NMR Studies of the Reaction of Amino Acids with Aqueous Chlorine

Author(s):  
Frank E. Scully, Jr ◽  
Barbara Conyers

Over the past 20 years, gas chromatography/mass spectroscopy (GC/MS) has been widely used to identify trace organic environmental contaminants and to study the mechanisms of the formation or transformation of organic compounds either by natural or man-made processes. In the area of water and wastewater disinfection, GC/MS has been highly successful in identifying numerous volatile organic chlorination by-products, some of which may pose undesirable health risks to humans and aquatic organisms at concentrations found in some waters. However, despite a considerable amount of research in this area much of the chemistry continues to be poorly understood. Analysis of trace organics by GC/MS relies on the assumption that the compounds to be analyzed are (1) volatile and (2) thermally stable to GC temperatures as high as 300 °C. Because nuclear magnetic resonance spectroscopy (NMR) is a mild and nondestructive method of analysis, it can reveal reactions that occur in water that cannot be observed by GC/MS. Until recently the reactions of amino acids with two or more equivalents of aqueous chlorine were believed to produce aldehydes and nitriles according to equation (1). LeCloirec and Martin have reported that the formation of nitriles in such situations may come in part from the reaction of monochloramine with aldehydes (equation (2)). Because reaction (2) may affect the distribution of products in reaction (1), it was important to determine the relationship between these two reactions. This chapter will review the applications of NMR we have used in studies of the products formed upon chlorination of amino acids.

2006 ◽  
Vol 26 (20) ◽  
pp. 7707-7718 ◽  
Author(s):  
Nadya Latysheva ◽  
Gairat Muratov ◽  
Sundaresan Rajesh ◽  
Matthew Padgett ◽  
Neil A. Hotchin ◽  
...  

ABSTRACT Tetraspanins are clustered in specific microdomains (named tetraspanin-enriched microdomains, or TERM) in the plasma membrane and regulate the functions of associated transmembrane receptors, including integrins and receptor tyrosine kinases. We have identified syntenin-1, a PDZ domain-containing protein, as a new component of TERM and show that syntenin-1 specifically interacts with the tetraspanin CD63. Detailed biochemical and heteronuclear magnetic resonance spectroscopy (NMR) studies have demonstrated that the interaction is mediated by the C-terminal cytoplasmic region of the tetraspanin and the PDZ domains of syntenin-1. Upon interaction, NMR chemical shift perturbations were predominantly localized to residues around the binding pocket of PDZ1, indicating a specific mode of recognition of the cytoplasmic tail of CD63. In addition, the C terminus of syntenin-1 has a stabilizing role in the CD63-syntenin-1 association, as deletion of the last 17 amino acids abolished the interaction. The CD63-syntenin-1 complex is abundant on the plasma membrane, and the elevated expression of the wild-type syntenin-1 slows down constitutive internalization of the tetraspanin. Furthermore, internalization of CD63 was completely blocked in cells expressing a syntenin-1 mutant lacking the first 100 amino acids. Previous results have shown that CD63 is internalized via AP-2-dependent mechanisms. Hence, our data indicate that syntenin-1 can counteract the AP-2-dependent internalization and identify this tandem PDZ protein as a new regulator of endocytosis.


2014 ◽  
Vol 16 (3) ◽  
pp. 561-577 ◽  

<p>It is well known that chlorine and its compounds, traditionally utilized for water and wastewater disinfection, react with some organic matter to form undesirable by-products, hazardous to human health, known as Disinfection By-Products (DBPs). In many countries very stringent limits for chlorination by-products such as trihalomethanes were set for wastewater reuse. Accordingly, the use of different oxidation/disinfection systems should be evaluated as possible alternative to chlorine. Ultrasound (US) was recently found to be effective for this purpose.</p> <p>Aim of this work is to review main US disinfection studies, pointing out ultrasound mechanisms as well as its effects in terms of different bacteria inactivation (<em>Total coliform, Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, Saccharomyces cerevisiae, Klebsiella pneumonia</em>) at both laboratory scale and pilot-scale. To this end, several experimental results were discussed and both focal interest points and encountered problems were summarized.</p> <div> <p>Moreover the intensification of cavitation phenomena by combined oxidation processes was overviewed and main advantages and disadvantages were pointed out, in order to address future research and promote efficient large scale operations.&nbsp;</p> </div> <p>&nbsp;</p>


1997 ◽  
Vol 161 ◽  
pp. 179-187
Author(s):  
Clifford N. Matthews ◽  
Rose A. Pesce-Rodriguez ◽  
Shirley A. Liebman

AbstractHydrogen cyanide polymers – heterogeneous solids ranging in color from yellow to orange to brown to black – may be among the organic macromolecules most readily formed within the Solar System. The non-volatile black crust of comet Halley, for example, as well as the extensive orangebrown streaks in the atmosphere of Jupiter, might consist largely of such polymers synthesized from HCN formed by photolysis of methane and ammonia, the color observed depending on the concentration of HCN involved. Laboratory studies of these ubiquitous compounds point to the presence of polyamidine structures synthesized directly from hydrogen cyanide. These would be converted by water to polypeptides which can be further hydrolyzed to α-amino acids. Black polymers and multimers with conjugated ladder structures derived from HCN could also be formed and might well be the source of the many nitrogen heterocycles, adenine included, observed after pyrolysis. The dark brown color arising from the impacts of comet P/Shoemaker-Levy 9 on Jupiter might therefore be mainly caused by the presence of HCN polymers, whether originally present, deposited by the impactor or synthesized directly from HCN. Spectroscopic detection of these predicted macromolecules and their hydrolytic and pyrolytic by-products would strengthen significantly the hypothesis that cyanide polymerization is a preferred pathway for prebiotic and extraterrestrial chemistry.


2019 ◽  
Vol 20 (7) ◽  
pp. 644-651 ◽  
Author(s):  
Changsong Gu ◽  
Xiangbing Mao ◽  
Daiwen Chen ◽  
Bing Yu ◽  
Qing Yang

Branched chain amino acids are the essential nutrients for humans and many animals. As functional amino acids, they play important roles in physiological functions, including immune functions. Isoleucine, as one of the branched chain amino acids, is also critical in physiological functions of the whole body, such as growth, immunity, protein metabolism, fatty acid metabolism and glucose transportation. Isoleucine can improve the immune system, including immune organs, cells and reactive substances. Recent studies have also shown that isoleucine may induce the expression of host defense peptides (i.e., &#946;-defensins) that can regulate host innate and adaptive immunity. In addition, isoleucine administration can restore the effect of some pathogens on the health of humans and animals via increasing the expression of &#946;-defensins. Therefore, the present review will emphatically discuss the effect of isoleucine on immunity while summarizing the relationship between branched chain amino acids and immune functions.


1994 ◽  
Vol 59 (11) ◽  
pp. 2523-2532 ◽  
Author(s):  
John Hondrelis ◽  
John Matsoukas ◽  
George Agelis ◽  
Paul Cordopatis ◽  
Ning Zhou ◽  
...  

The conformation of [Sar1]angiotensin II in water at neutral pH has been examined by proton magnetic resonance spectroscopy at 400 MHz and in particular by comparing its 1H NMR spectral data with those of analogues modified at positions 1,4 and 6, namely [Sar1,Cha8]ANGII, [Des Asp1,Cha8]ANGII, [Aib1,Tyr(Me)4]ANGII, [Aib1,Tyr(Me)4,Ile8]ANGII, [N-MeAib1,Tyr(Me)4]ANGII, [N-MeAib1,Tyr(Me)4,Ile8]ANGII, ANGIII and [Sar1,Ile8]ANGII. Assignment of all proton resonances in these analogues was made possible by 2D COSY NMR experiments. The H-2 and H-4 protons for the histidine ring in [Sar1]ANGII, ANGII and ANGIII were shielded compared with the same protons in [Sar1,Ile8]ANGII, [Sar1,Cha8]ANGII and [Des Asp1,Cha8]ANGII; this shielding effect was not disturbed upon methylation of the tyrosine hydroxyl and/or replacement of residue 1 (sarcosine or aspartic acid) with aminoisobutyric acid (Aib) or N-methyl aminoisobutyric acid (N-MeAib). These data are consistent with our previous suggestion based on NMR studies in neutral DMSO that a characteristic folded conformation for ANGII previously observed in non-polar solvents can also be detected in water at neutral pH, but to a lesser degree.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Robert A. McCutcheon ◽  
Toby Pillinger ◽  
Maria Rogdaki ◽  
Juan Bustillo ◽  
Oliver D. Howes

AbstractAlterations in cortical inter-areal functional connectivity, and aberrant glutamatergic signalling are implicated in the pathophysiology of schizophrenia but the relationship between the two is unclear. We used multimodal imaging to identify areas of convergence between the two systems. Two separate cohorts were examined, comprising 195 participants in total. All participants received resting state functional MRI to characterise functional brain networks and proton magnetic resonance spectroscopy (1H-MRS) to measure glutamate concentrations in the frontal cortex. Study A investigated the relationship between frontal cortex glutamate concentrations and network connectivity in individuals with schizophrenia and healthy controls. Study B also used 1H-MRS, and scanned individuals with schizophrenia and healthy controls before and after a challenge with the glutamatergic modulator riluzole, to investigate the relationship between changes in glutamate concentrations and changes in network connectivity. In both studies the network based statistic was used to probe associations between glutamate and connectivity, and glutamate associated networks were then characterised in terms of their overlap with canonical functional networks. Study A involved 76 individuals with schizophrenia and 82 controls, and identified a functional network negatively associated with glutamate concentrations that was concentrated within the salience network (p < 0.05) and did not differ significantly between patients and controls (p > 0.85). Study B involved 19 individuals with schizophrenia and 17 controls and found that increases in glutamate concentrations induced by riluzole were linked to increases in connectivity localised to the salience network (p < 0.05), and the relationship did not differ between patients and controls (p > 0.4). Frontal cortex glutamate concentrations are associated with inter-areal functional connectivity of a network that localises to the salience network. Changes in network connectivity in response to glutamate modulation show an opposite effect compared to the relationship observed at baseline, which may complicate pharmacological attempts to simultaneously correct glutamatergic and connectivity aberrations.


Cosmetics ◽  
2021 ◽  
Vol 8 (2) ◽  
pp. 48
Author(s):  
Carmen G. Sotelo ◽  
María Blanco ◽  
Patricia Ramos ◽  
José A. Vázquez ◽  
Ricardo I. Perez-Martin

Long life expectancy of populations in the developing world together with some cultural and social issues has driven the need to pay special attention to health and physical appearance. Cosmeceuticals are gaining interest in the cosmetic industry as their uses fulfills a double purpose: the requirements of a cosmetic (clean, perfume, protect, change the appearance of the external parts of the body or keeping them in good condition) with a particular bioactivity function. The cosmetics industry, producing both cosmetics and cosmeceuticals, is currently facing numerous challenges to satisfy different attitudes of consumers (vegetarianism, veganism, cultural or religious concerns, health or safety reasons, eco-friendly process, etc.). A currently growing trend in the market is the interest in products of low environmental impact. Marine origin ingredients are increasingly being incorporated into cosmeceutical preparations because they are able to address several consumer requirements and also due to the wide range of bioactivities they present (antioxidant, whitening, anti-aging, etc.). Many companies claim “Marine” as a distinctive marketing signal; however, only a few indicate whether they use sustainable ingredient sources. Sustainable marine ingredients might be obtained using wild marine biomass through a sustainable extractive fishing activity; by adopting valorization strategies including the use of fish discards and fish by-products; and by sustainably farming and culturing marine organisms.


2019 ◽  
Vol 183 ◽  
pp. 109493 ◽  
Author(s):  
Rose Marie O.F. Sousa ◽  
Carla Amaral ◽  
Joana M.C. Fernandes ◽  
Irene Fraga ◽  
Sabrina Semitela ◽  
...  

1984 ◽  
Vol 38 (2) ◽  
pp. 177-179 ◽  
Author(s):  
B.S. Chauhan ◽  
N.C. Desai ◽  
Ramesh Bhatnagar ◽  
S.P. Garg

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