This study unveils a new catalytic crossover reaction of sulfinamides. Leveraging mild acid catalysis, the reaction demonstrates a high tolerance to structural variations, yielding equimolar products across diverse sulfinamide substrates. Notably, small sulfinamide libraries can be selectively oxidized to sulfonamides, providing a new platform for ligand optimization and discovery in medicinal chemistry.
View Article and Find Full Text PDFAn anesthetized cat animal model was used to evaluate changes in cough and swallow after a small midline upper abdominal incision (laparotomy). Two additional conditions were tested: sealing the laparotomy with gentle suctioning via a small cannula, and subsequent closure of the abdominal wall with suture. These abdominal wall manipulations resulted in no changes in the cough reflex, but produced higher motor drive to pharyngeal musculature (thyropharyngeus and geniohyoid muscles) during swallow.
View Article and Find Full Text PDFMobile wireless communication technologies have now become an everyday part of our lives, 24 hours a day, 7 days a week. Monitoring the autonomous system under exposition to electromagnetic fields may play an important role in broading of our still limited knowledge on their effect on human body. Thus, we studied the interaction of the high frequency electromagnetic field (HF EMF) with living body and its effect on the autonomic control of heart rate using Heart Rate Variability (HRV) linear and nonlinear analyses in healthy volunteers.
View Article and Find Full Text PDFWe describe a straightforward one-pot reductive protocol for the synthesis of sulfinamides from sulfonyl chlorides. This method enables the preparation of sulfinamides with a broad range of functional groups. Furthermore, we have expanded a known oxidative pathway to sulfinamides starting from thiols.
View Article and Find Full Text PDFPurpose: We investigated iron accumulation and the possible mechanisms in the rabbit cerebellum after the exposure to the real GSM and generated radiofrequency electromagnetic fields (RF EMF) using inductively coupled plasma mass spectrometry (ICP MS) and particles induced X-ray emission (PIXE).
Materials And Methods: Four groups of rabbits were exposed to the real EMF, generated EMF, combination of both the real and generated signals and the control group with no exposition. For determination of iron concentration in the four groups of cerebellum samples ICP MS was used.
Many serious diseases are associated with degenerative changes caused by oxidative stress triggered by elevated concentrations of reactive oxygen species (ROS) in cells. Therefore, the development of suitable probes for monitoring such processes is of great importance. Here, we introduce a series of sulfur- and selenium-substituted BODIPY derivatives as reversible redox sensors for ROS and enzymatic redox processes.
View Article and Find Full Text PDFA novel concept of nonhydrolytic enzyme sensing based on aggregation-induced emission is described. As a proof of principle, fluorogenic probes for methionine sulfoxide reductases have been developed. Changes in the polarity and electronic nature upon reduction of sulfoxide to sulfide are translated to the aggregation potential of the probe.
View Article and Find Full Text PDFDephosphorylation inhibitor calyculin A (cal A) has been reported to inhibit the disappearance of radiation-induced γH2AX DNA repair foci in human lymphocytes. However, other studies reported no change in the kinetics of γH2AX focus induction and loss in irradiated cells. While apoptosis might interplay with the kinetics of focus formation, it was not followed in irradiated cells along with DNA repair foci.
View Article and Find Full Text PDFThe aim of this study was to assess the effects of radiofrequency electromagnetic field (RF EMF) on heart rate variability (HRV) in rabbits with intensity slightly exceeding the limits for occupations. Totally 21 New Zealand white rabbits divided into two groups were used in this double-blind study. The first group of animals without general anesthesia was subjected to HRV examination under exposure to a device generated RF EMF source (frequency 1788 MHz, intensity 160 V/m, lasting 150 min.
View Article and Find Full Text PDFWe report on the development of high-throughput fluorogenic assay that can streamline directed evolution of enantioselective sulfoxide reductases. As a model, methionine sulfoxide reductase A (MsrA) has been evolved to expand its limited substrate scope. The resulting mutant MsrA can resolve a range of new challenging racemic sulfoxides with high efficiency including the pharmaceutically relevant albendazole sulfoxide.
View Article and Find Full Text PDFOptogenetic tools have revolutionized the study of receptor-mediated processes, but such tools are lacking for RNA-controlled systems. In particular, light-activated regulatory RNAs are needed for spatiotemporal control of gene expression. To fill this gap, we used in vitro selection to isolate a novel riboswitch that selectively binds the isoform of a stiff-stilbene (amino-SS)-a rapidly and reversibly photoisomerizing small molecule.
View Article and Find Full Text PDFChem Commun (Camb)
August 2019
A new enzymatic assay for the preparation of chiral sulfoxides that is enantiocomplementary to the known (S)-enantiomer-reducing activity of methionine sulfoxide reductase A (MsrA) is described. To this end, we have utilized the enzyme DMSO reductase (DmsABC), recently discovered by us being highly upregulated in stationary phase E. coli bacteria.
View Article and Find Full Text PDFNonenzymatic oxidative processes in living organisms are among the inevitable consequences of respiration and environmental conditions. These oxidative processes can lead to the formation of two stereoisomers (R and S) of methionine sulfoxide, and the redox balance between methionine and methionine sulfoxide in proteins has profound implications on their function. Methionine oxidation can be reverted enzymatically by methionine sulfoxide reductases (Msrs).
View Article and Find Full Text PDFThe role of pulmonary stretch receptor discharge and volume feedback in modulation of tracheobronchial cough is not fully understood. The current study investigates the effect of expiratory occlusion with or without preceding inspiratory resistance (delivery of tidal or cough volume by the ventilator lasting over the active cough expiratory period) on the cough motor pattern. Experiments on 9 male cats under pentobarbital sodium anesthesia have shown that inspiratory resistance followed by expiratory occlusion increased cough inspiratory and expiratory efforts and prolonged several time intervals (phases) related to muscle activation during cough.
View Article and Find Full Text PDFPrevious studies of physiological responses to music and noise showed the effect on the autonomic nervous system. The heart rate variability (HRV) has been used to assess the activation of the sympathetic and the parasympathetic nervous systems. The present study was aimed to examine HRV with exposure to four sine-wave pure tones (20 Hz, 50 Hz, 2 kHz and 15 kHz) in an environment where the sound intensity exceeded level 65 dB (A-weighted).
View Article and Find Full Text PDFThe highly enantioselective enzyme methionine sulfoxide reductase A was combined with an oxaziridine-type oxidant in a biphasic setup for the deracemization of chiral sulfoxides. Remarkably, high ee values were observed with a wide range of substrates, thus providing a practical route for the synthesis of enantiomerically pure sulfoxides.
View Article and Find Full Text PDFRespir Physiol Neurobiol
November 2018
GABA, muscimol, and baclofen were microinjected into the rostral (rNTS) and caudal solitary tract nucleus (cNTS) in 24 anesthetized cats. Electromyograms (EMGs) of diaphragm (DIA) and abdominal muscles (ABD), blood pressure and esophageal pressure (EP) were recorded and analysed. Bilateral microinjections of 1 mM GABA (total 66 ± 4 nl), 1 mM baclofen (64 ± 4 nl) and unilateral microinjections of 0.
View Article and Find Full Text PDFThis study examines the possible effect of radiofrequency (RF) electromagnetic fields (EMF) on the autonomic nervous system (ANS). The effect of RF EMF on ANS activity was studied by measuring heart rate variability (HRV) during ortho-clinostatic test (i.e.
View Article and Find Full Text PDFBackground: Mobile phone application may cause structural, functional changes and accumulation of toxic elements in brain.
Objectives: The aim of this study was to investigate iron accumulation in rabbit cerebellum after exposure to RF EMF with light and scanning electron microscopy.
Materials And Methods: Histochemical analysis of iron distribution by light and electron microscopy with energy-dispersive microanalysis was used.
Reversal of the sense of enantioselectivity was observed between 1-aza[6]helicene 2 and 2-aza[6]helicene 3 employed as chiral inducers of asymmetric autocatalysis of pyrimidyl alkanol. In the presence of (P)-(+)-1-aza[6]helicene 2, the reaction of pyrimidine-5-carbaldehyde 1 with diisopropylzinc afforded, in conjunction with asymmetric autocatalysis, (S)-pyrimidyl alkanol 4 with high ee. Surprisingly, the reaction in the presence of (P)-(+)-2-aza[6]helicene 3 gave the opposite enantiomer of (R)-alkanol 4 with high ee.
View Article and Find Full Text PDFMethionine sulfoxide reductase A (MsrA) is an enzyme involved in redox balance and signaling, and its aberrant activity is implicated in a number of diseases (for example, Alzheimer's disease and cancer). Since there is no simple small molecule tool to monitor MsrA activity in real time in vivo, we aimed at developing one. We have designed a BODIPY-based probe called (S)-Sulfox-1, which is equipped with a reactive sulfoxide moiety.
View Article and Find Full Text PDFThe effect of volume-related feedback and output airflow resistance on the cough motor pattern was studied in 17 pentobarbital anesthetized spontaneously-breathing cats. Lung inflation during tracheobronchial cough was ventilator controlled and triggered by the diaphragm electromyographic (EMG) signal. Altered lung inflations during cough resulted in modified cough motor drive and temporal features of coughing.
View Article and Find Full Text PDFA comprehensive study on the physicochemical properties of a series of mono- and diaza[5]helicenes as well as mono- and diaza[6]helicenes is reported. Through the use of both computational and experimental methods, these helically chiral pyridohelicenes with the nitrogen atom(s) in various positions are characterised according to their inversion barriers, protonation constants and redox potentials. By using DFT calculations, kinetic measurements, UV/Vis titrations, cyclic voltammetry and EPR spectroscopy, a self-contained picture of their behaviour under conventional treatment by heat, acids and oxidising/reducing agents is provided.
View Article and Find Full Text PDFA general synthetic methodology for the preparation of functionalized (hetero)helicenes has been developed. It employs the sequence of a double propargyl organometallics (Li, Mg, Ga/In) addition to a tolan-2,2'-dialdehyde-type intermediate, a cobalt-catalyzed/cobalt-mediated [2 + 2 + 2] cycloisomerization of a triyne intermediate, and a double silica gel-assisted acetic acid elimination to receive pentahelicene, 1,14-diazapentahelicene, and 3,12-dichloro-, 3,12-dichloro-7-trimethylsilyl-, and 3,12-di-tert-butylpentahelicene. 3,12-Dichloropentahelicene undergoes a Suzuki-Miyaura coupling with aryl boronic acids (or ester) under palladium catalysis to afford 3,12-diarylpentahelicenes.
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