be used for simulations of any reactive system coupled to a reservoir of a known composition. To demonstrate the advantages of the grand-reaction method, we simulated a model system: A solution of weak polyelectrolytes in equilibrium with a buffer solution. By carefully accounting for the exchange of all constituents, the method ensures that all chemical potentials are equal in the system and in the multi-component reservoir. Thus, the grand-reaction method is able to predict non-monotonic swelling of weak polyelectrolytes as a function of pH, that has been known from mean-field predictions and from experiments but has never been observed in coarse-grained simulations. Finally, we outline possible extensions and further generalizations of the method, and provide a set of guidelines to enable safe usage of the method by a broad community of users.<br><br>


2019 ◽  
Vol 26 (10) ◽  
pp. 743-750 ◽  
Author(s):  
Remya Radha ◽  
Sathyanarayana N. Gummadi

Background:pH is one of the decisive macromolecular properties of proteins that significantly affects enzyme structure, stability and reaction rate. Change in pH may protonate or deprotonate the side group of aminoacid residues in the protein, thereby resulting in changes in chemical and structural features. Hence studies on the kinetics of enzyme deactivation by pH are important for assessing the bio-functionality of industrial enzymes. L-asparaginase is one such important enzyme that has potent applications in cancer therapy and food industry.Objective:The objective of the study is to understand and analyze the influence of pH on deactivation and stability of Vibrio cholerae L-asparaginase.Methods:Kinetic studies were conducted to analyze the effect of pH on stability and deactivation of Vibrio cholerae L-asparaginase. Circular Dichroism (CD) and Differential Scanning Calorimetry (DSC) studies have been carried out to understand the pH-dependent conformational changes in the secondary structure of V. cholerae L-asparaginase.Results:The enzyme was found to be least stable at extreme acidic conditions (pH< 4.5) and exhibited a gradual increase in melting temperature from 40 to 81 °C within pH range of 4.0 to 7.0. Thermodynamic properties of protein were estimated and at pH 7.0 the protein exhibited ΔG37of 26.31 kcal mole-1, ΔH of 204.27 kcal mole-1 and ΔS of 574.06 cal mole-1 K-1.Conclusion:The stability and thermodynamic analysis revealed that V. cholerae L-asparaginase was highly stable over a wide range of pH, with the highest stability in the pH range of 5.0–7.0.


2001 ◽  
Vol 675 ◽  
Author(s):  
Jeong-Seo Park ◽  
Han-Chang Kang ◽  
Kurt E. Geckeler

ABSTRACTAs [60]fullerene is a very hydrophobic macromolecule, there have been a number of attempts to make it more hydrophilic for biomedical applications. By attaching hydrophilic moieties such as poly(oxyethylene)(POE) chains and cyclodextrin molecules to [60]fullerene, novel water-soluble and biocompatible materials have been successfully prepared [1,2].The synthesis of novel macrocyclic fullerene conjugates which are water-soluble is reported. The telechelic fullerene derivatives have been prepared via addition reaction of POE-based arms with covalently bonded β-cyclodextrin (CD) to [60]fullerene. To this end, a mono-tosylated CD derivative has been prepared in pyridine and then reacted with an amino-functional POE in the presence of triethylamine. The subsequent reaction of [60]fullerene with the hydrophilic POE-conjugated CD-derivative yielded the macrofullerene after separation and purification procedures.The macrocyclic [60]fullerene derivatives obtained were soluble in water and characterized by UV-VIS and FT-IR spectroscopy as well as light scattering measurements and thermogravimetric analysis.


1999 ◽  
Vol 112 (5) ◽  
pp. 613-622 ◽  
Author(s):  
J.V. Jester ◽  
T. Moller-Pedersen ◽  
J. Huang ◽  
C.M. Sax ◽  
W.T. Kays ◽  
...  

In vivo corneal light scattering measurements using a novel confocal microscope demonstrated greatly increased backscatter from corneal stromal fibrocytes (keratocytes) in opaque compared to transparent corneal tissue in both humans and rabbits. Additionally, two water-soluble proteins, transketolase (TKT) and aldehyde dehydrogenase class 1 (ALDH1), isolated from rabbit keratocytes showed unexpectedly abundant expression (approximately 30% of the soluble protein) in transparent corneas and markedly reduced levels in opaque scleral fibroblasts or keratocytes from hazy, freeze injured regions of the cornea. Together these data suggest that the relatively high expressions of TKT and ALDH1 contribute to corneal transparency in the rabbit at the cellular level, reminiscent of enzyme-crystallins in the lens. We also note that ALDH1 accumulates in the rabbit corneal epithelial cells, rather than ALDH3 as seen in other mammals, consistent with the taxon-specificity observed among lens enzyme-crystallins. Our results suggest that corneal cells, like lens cells, may preferentially express water-soluble proteins, often enzymes, for controlling their optical properties.


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