Proton Magnetic Resonance Research Articles

Monometallic heteroleptic complexes of Dy(III) ion incorporating β-diketone and ancillary moieties: Photophysical and electrochemical analyses

Several luminescent ternary dysprosium complexes were synthesized and examined using diketone ligand 1,3-diphenylprop-1,3-dione (DPD) and various auxiliary ligands. Spectroscopic analysis was carried out to determine the structural and photophysical features of Dy (III) complexes. IR and proton NMR spectroscopic studies suggested the bonding of chelating moieties to the metal ion through oxygen and nitrogen atom. The optical and electronic band gap is evaluated which proposed the conducting behaviour of dysprosium complexes. Upon excitation with UV radiation, three distinct emission peaks of the Dy (III) ion are appeared at about 485 nm (J = 15/2), 575 nm (13/2) and 664 nm (11/2) corresponding to the transitions of type 4F9/2 → 6HJ. The strongest emission peak obtained at ∼ 575 nm is responsible for yellow emission of Dy (III) complexes. The yellow to blue (Y/B) ratio estimated for the transition J = 13/2 / J = 15/2 were found to be in the range of 4.19 – 2.80. The quantum yield was also determined for the Dy (III) complexes which is as: Φ1 = 0.315, Φ2 = 0.261, Φ3 = 0.183, Φ4 = 0.157. The synthesized dysprosium complexes demonstrate luminescence lifetime in decreasing order i.e. 0.600 ms > 0.510 ms > 0.431 ms > 0.323 ms. Furthermore, the chromaticity coordinates also confirm their yellow luminous behavior. These newly synthesized complexes could be utilized for developing systems significant for lighting, OLEDs and displays due to their luminous features.

Evaluation of adsorption behaviour of benzylidene chitosan derivatives at mild steel/ 0.5 M H2SO4 solution interface

Four green benzylidene chitosan derivatives (BCs) were synthesized and evaluated as anti-corrosive substances for the first time against mild steel corrosion in 0.5 M H2SO4 solution. The synthesized BCs were laid to infrared spectroscopy and proton resonance spectroscopy for structural confirmation. Gravimetric and electrochemical experiments were accustomed to appraise the effectiveness of inhibitors, however, Scanning Electron Microscopy-Electron Dispersive Spectroscopy (SEM-EDS), Atomic Force Microscopy (AFM), and X-ray Photoelectron Spectroscopy (XPS) were exploited to evaluate the protective mechanism offered by benzylidene chitosan derivatives. Experimental results demarcate the synthesized inhibitors; Anisaldehyde modified Chitosan (CMB), 2-Hydroxy-4-methoxybenzaldehyde modified Chitosan (CHMB), 2,4-Dimethoxybenzaldehyde modified Chitosan (CDMB) and 2-Bromo-4-methoxybenzaldehyde modified Chitosan (CBMB) exhibiting praising inhibitory properties for mild steel corrosion and CDMB was seen possessed preferable inhibition potential at the finest concentration of 500 mgL-1 owing to the proximity of two electron-donating OCH3 groups. Furthermore, the inhibitors have been recorded to behave mixed type with pronounced impact on hydrogen evolution kinetics. The order of inhibition efficacy obtained was CDMB (98.8 %) > CHMB (95.4 %) > CMB (92.8 %) > CBMB (89.2 %) which was further validated by quantum chemical calculations which later opened up about the mechanistic approach involved in electron transfer from inhibitors to metallic vacant orbitals. Additionally, the effect of molecular structure possessed by synthesized inhibitors has been correlated with observed variation in their corrosion inhibition efficiency.

In vitro analysis of quercetin-like compounds from mistletoe Dendrophthoe pentandra (L.) Miq as a potential antiviral agent for Newcastle disease

Background Recent evidence suggests that some flavonoid compounds obtained from crude methanol extract of mistletoe leaves (Dendrophthoe pentandra L. Miq), also known as Benalu Duku (BD), have antimicrobial effects. Thus, the plant has the potential to eliminate viruses that may cause outbreaks in chicken farms. This study aimed to prove the in vitro ability of flavonoid compounds, namely quercetin-like compounds (QLCs), to eliminate field viruses, specifically the Newcastle disease virus (NDV). Methods This research was performed in two stages. An in vitro test was used with a post-test of the control groups designed at a significance of 0.05. BD leaves (5 kg) were extracted using a maceration method with methanol and then separated into hexane, chloroform, ethyl acetate, and methanol fractions. The final extracted products were separated using semi-preparative high-performance liquid chromatography (HPLC) to obtain QLCs. The QLCs were identified and compared with quercetin using HPLC, proton and carbon nuclear magnetic resonance spectrometry, Fourier transform infrared spectrophotometry and ultra-performance liquid chromatography-mass spectrometry. The activity of QLCs was tested in vitro against the NDV at a virulence titter of 10−5 Tissue Culture Infectious Dose 50% (TCID50) in chicken kidney cell culture. Results Solutions of 0.05% (w/v) QLCs were discovered to have antiviral activity against NDVs, with an average cytopathogenic effect antigenicity at a 10−5 dilution (p<0.05). Conclusions QLCs from flavonoids from the leaves of BD have in vitro antiviral bioactivity against NDV at a virulence titter of 10-5 Tissue Culture Infectious Dose 50% (TCID50) in chicken kidney cell culture. QLCs may have the potential to be developed as medicinal compounds for the treatment of other human or animal viral infections.

Rising Importance of Proton Magnetic Resonance Spectroscopy in the Diagnosis of Selected Neurodegenerative Diseases of the Brain

Introduction: Neurodegenerative diseases pose a significant diagnostic challenge due to the increasing elderly population and the rising prevalence of these conditions. State of Knowledge: Differential diagnosis among these diseases is particularly challenging; thus, numerous clinical trials have been conducted to identify markers that could facilitate accurate disease diagnosis. Among various diagnostic approaches, imaging techniques play a crucial role, especially magnetic resonance imaging (MRI), which includes advanced modalities such as proton magnetic resonance spectroscopy (¹H-MRS). ¹H-MRS offers a non-invasive assessment of neurometabolite profiles, providing critical information that aids in precise diagnosis. Conclusions: With ongoing clinical trials, the importance of ¹H-MRS in diagnosing neurodegenerative diseases continues to grow. This paper reviews the results of recent and relevant clinical trials examining changes in ¹H-MRS in the most prevalent neurodegenerative diseases.

Imbalance of thalamic metabolites in an experimental model of hypertension: role of bergamot polyphenols

Abstract Funding Acknowledgements None. Hypertension is emerging as a pathogenic factor in vascular-based cognitive impairment, altering the structure and function of cerebral vasculature, and representing the main risk factor for cerebral small vessel diseases and neuronal loss. Some studies correlated a reduction in regional cerebral blood flow in the thalamus of elderly hypertensive brains with the decrease in certain cerebral metabolites, because of hypoperfusion. Patients with severe hypertension show a reduced oxygen consumption in regions with reduced cerebral blood flow suggesting that, the vascular dysfunction and the reduced cerebral blood flow could be related to reduced metabolic demands due to brain dysfunction and damage. Chronic cerebral hypoperfusion is associated with increased inflammatory state and oxidative stress. Herein, we hypothesized to prevent or reduce the onset of oxidative stress using natural occurring antioxidant compounds could be of particular importance for the management of hypertension-induced cerebral complications. Hypertension was induced on Wistar male rats by left renal artery ligation (RAL). After complete recovery from surgery, the animals were treated with 20 mg/kg deoxycorticosterone acetate twice a week for 4 weeks, and 1% sodium chloride (NaCl) water. A subgroup of hypertensive rats received Bergamot Polyphenolic Fraction (BPF) by gavage. A control group was treated with sub-cutaneous injection of saline. At baseline (T0), after 2 weeks (T1) and at the end of the experimental period (T2), the thalamic neurochemical profile were evaluated using proton magnetic resonance spectroscopy (1H-MRS), performed with a Bruker Pharmascan 70/16 7T. VAPOR water-suppression module was used and optimized to reduce residual water, then thalamic spectra were acquired using a short echo time single voxel point-resolved spectroscopy technique (voxel size 3x3x3 mm). The absolute quantification of metabolite concentrations has been performed using TARQUIN (v.4.3.10). A reduction tending to significance of the tNAA/tCr ratio, emerged in the thalamus of RAL DOCA-Salt rats compared to control rats at T2. A significant reduction of the tNAA/tCr ratio was observed in the group of RAL DOCA-Salt rats at the T2 compared to the same animals at the T1. In addition, a significantly decrease of the tCho/tCr ratio was highlighted in the RAL DOCA-Salt animals compared to the CTRL rats starting from the T1. The administration of BPF ameliorates the tNAA/tCr ratios in the thalamus of RAL DOCA-Salt rats. Such evidence of the influence of hypertension on tNAA/tCr and tCho/tCr ratios could better explain the relationship between brain structure and modulation of some metabolites, providing new insights into hypertension-induced brain complications and the contribution that the use of natural compounds could give to their management.

Glutamatergic neurotransmission in schizophrenia: A systematic review and quantitative synthesis of proton magnetic resonance spectroscopy studies across schizophrenia spectrum disorders.

Studies using proton magnetic resonance spectroscopy reveal substantial inconsistencies in the levels of brain glutamate, glutamine and glutamate + glutamine across schizophrenia spectrum disorders. This systematic review employs qualitative and quantitative methods to analyse the patterns and relationships between glutamatergic metabolites, schizophrenia spectrum disorders and brain regions. A literature search was conducted using various databases with keywords including glutamate, glutamine, schizophrenia, psychosis and proton magnetic resonance spectroscopy. Inclusion criteria were limited to case-control studies that reported glutamatergic metabolite levels in adult patients with a schizophrenia spectrum disorder diagnosis - i.e. first-episode psychosis, schizophrenia, treatment-resistant schizophrenia and/or ultra-treatment-resistant schizophrenia - using proton magnetic resonance spectroscopy at 3 T or above. Pooled study data were synthesized and analysed. A total of 92 studies met the inclusion criteria, including 2721 healthy controls and 2822 schizophrenia spectrum disorder participants. Glu levels were higher in the basal ganglia, frontal cortex and medial prefrontal of first-episode psychosis participants, contrasting overall lower levels in schizophrenia participants. For Gln, strong differences in metabolite levels were evident in the basal ganglia, dorsolateral prefrontal cortex and frontal cortex, with first-episode psychosis showing significantly higher levels in the basal ganglia. In glutamate + glutamine, higher metabolite levels were found across schizophrenia spectrum disorder groups, particularly in the basal ganglia and dorsolateral prefrontal cortex of treatment-resistant schizophrenia participants. Significant relationships were found between metabolite levels and medication status, clinical measures and methodological variables. The review highlights abnormal glutamatergic metabolite levels throughout schizophrenia spectrum disorders and in specific brain regions. The review underscores the importance of standardized future research assessing glutamatergic metabolites using proton magnetic resonance spectroscopy due to considerable literature heterogeneity.

Characterization of the surface-active exopolysaccharide produced by Halomonas sp TGOS-10: Understanding its role in the formation of marine oil snow.

In this study, we characterize the exopolymer produced by Halomonas sp. strain TGOS-10 -one of the organisms found enriched in sea surface oil slicks during the Deepwater Horizon oil spill. The polymer was produced during the early stationary phase of growth in Zobell's 2216 marine medium amended with glucose. Chemical and proton NMR analysis showed it to be a relatively monodisperse, high-molecular-mass (6,440,000 g/mol) glycoprotein composed largely of protein (46.6% of total dry weight of polymer). The monosaccharide composition of the polymer is typical to that of other marine bacterial exopolymers which are generally rich in hexoses, with the notable exception that it contained mannose (commonly found in yeast) as a major monosaccharide. The polymer was found to act as an oil dispersant based on its ability to effectively emulsify pure and complex oils into stable oil emulsions-a function we suspect to be conferred by the high protein content and high ratio of total hydrophobic nonpolar to polar amino acids (52.7:11.2) of the polymer. The polymer's chemical composition, which is akin to that of other marine exopolymers also having a high protein-to-carbohydrate (P/C) content, and which have been shown to effect the rapid and non-ionic aggregation of marine gels, appears indicative of effecting marine oil snow (MOS) formation. We previously reported the strain capable of utilising aromatic hydrocarbons when supplied as single carbon sources. However, here we did not detect biodegradation of these chemicals within a complex (surrogate Macondo) oil, suggesting that the observed enrichment of this organism during the Deepwater Horizon spill may be explained by factors related to substrate availability and competition within the complex and dynamic microbial communities that were continuously evolving during that spill.

Highly efficient CdS/CeO2/Ag3PO4 nanocomposite as novel heterogenous catalyst for Knoevenagel condensation and acetylation reactions

In light of environmental and economic concerns, the use of heterogeneous catalysts that can function under gentler reaction conditions has recently become popular. In this study by using the precipitation method, CdS/CeO2/Ag3PO4 ternary nanocomposites with varied molar proportions of CdS:CeO2/Ag3PO4 were produced. The catalysts' surface functional groups; morphology and crystal structures were examined using FTIR, SEM-EDX and XRD respectively. The catalytic efficiency of all synthesized nanomaterials was tested on a model Knoevenagel condensation reaction. For the best catalyst, selected from the screening, the optimization of reaction conditions such as the solvent, catalyst load, concentration of reagents such as malononitrile/acetic anhydride, and temperature. The ternary nanocomposite CdS/CeO2/Ag3PO4 (4:1) displayed higher catalytic activity (95.4 ± 3.2 %) than the rest of the nanomaterials prepared. Thus, the ternary nanocomposite CdS/CeO2/Ag3PO4 with 4:1 mol ratio with optimized reaction conditions was used to check the substrate scope of Knoevenagel condensation and acetylation reaction. The synthesized Knoevenagel condensation and acetylation reaction products were also characterized by proton and carbon NMR for their structure determination. The nanocomposite's reusability was carried out and only 7.5 ± 2 % decrement was witnessed after four runs and 23.3 % after the fifth run. and this indicates the potential application of the catalyst to organic reactions. Furthermore, we have proposed the possible catalytic mechanisms for both organic reactions.

Reactivity-based detection of nitrite ion: Rapid colorimetric and fluorometric response down to nM level

Recent developments in our lab provided significant insight into the structure–reactivity relationship between electronic properties and the detection of nitrite ions. By fine-tuning electron-withdrawing and electron-donating power, the sulfonamide group on aniline moiety was found to be the fastest nitrite probe among the first generation of probe molecules. Based on our understanding of the detection mechanism, our attention was moved to additional modification by installing stronger electron-donating groups on the azo-coupling partner. Accordingly, the bis methoxy group version of the probe molecule was prepared. It showed clean conversion from the probe to the benzo[c]cinnoline product and excellent linear response to very low levels of nitrite ions. Proton NMR and high-resolution mass spectrometer captured the reaction between the probe molecule and nitrite ions. As the reaction with nitrite ion triggers diazonium intermediate formation followed by intramolecular cyclization, both absorption and emission property changes were monitored as the signal readout to assay nitrite ion. In this report, our design principle of a probe molecule and its performance in colorimetric and fluorimetric responses will be discussed. In addition, the low detection limit achieved by leveraging chromatographic separation and assaying by the mass detector will be discussed.

Combining Dipole and Loop Coil Elements for 7 T Magnetic Resonance Studies of the Human Calf Muscle.

Combining proton and phosphorus magnetic resonance spectroscopy offers a unique opportunity to study the oxidative and glycolytic components of metabolism in working muscle. This paper presents a 7 T proton calf coil design that combines dipole and loop elements to achieve the high performance necessary for detecting metabolites with low abundance and restricted visibility, specifically lactate, while including the option of adding a phosphorus array. We investigated the transmit, receive, and parallel imaging performance of three transceiver dipoles with six pair-wise overlap-decoupled standard or twisted pair receive-only coils. With a higher SNR and more efficient transmission decoupling, standard loops outperformed twisted pair coils. The dipoles with standard loops provided a four-fold-higher image SNR than a multinuclear reference coil comprising two proton channels and 32% more than a commercially available 28-channel proton knee coil. The setup enabled up to three-fold acceleration in the right-left direction, with acceptable g-factors and no visible aliasing artefacts. Spectroscopic phantom measurements revealed a higher spectral SNR for lactate with the developed setup than with either reference coil and fewer restrictions in voxel placement due to improved transmit homogeneity. This paper presents a new use case for dipoles and highlights their advantages for the integration in multinuclear calf coils.

Adsorption simulation of 2,4-D pesticide on novel zinc-based 2-amino-4-(1H-1,2,4-triazole-4-yl)benzoic acid coordination complexes using machine learning approach.

The capacity of zinc-based 2-amino-4-(1H-1,2,4-triazole-4-yl)benzoic acid coordination complex (Zn(NH2-TBA)2) and modified Zn(NH-TBA)2COMe complex for removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solutions was investigated through adsorption modeling and artificial intelligence tools. Analyzing the adsorption characteristics of pesticides helps in studying the groundwater pollution by pesticides in agriculture area.In this study, Zn(NH2-TBA)2 was synthesized using Schiff base and its surface was modified using acetic anhydride group and their physical characteristics were identified using proton NMR, FTIR, and XRD. NMR results showed maximum modification yield obtained was 65% after 5days. The porous structure and surface area monitored using nitrogen isotherm and BET surface area analysis presented relatively less surface area and porosity after modification. Adsorption modelling indicated that Toth model with a maximum adsorption capacity of 150.8mg/g and 100.7mg/g represents the homogenous adsorption systems which satisfy both low- and high-end boundary of adsorbate concentration in all settings according to the optimum point, while the kinetics and rate of 2,4-D adsorption follow the pseudo-first-order kinetic model in all situations. Artificial neural network (ANN), support vector regression, and particle swarm optimized least squares-support vector regression (PSO-LSSVR) were used for the optimization and modelling of adsorbent mass, adsorbate concentration, contact time, and temperature to develop predictive equations for the simulation of the adsorption efficiency of 2,4-D pesticide. The obtained results exhibited the better performance of ANN and PSO-LSSVR for prediction of adsorption results. The mean square error values of ANN (0.001, 0.012) and PSO-LSSVR (0.121, 0.105) were obtained for Zn(NH2-TBA)2 and Zn(NH-TBA)2COMe, respectively, while their respective coefficient of determination (R2) obtained were 0.999 and 0.988 for ANN and 0.980 and 0.825 for PSO-LSSVR. The study specified that machine learning predictive behavior performed better for Zn(NH2-TBA)2 compared to Zn(NH-TBA)2COMe that is also supported by theoretical kinetics and isotherm models. The research concludes that artificial intelligence models are the most efficient tools for studying the predictive behavior of adsorption data.

Evaluation of the Glymphatic System in Schizophrenia Spectrum Disorder Using Proton Magnetic Resonance Spectroscopy Measurement of Brain Macromolecule and Diffusion Tensor Image Analysis Along the Perivascular Space Index.

The glymphatic system (GS), a brain waste clearance pathway, is disrupted in various neurodegenerative and vascular diseases. As schizophrenia shares clinical characteristics with these conditions, we hypothesized GS disruptions in patients with schizophrenia spectrum disorder (SCZ-SD), reflected in increased brain macromolecule (MM) and decreased diffusion-tensor-image-analysis along the perivascular space (DTI-ALPS) index. Forty-seven healthy controls (HCs) and 103 patients with SCZ-SD were studied. Data included 135 proton magnetic resonance spectroscopy (1H-MRS) sets, 96 DTI sets, with 79 participants contributing both. MM levels were quantified in the dorsal-anterior cingulate cortex (dACC), dorsolateral prefrontal cortex, and dorsal caudate (point resolved spectroscopy, echo-time = 35ms). Diffusivities in the projection and association fibers near the lateral ventricle were measured to calculate DTI-ALPS indices. General linear models were performed, adjusting for age, sex, and smoking. Correlation analyses examined relationships with age, illness duration, and symptoms severity. MM levels were not different between patients and HCs. However, left, right, and bilateral DTI-ALPS indices were lower in patients compared with HCs (P < .001). In HCs, age was positively correlated with dACC MM and negatively correlated with left, right, and bilateral DTI-ALPS indices (P < .001). In patients, illness duration was positively correlated with dACC MM and negatively correlated with the right DTI-ALPS index (P < .05). In the entire population, dACC MM and DTI-ALPS indices showed an inverse correlation (P < .01). Our results suggest potential disruptions in the GS of patients with SCZ-SD. Improving brain's waste clearance may offer a potential therapeutic approach for patients with SCZ-SD.

The Utility of Multiparametric Magnetic Resonance Imaging in Reducing Diagnostic Uncertainty for Primary Central Nervous System Lymphoma

AimA key limitation in the early treatment initiation in primary central nervous system lymphoma (PCNSL) is the diagnostic delay caused by lack of recognition of a lesion as a possible lymphoma, steroid initiation, and lesion involution, often resulting in inconclusive biopsy. We highlight the importance of multiparametric MRI (MPMRI), which incorporates diffusion weighted imaging (DWI), dynamic susceptibility contrast-enhanced perfusion weighted imaging (DSC-PWI) and proton magnetic resonance spectroscopy (1H-MRS) in addition to standard MRI sequences in resolving diagnostic uncertainty for PCNSL. Materials and methodsWe present a consecutive series of 10 patients at our centre with histology-proven PCNSL (specifically, diffuse large B-cell lymphoma of the CNS) who underwent multiparametric MRI. We retrospectively analyse the qualitative and semi-quantitative parameters and assess their radiological concordance for this diagnosis. ResultsWe note overall low apparent diffusion coefficient on DWI (mean ADCmin of 0.74), high percentage signal recovery on perfusion weighted imaging (mean 170%), a high choline-creatine ratio and a high-grade lipid peak on MRS giving a “twin-tower” appearance. Nine of ten patients had MRMRI findings concordant for PCNSL, defined as at least 3 of 4 parameters being consistent for PCNSL. ConclusionWe propose that concordance between these imaging multiparametric modalities could be used as a radiological predictor of PCNSL, reducing diagnostic delays, providing a more accurate biopsy target, and resulting in quicker treatment initiation.

α-Zr(HPO4)2·H2O: As an effective and recoverable catalyst for the synthesis of a family of quinoxalines in semi-aqueous conditions

In our work, we have established a straightforward and friendly process for the preparation of a family of quinoxaline. This method relies on using α-Zr(HPO4)2·H2O as a catalyst and an ethanol/water mixture as an ecological solvent. Firstly, we prepared α-Zr(HPO4)2·H2O by a simple hydrothermal procedure and conducted comprehensive characterization employing various analytical methods. On the other hand, we produced the quinoxalines by means of a condensation reaction between 1,2-dicarbonyl compounds and various 1,2-diamines. The synthesized quinoxaline and its derivative products were characterized by melting point, proton, and carbon nuclear magnetic resonance analysis. As a result, the optimal reaction conditions that resulted in a high yield (97–98 %) were an amount of catalyst of 0.03 g, a stirring time of 8 min, a volume of solvent of 2 mL, and a reaction temperature of 50 °C. This approach is advantageous due to its simple and eco-friendly procedure, green solvent, quick reaction time, low cost, and high yields. Additionally, it offers the possibility to recycle the catalyst for a minimum of five cycles with no decrease in its catalytic activity.

Differentiation of hemispheric white matter lesions in migraine and multiple sclerosis with similar radiological features using advanced MRI.

White matter hyperintensities (WMHs), presented on T2-weighted or fluid-attenuated inversion recovery magnetic resonance imaging (MRI) sequences, are lesions in the human brain that can be observed in both migraine and multiple sclerosis (MS). Seventeen migraine patients and 15 patients with relapsing-remitting multiple sclerosis with WMHs, and 17 healthy subjects age-and sex-matched to the migraine group were prospectively enrolled and underwent conventional and advanced MRI studies with diffusion-and perfusion-weighted imaging and single voxel proton magnetic resonance spectroscopy. In both disease groups, elevated T2 relaxation time, apparent diffusion coefficient (ADC) values, and decreased N-acetyl-aspartate levels were found in the intralesional white matter compared to the contralateral normal-appearing white matter (NAWM), while there was no difference between the hemispheres of the control subjects. Migraine patients had the lowest intralesional creatine + phosphocreatine and myo-inositol (mI) values among the three groups, while patients with MS showed the highest intralesional T1 and T2 relaxation times, ADC, and mI values. In the contralateral NAWM, the same trend with mI changes was observed in migraineurs and MS patients. No differences in perfusion variables were observed in any groups. Our multimodal study showed that tissue damage is detectable in both diseases. Despite the differences in various advanced MRI measures, with more severe injury detected in MS lesions, we could not clearly differentiate the two white matter lesion types.

Photo-responsive supramolecular polymer bottle-brushes: The key role of the solvent on self-assembly and responsiveness

HypothesisSupramolecular polymer bottlebrushes (SPBs) consist in the 1D self-assembly of building blocks composed of a self-assembling core with pendant polymer arms. Kinetic hurdles often hinder their stimuli-responsiveness in solution. Changing the nature of the solvent should alleviate these hurdles by modulating the self-association strength, leading to stimuli-responsive SPBs. ExperimentsThe SPBs were formed, in various solvents, by hydrogen bond-driven self-assembly of an azobenzene-bisurea decorated with poly(ethylene oxide) polymer arms. The photo-isomerization of the azobenzene unit was studied by UV/visible spectroscopy and proton NMR spectroscopy, whereas the consequences on supramolecular self-assembly were studied by small angle neutron and X-ray scattering. FindingsIn water, the assembly was previously shown to be driven by both hydrogen-bonds and strong hydrophobic effects, the latter rendering the system kinetically frozen and the disassembly irreversible. Here we show that in organic solvents such as toluene or chloroform, reversible light-responsive dissociation is achieved. Solvophobic effects in these solvents are expected to be much weaker than in water, which probably allows reversibility of the light-response in the former solvents. The key role of the solvent on the reversibility of the process opens up new perspectives for the design of stimuli-responsive SPBs and their applications in various fields.

Gender-related alterations of serum trace elements and neurometabolism in the anterior cingulate cortex of patients with major depressive disorder

BackgroundIt is widely known that sex differences have a significant impact on patients with major depressive disorder (MDD). This study aims to evaluate the sex-related connection between serum trace elements and changes in neurometabolism in the anterior cingulate cortex (ACC) of MDD patients. Methods109 untreated MDD patients and 59 healthy controls underwent proton magnetic resonance spectroscopy (1H-MRS) under resting conditions. We measured metabolic ratios in the ACC from both sides. Additionally, venous blood samples were taken from all participants to detect calcium (Ca), phosphorus, magnesium (Mg), copper (Cu), ceruloplasmin (CER), zinc (Zn), and iron (Fe) levels. We performed association and interaction analyses to explore the connections between the disease and gender. ResultsIn individuals with MDD, the Cu/Zn ratio increased, while the levels of Mg, CER, Zn and Fe decreased. Male MDD patients had lower Cu levels, while female patients had an increased Cu/Zn ratio. We observed significant gender differences in Cu, CER and the Cu/Zn ratio in MDD. Male patients showed a reduced N-acetyl aspartate (NAA)/phosphocreatine + creatine (PCr + Cr) ratio in the left ACC. The NAA/PCr + Cr ratio decreased in the right ACC in patients with MDD. In the left ACC of male MDD patients, the Cu/Zn ratio was inversely related to the NAA/PCr + Cr ratio, and Fe levels were negatively associated with the GPC + PC/PCr + Cr ratio. ConclusionsOur findings highlight gender-specific changes in Cu homeostasis among male MDD patients. The Cu/Zn ratio and Fe levels in male MDD patients were significantly linked to neurometabolic alterations in the ACC.

Preliminary study of proton magnetic resonance spectroscopy to assess bone marrow adiposity in the third metacarpus or metatarsus in Thoroughbred racehorses.

Magnetic resonance spectroscopy (MRS) has been used to investigate metabolic changes within human bone. It may be possible to use MRS to investigate bone metabolism and fracture risk in the distal third metacarpal/tarsal bone (MC/MTIII) in racehorses. To determine the feasibility of using MRS as a quantitative imaging technique in equine bone by using the 1H spectra for the MC/MTIII to calculate fat content (FC). Observational cross-sectional study. Limbs from Thoroughbred racehorses were collected from horses that died or were subjected to euthanasia on racecourses. Each limb underwent magnetic resonance imaging (MRI) at 3 T followed by single-voxel MRS at three regions of interest (ROI) within MC/MTIII (lateral condyle, medial condyle, proximal bone marrow [PBM]). Percentage FC was calculated at each ROI. Each limb underwent computed tomography (CT) and bone mineral density (BMD) was calculated for the same ROIs. All MR and CT images were graded for sclerosis. Histology slides were graded for sclerosis and proximal marrow space was calculated. Pearson or Spearman correlations were used to assess the relationship between BMD, FC and marrow space. Kruskal-Wallis tests were used to check for differences between sclerosis groups for BMD or FC. Eighteen limbs from 10 horses were included. A negative correlation was identified for mean BMD and FC for the lateral condyle (correlation coefficient = -0.60, p = 0.01) and PBM (correlation coefficient = -0.5, p = 0.04). There was a significant difference between median BMD for different sclerosis grades in the condyles on both MRI and CT. A significant difference in FC was identified between sclerosis groups in the lateral condyle on MRI and CT. Small sample size. 1H Proton MRS is feasible in the equine MC/MTIII. Further work is required to evaluate the use of this technique to predict fracture risk in racehorses.

Blood brain barrier disruption and glutamatergic excitotoxicity in post-acute sequelae of SARS COV-2 infection cognitive impairment: potential biomarkers and a window into pathogenesis.

To investigate the association between blood-brain barrier permeability, brain metabolites, microstructural integrity of the white matter, and cognitive impairment (CI) in post-acute sequelae of SARS-COV-2 infection (PASC). In this multimodal longitudinal MRI study 14 PASC participants with CI and 10 healthy controls were enrolled. All completed investigations at 3 months following acute infection (3 months ± 2 weeks SD), and 10 PASC participants completed at 12 months ± 2.22 SD weeks. The assessments included a standard neurological assessment, a cognitive screen using the brief CogState battery and multi-modal MRI derived metrics from Dynamic contrast enhanced (DCE) perfusion Imaging, Diffusion Tensor Imaging (DTI), and single voxel proton Magnetic Resonance Spectroscopy. These measures were compared between patients and controls and correlated with cognitive scores. At baseline, and relative to controls, PASC participants had higher K-Trans and Myo-inositol, and lower levels of Glutamate/Glutamine in the frontal white matter (FWM) (p < 0.01) as well as in brain stem (p < 0.05), and higher FA and lower MD in the FWM (p < 0.05). In PASC participants, FA and MD decreased in the FWM at 12 months compared to baseline (p < 0.05). K-Trans and metabolite concentrations did not change significantly over time. Neurocognitive scores did not correlation with the increased permeability (K trans). PASC with CI is associated with BBB impairment, loss of WM integrity, and inflammation at 3 months which significantly but not uniformly improved at 12 months. The loss of WM integrity is possibly mediated by BBB impairment and associated glutamatergic excitotoxicity.

Quantifying in vivo Mitochondrial Effciency at Rest and during Exercise in Human Skeletal Muscle

Introduction: Mitochondrial effciency provides an additional mechanism to fine-tune oxidative phosphorylation rate to match ATP demand in skeletal muscle with far-reaching consequences on exercise tolerance. However, the direct measurement of both oxygen consumption (VO2) and ATP production from the same region of the contracting muscle in vivo remains a technical challenge. Purpose: Using an innovative approach combining noninvasive phosphorus and proton magnetic resonance spectroscopy (31P/1H-MRS), the present study aimed to characterize skeletal muscle ATP synthesis rate and muscle VO2 at rest and during a graded dynamic plantar flexion exercise to determine mitochondrial effciency in the gastrocnemius muscle. Method: We assessed mitochondrial effciency in the gastrocnemius muscles of 12 healthy adults (21± 1 yrs.). 31P and 1H magnetic resonance spectroscopy (MRS) was performed using a whole-body 3T MR system (Skyra, Siemens) at rest and during a series of constant workloads coupled to brief transient ischemia to quantify both oxidative ATP synthesis (ATPox) rate and myoglobin-derived oxygen consumption (Mb-derived VO2). The MRS data were acquired with a dual-tuned 31P/1H surface coil with linear polarization positioned over the gastrocnemius muscle. Results: As expected, the end-exercise PCr concentration decreased from 29 ± 2 mM of WRmax to 18 ± 1 mM with increasing workload. Likewise, the end-exercise Mb oxygenation level declined linearly with increasing workload. As the exercise workload increased, the ATPox synthesis rate increased linearly (r2 = 0.45), whereas there was no significant change in Mb-derived VO2. At rest, the estimated P/O ratio in the gastrocnemius muscle was 1.95 ± 0.68, whereas non-physiological values were obtained during exercise. Conclusion: During exercise, Mb-derived VO2 was likely limited by O2 availability with the methodology employed (30-sec occlusion, spectrum time resolution of 10 sec), which precluded the accurate quantification of mitochondrial effciency. However, mitochondrial effciency calculated at rest is in agreement with previously documented values ex vivo and thus provides an additional parameter to evaluate mitochondrial function in vivo. This work was funded in part by National Heart, Lung, and Blood Institute Grant R00HL125756. This is the full abstract presented at the American Physiology Summit 2024 meeting and is only available in HTML format. There are no additional versions or additional content available for this abstract. Physiology was not involved in the peer review process.