scholarly journals Metal Coordination Properties of a Chromophoric Desferrioxamine (DFO) Derivative: Insight on the Coordination Stoichiometry and Thermodynamic Stability of Zr4+ Complexes

Molecules ◽  
2021 ◽  
Vol 27 (1) ◽  
pp. 184
Author(s):  
Matteo Savastano ◽  
Francesca Boscaro ◽  
Antonio Bianchi
Keyword(s):  
Mass Spectrometry ◽  
Gold Standard ◽  
Critical Case ◽  
Model System ◽  
Emission Tomography ◽  
Metal Coordination ◽  
Coordination Properties ◽  
Coordination Model ◽  
Potentiometric Measurements ◽  
The Stability

Desferrioxamine (DFO) is the current “gold standard” chelator for 89Zr4+, which is used to label monoclonal antibodies for applications in immunopositron emission tomography. Recently, controversial data have been reported regarding the speciation and the stability of the complexes formed by DFO with Zr4+ in solution. To shed some light on this point, we studied the coordination properties in solution ofa chromophoric DFO derivative bearing a substituted pyrimidine residue (DFO–Pm) toward several metal ions (Zr4+, Cu2+, Zn2+, Mg2+, Ca2+, Na+, K+). Potentiometric titrations showed that DFO–Pm and pristine DFO form complexes with very similar stoichiometry and stability. DFO–Pm, which can consequently be taken as a model system for DFO, provides a photochemical response to metal coordination that can be used to further define the complexes formed. In the critical case of Zr4+, spectrophotometric measurements allowed the verification of the formation of 1:1 and 2:3 complexes that, together with 2:2 complexes form the coordination model that was obtained through the use of our potentiometric measurements. Additionally, mass spectrometry measurements verified the formation of 1:1 and 2:3 complexes and showed that 1:2 species can be easily generated through the fragmentation of the 2:3 species. In conclusion, the results obtained with DFO–Pm validate the complexation model of Zr4+/DFO composed of 1:1, 2:2, and 2:3 metal-to-ligand complexes. Convergences and conflicts with other works are addressed.

Stability and Folding of the Unusually Stable Hemoglobin from Synechocystis is Subtly Optimized and Dependent on the Key Heme Pocket Residues.

2020 ◽  
Vol 27 ◽  
Author(s):  
Sheetal Uppal ◽  
Mohd. Asim Khan ◽  
Suman Kundu
Keyword(s):  
Molten Globule ◽  
Life Forms ◽  
Model System ◽  
Heme Pocket ◽  
The Past ◽  
Specific Manner ◽  
Delivery Vehicles ◽  
The Stability ◽  
Key Residues ◽  
Synechocystis Sp

Aims: The aim of our study is to understand the biophysical traits that govern the stability and folding of Synechocystis hemoglobin, a unique cyanobacterial globin that displays unusual traits not observed in any of the other globins discovered so far. Background: For the past few decades, classical hemoglobins such as vertebrate hemoglobin and myoglobin have been extensively studied to unravel the stability and folding mechanisms of hemoglobins. However, the expanding wealth of hemoglobins identified in all life forms with novel properties, like heme coordination chemistry and globin fold, have added complexity and challenges to the understanding of hemoglobin stability, which has not been adequately addressed. Here, we explored the unique truncated and hexacoordinate hemoglobin from the freshwater cyanobacterium Synechocystis sp. PCC 6803 known as “Synechocystis hemoglobin (SynHb)”. The “three histidines” linkages to heme are novel to this cyanobacterial hemoglobin. Objective: Mutational studies were employed to decipher the residues within the heme pocket that dictate the stability and folding of SynHb. Methods: Site-directed mutants of SynHb were generated and analyzed using a repertoire of spectroscopic and calorimetric tools. Result: The results revealed that the heme was stably associated to the protein under all denaturing conditions with His117 playing the anchoring role. The studies also highlighted the possibility of existence of a “molten globule” like intermediate at acidic pH in this exceptionally thermostable globin. His117 and other key residues in the heme pocket play an indispensable role in imparting significant polypeptide stability. Conclusion: Synechocystis hemoglobin presents an important model system for investigations of protein folding and stability in general. The heme pocket residues influenced the folding and stability of SynHb in a very subtle and specific manner and may have been optimized to make this Hb the most stable known as of date. Other: The knowledge gained hereby about the influence of heme pocket amino acid side chains on stability and expression is currently being utilized to improve the stability of recombinant human Hbs for efficient use as oxygen delivery vehicles.

scholarly journals Dynamical study of infochemical influences on tropic interaction of diffusive plankton system

2021 ◽  
Vol 3 (3) ◽  
Author(s):  
Satish Kumar Tiwari ◽  
Ravikant Singh ◽  
Nilesh Kumar Thakur
Keyword(s):  
Dimethyl Sulfide ◽  
Algal Bloom ◽  
Turing Instability ◽  
Model System ◽  
Ode Model ◽  
Estuarine Ecosystem ◽  
Dynamical Study ◽  
Oscillatory Dynamics ◽  
The Stability ◽  
Microzooplankton Grazing

AbstractWe propose a model for tropic interaction among the infochemical-producing phytoplankton and non-info chemical-producing phytoplankton and microzooplankton. Volatile information-conveying chemicals (infochemicals) released by phytoplankton play an important role in the food webs of marine ecosystems. Microzooplankton is an ecologically important grazer of phytoplankton for coexistence of a large number of phytoplankton species. Here, we discuss how information transferred by dimethyl sulfide shapes the interaction of phytoplankton. Phytoplankton deterrents may lead to propagation of IPP bloom. The interaction between IPP and microzooplankton follows the Beddington–DeAngelis-type functional response. Analytically, we discuss boundedness, stability and Turing instability of the model system. We perform numerical simulation for temporal (ODE model) as well as a spatial model system. Our numerical investigation shows that microzooplankton grazing refuse of IPP leads to oscillatory dynamics. Increasing diffusion coefficient of microzooplankton shows Turing instability. Time evolution also plays an important role in the stability of system dynamics. The results obtained in this paper are useful to understand the dominance of algal bloom in coastal and estuarine ecosystem.

scholarly journals Superiority of MALDI-TOF Mass Spectrometry over Real-Time PCR for SARS-CoV-2 RNA Detection

Viruses ◽  
2021 ◽  
Vol 13 (5) ◽  
pp. 730
Author(s):  
Magda Rybicka ◽  
Ewa Miłosz ◽  
Krzysztof Piotr Bielawski
Keyword(s):  
Mass Spectrometry ◽  
Gold Standard ◽  
Viral Genome ◽  
False Negative ◽  
Rt Pcr ◽  
Rna Detection ◽  
Maldi Tof ◽  
Negative Results ◽  
False Negative Results ◽  
Pcr Test

At present, the RT-PCR test remains the gold standard for early diagnosis of SARS-CoV-2. Nevertheless, there is growing evidence demonstrating that this technique may generate false-negative results. Here, we aimed to compare the new mass spectrometry-based assay MassARRAY® SARS-CoV-2 Panel with the RT-PCR diagnostic test approved for clinical use. The study group consisted of 168 suspected patients with symptoms of a respiratory infection. After simultaneous analysis by RT-PCR and mass spectrometry methods, we obtained discordant results for 17 samples (10.12%). Within fifteen samples officially reported as presumptive positive, 13 were positive according to the MS-based assay. Moreover, four samples reported by the officially approved RT-PCR as negative were positive in at least one MS assay. We have successfully demonstrated superior sensitivity of the MS-based assay in SARS-CoV-2 detection, showing that MALDI-TOF MS seems to be ideal for the detection as well as discrimination of mutations within the viral genome.

scholarly journals Application of Lipid Class Ratios for Sample Stability Monitoring—Evaluation of Murine Tissue Homogenates and SDS as a Stabilizer

Metabolites ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 277
Author(s):  
Sabrina Krautbauer ◽  
Raquel Blazquez ◽  
Gerhard Liebisch ◽  
Marcus Hoering ◽  
Philip Neubert ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Lipid Class ◽  
High Resolution Mass Spectrometry ◽  
Lipolytic Activity ◽  
Sodium Dodecyl ◽  
Lipid Profiles ◽  
Lipolytic Action ◽  
Sample Stability ◽  
Tissue Homogenates ◽  
The Stability

Lipids are a ubiquitous class of structurally complex molecules involved in various biological processes. In the fast-growing field of lipidomics, preanalytical issues are frequently neglected. Here, we investigated the stability of lipid profiles of murine liver, brain, lung, heart, and spleen homogenates by quantitative flow injection analysis using tandem mass spectrometry and high-resolution mass spectrometry. Storage of tissue homogenates at room temperature showed substantial alterations of the lipid profiles reflecting lipolytic action. Therefore, ratios of ceramide to sphingomyelin, lysophosphatidylethanolamine to phosphatidylethanolamine, lysophosphatidylcholine to phosphatidylcholine, and diglyceride to triglyceride were applied to monitor sample stability and the effect of sodium dodecyl sulfate (SDS) as a potential stabilizing agent. The addition of SDS led to a concentration-dependent stabilization of lipid profiles in liver, brain, and heart homogenates, while in lung and spleen homogenates, in particular, the lysophosphatidylethanolamine to phosphatidylethanolamine ratio increased upon addition of SDS. In conclusion, we demonstrated that lipid class ratios reflecting lipolytic activity could be applied to evaluate both the stability of samples and the influence of stabilizers.

scholarly journals Stability of Nonlinear Autonomous Quadratic Discrete Systems in the Critical Case

2010 ◽  
Vol 2010 ◽  
pp. 1-23 ◽  
Author(s):  
Josef Diblík ◽  
Denys Ya. Khusainov ◽  
Irina V. Grytsay ◽  
Zdenĕk Šmarda
Keyword(s):  
Lyapunov Functions ◽  
Critical Case ◽  
Autonomous Systems ◽  
Discrete Systems ◽  
Simple Eigenvalue ◽  
Discrete Equations ◽  
The Matrix ◽  
The Stability ◽  
Important Characterization

Many processes are mathematically simulated by systems of discrete equations with quadratic right-hand sides. Their stability is thought of as a very important characterization of the process. In this paper, the method of Lyapunov functions is used to derive classes of stable quadratic discrete autonomous systems in a critical case in the presence of a simple eigenvalueλ=1of the matrix of linear terms. In addition to the stability investigation, we also estimate stability domains.

scholarly journals Development and validation of the method for the detection of glimepiride via derivatization employing N-methyl-N-(trimethylsilyl) trifluoroacetamide using gas chromatography-mass spectrometry

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Priyanka Verma ◽  
Atul Bajaj ◽  
R. M. Tripathi ◽  
Sudhir K. Shukla ◽  
Suman Nagpal
Keyword(s):  
Diabetes Mellitus ◽  
Mass Spectrometry ◽  
Gas Chromatography ◽  
Drug Users ◽  
Coefficient Of Determination ◽  
Gas Chromatography Mass Spectrometry ◽  
Biological Matrices ◽  
Chromatography Mass Spectrometry ◽  
Ms Analysis ◽  
The Stability

Abstract Background Recent advances in the diversified anti-diabetic drugs have appeared in the startling increase in the count of poisoning cases. The epidemics of diabetes mellitus are increasing; hence, the no. of anti-diabetic drug users raised by 42.9%. The use of glimepiride raised to 24%. As the toxicity and drug cases are also escalating with increasing epidemics of diabetes mellitus, a novel gas chromatography-mass spectrometry (GC-MS) method for detecting glimepiride in biological matrices is developed. Results Liquid-liquid extraction method was employed by using 1-butanol: hexane (50:50, v/v) under an alkaline medium, and then back extraction was done via acetic acid. Distinct derivatization techniques were employed for the sample preparation for GC-MS analysis, i.e., silylation and acylation. Derivatization approaches were optimized under different parameters, i.e., reaction temperature and reaction time. N-Methyl-N-(trimethylsilyl) trifluoroacetamide [MSTFA] was found to be the best sound derivatization reagent for the GC-MS analysis of glimepiride. Total ion current (TIC) mode was selected for the monitoring of ions of trimethylsilyl (TMS) derivative of glimepiride with an m/z ratio of 256. Distinct parameters like specificity, carryover, stability, precision, and accuracy were evaluated for validating the identification method. The GC-MS method is found to be linear and illustrated within the range 500 to 2500 ng/ml with the value of R2 (coefficient of determination) at 0.9924. The stability of the extracted and derivatized glimepiride was accessed with regard to processed/extracted sample conditions and autosampler conditions, respectively. Accuracy at each concentration level was within the + 15% of the nominal concentration. Precision (%) for the interday and intraday analysis was found to be in the respectable spectrum. Conclusion Henceforth, the proposed GC-MS method can be employed for the determination of glimepiride in biological matrices.

scholarly journals Mass Spectrometry Imaging Using Dynamically Harmonized FT-ICR at Million Resolving Power: Rationalizing and Optimizing Sample Preparation and Instrumental Parameters

2020 ◽  
Author(s):  
Mathieu Tiquet ◽  
Raphaël La Rocca ◽  
Daan van Kruining ◽  
Pilar Martinez-Martinez ◽  
Gauthier Eppe ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
High Resolution ◽  
Mass Spectrometry Imaging ◽  
Mass Range ◽  
Maldi Mass Spectrometry ◽  
Mass Accuracy ◽  
Ion Current ◽  
Resolving Power ◽  
Lipid Mass ◽  
The Stability

<p><i>MALDI mass spectrometry imaging (MSI) is a powerful analytical method giving access to the 2D localizations of compounds in a thin section of a sample. To properly discern isobaric compounds in complex biological samples, dynamically harmonized ICR cell (ParaCell©) has been introduce to achieve extreme spectral resolution. However, high resolution MS images realized on a 9.4T FTICR High resolution instrument with recommended parameters suffered from an abnormal shifting of m/z ratios pixel to pixel. Resulting datasets show poor mass accuracy measurements and resolutions under estimations. By following the behavior of the Total Ion Current in function of the number of laser shots, the abnormal mass shifting phenomenon has been linked to the stability of the Total Ion Current (TIC) during images acquisitions. An optimization of laser parameters is proposed in order to limit the observed mass shift to retain machine specifications during MSI analyses. It is also shown that the method has been successfully employed to realize quality MS images with resolution above 1,000,000 in the lipid mass range across the whole image.</i></p>

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