Determination of the pK Value of a Brønsted Acid by F NMR Spectroscopy.

Brønsted acids, such as phosphoric acids derived from chiral 1,1'-bi-2-naphthol (BINOL), are important catalysts in the formation of carbon-carbon and carbon-heteroatom bonds, for example. The catalytic activity of these Brønsted acids is strongly linked to their acidity, and as such, the evaluation of compounds to determine pK values provides insight into their catalytic activity. Herein, a F{H} NMR methodology is detailed to determine the pK of a fluorinated binaphthyl-derived phosphinic acid, rac-1, in acetonitrile and in the presence of a fluorinated sulfonamide reference compound (2-4).

An IL-5 Single-Nucleotide Polymorphism Influences Neuroinflammation and Prospective Disease Activity in Multiple Sclerosis.

(1) Multiple sclerosis (MS) is identified by a complex interaction between central inflammation and neurodegeneration. Genetic individual variability could play a significative role in clinical presentation. The interleukin-5 (IL-5) rs2069812 single-nucleotide polymorphism (SNP) seems to define the clinical course of Th2 autoimmune diseases, while its role in MS has never been investigated.

Low-contrast visual acuity test is associated with central inflammation and predicts disability development in newly diagnosed multiple sclerosis patients.

Introduction: The visual system is a prominent site of damage in MS since the earliest phases of the disease. Altered low-contrast visual acuity (LCVA) test has been associated with visual impairment and retinal degeneration, predicting medium- and long-term disability. However, it is unclear whether LCVA may also represent a reliable measure of neuroinflammation and a predictor of disease evolution in the very early stages of MS.

mCRP-Induced Focal Adhesion Kinase-Dependent Monocyte Aggregation and M1 Polarization, Which Was Partially Blocked by the C10M Inhibitor.

Monomeric C-reactive protein (mCRP) has recently been implicated in the abnormal vascular activation associated with development of atherosclerosis, but it may act more specifically through mechanisms perpetuating damaged vessel inflammation and subsequent aggregation and internalization of resident macrophages. Whilst the direct effects of mCRP on endothelial cells have been characterized, the interaction with blood monocytes has, to our knowledge, not been fully defined. Here we showed that mCRP caused a strong aggregation of both U937 cell line and primary peripheral blood monocytes (PBMs) obtained from healthy donors.

Effects of dopaminergic treatment on inhibitory control differ across Hoehn and Yahr stages of Parkinson's disease.

Motor inhibitory control, a core component of cognitive control, is impaired in Parkinson's disease, dramatically impacting patients' abilities to implement goal-oriented adaptive strategies. A progressive loss of the midbrain's dopamine neurons characterizes Parkinson's disease and causes motor features responsive to dopaminergic treatments. Although such treatments restore motor symptoms, their impact on response inhibition is controversial.

Distinct intrathecal inflammatory signatures following relapse and anti-COVID-19 mRNA vaccination in multiple sclerosis.

Background: The role of vaccine-mediated inflammation in exacerbating multiple sclerosis (MS) is a matter of debate.

Objective: In this cross-sectional study, we compared the cerebrospinal fluid (CSF) inflammation associated with MS relapses or anti-COVID-19 mRNA vaccinations in relapsing-remitting multiple sclerosis (RRMS).

Methods: We dosed CSF cytokines in 97 unvaccinated RRMS patients with clinical relapse within the last 100 days.

Solar ultraviolet light collector for germicidal irradiation on the moon.

Prolonged human-crewed missions on the Moon are foreseen as a gateway for Mars and asteroid colonisation in the next decades. Health risks related to long-time permanence in space have been partially investigated. Hazards due to airborne biological contaminants represent a relevant problem in space missions.

Asymmetric Construction of Alkaloids by Employing a Key ω-Transaminase Cascade.

An ω-transaminase-triggered intramolecular aza-Michael reaction has been employed for the preparation of cyclic β-enaminones in good yield and excellent enantio- and diastereoselectivity, starting from easily accessible prochiral ketoynones and commercially available enzymes. The powerful thermodynamic driving force associated with the spontaneous aza-Michael reaction effectively displaces the transaminase reaction equilibrium towards product formation, using only two equivalents of isopropylamine. To demonstrate the potential of this methodology, this biocatalytic aza-Michael step was combined with annulation chemistry, affording unique stereo-defined fused alkaloid architectures.

Early-stage Parkinson's patients show selective impairment in reactive but not proactive inhibition.

Background: It is well known that a deficit in inhibitory control is a hallmark of Parkinson's disease (PD). However, inhibition is not a unitary construct, and it is unclear whether patients in the early stage of the disease (Hoehn and Yahr stage 1) exhibit a deficit in outright stopping (reactive inhibition), a deficit in the ability to shape their response strategies according to the context (proactive inhibition), or both.

Objective: We assessed whether PD patients at Hoehn and Yahr stage 1 show a global or selective impairment in inhibitory control.

Acetylcholine Inhibits Monomeric C-Reactive Protein Induced Inflammation, Endothelial Cell Adhesion, and Platelet Aggregation; A Potential Therapeutic?

In this study, we examined the possibility of using targeted antibodies and the potential of small molecular therapeutics (acetylcholine, nicotine and tacrine) to block the pro-inflammatory and adhesion-related properties of monomeric C-reactive protein (mCRP). We used three established models (platelet aggregation assay, endothelial leucocyte binding assay and monocyte inflammation via ELISA and Western blotting) to assess the potential of these therapeutics. The results of this study showed that monocyte induced inflammation (raised tumor necrosis factor-alpha-TNF-α) induced by mCRP was significantly blocked in the presence of acetylcholine and nicotine, whilst tacrine and targeted antibodies (clones 8C10 and 3H12) had less of or no significant effects.

Stereoselective synthesis of 1,3-disubstituted dihydroisoquinolines vial-phenylalanine-derived dihydroisoquinoline N-oxides.

The preparation of chiral pool-derived nitrone 3 and its use in the protecting-group free, stereoselective synthesis of a range of 1,3-disubstituted tetrahydroisoquinolines is described. Grignard reagent additions to nitrone 3 yielded trans-1,3-disubstituted N-hydroxytetrahydroisoquinolines 6 with good levels of selectivity, while 1,3-dipolar cycloadditions to this nitrone provided access to 3-(2-hydroxyalkyl)isoquinolines 12 as single diastereomers.

pCRP-mCRP Dissociation Mechanisms as Potential Targets for the Development of Small-Molecule Anti-Inflammatory Chemotherapeutics.

Circulating C-reactive protein (CRP) is a key acute-phase protein and one of the main clinical biomarkers for inflammation and infection. CRP is an important upstream mediator of inflammation and is associated with the onset of a number of important disease states including cardiovascular disease and neurodegenerative disorders such as Alzheimer's disease. This pentraxin exerts pro-inflammatory properties dissociation of the pentamer (pCRP) to a monomeric form (mCRP).

Transaminase Triggered Aza-Michael Approach for the Enantioselective Synthesis of Piperidine Scaffolds.

The expanding "toolbox" of biocatalysts opens new opportunities to redesign synthetic strategies to target molecules by incorporating a key enzymatic step into the synthesis. Herein, we describe a general biocatalytic approach for the enantioselective preparation of 2,6-disubstituted piperidines starting from easily accessible pro-chiral ketoenones. The strategy represents a new biocatalytic disconnection, which relies on an ω-TA-mediated aza-Michael reaction.

Fe(III)-photocatalytic partial oxidation of benzyl alcohol to benzaldehyde under UV-solar simulated radiation.

A great deal of interest is recorded among researchers in the identification of new catalytic systems that make possible the selective oxidation of organic species in the presence of non-toxic solvents, primarily water, through the use of inexpensive catalysts. The possibility to selectively oxidize benzyl alcohol to benzaldehyde is studied in the present work by using ferric ions as homogeneous catalysts and oxygen as an oxidant under UV-solar simulated radiation. Due to the possibility that Fe(III) aquo-complex photolysis could generate undesired reactive OH radicals with the consequent occurrence of side reactions, most of the runs are carried out at pH = 0.

A divergent approach to 3-piperidinols: a concise syntheses of (+)-swainsonine and access to the 1-substituted quinolizidine skeleton.

Nucleophilic addition of Grignard reagents and organolithium species to a 3-silyloxy-3,4,5,6-tetrahydropyridine N-oxide provides trans-2,3-disubstituted N-hydroxypiperidines exclusively. The application of this methodology to the preparation of a diversity of useful trans-2-substituted-3-hydroxypiperidines, a concise synthesis of (+)-swainsonine, and an enantiopure 1-substituted quinolizidine of utility in target-directed synthesis is reported.

Kinetic and chemical characterization of thermal decomposition of dicumylperoxide in cumene.

Dicumylperoxide (DCP) is one of the most used peroxides in the polymer industry. It has been reported that its thermal decomposition can result in runaway phenomena and thermal explosions with significant economic losses and injuries to people. In the present paper thermal behaviour of dicumylperoxide in cumene was investigated over the temperature range of 393-433 K under aerated and de-aerated conditions.

A concise approach to the core structures of pinnaic acid and halichlorine.

An efficient and flexible synthetic approach to the core structures of pinnaic acid and halichlorine is described using spirocyclic nitrone 4 as a key intermediate. 1,3-Dipolar cycloaddition of 4 with dipolarophile 8 provides access to the azaspirocyclic core of pinnaic acid 5 while the spiroquinolizidine core of halichlorine 6 has been synthesised via cycloaddition of 4 with dipolarophile 29. Nitrone 4 is accessed by oxidative ring opening of isoxazolidine 9.

Energy recovery in wastewater decontamination: simultaneous photocatalytic oxidation of an organic substrate and electricity generation.

The contemporary removal of organic pollutants from aqueous solution and electricity generation is studied in the present work by means of an experimental device resulting from the combination of a photocatalytic reactor and an electrochemical cell. The proposed system relies on the capability of Cu2+ ions to reduce in the presence of TiO2, (solar) UV radiations and a sacrificial organic agent. In the anodic solution of the combined photoreactor-cell, Cu0 is oxidized to Cu2+ and the latter is reduced again to the lowest oxidation state.

Use of an amorphous iron oxide hydrated as catalyst for hydrogen peroxide oxidation of ferulic acid in water.

The abatement of ferulic acid (FA), a polyphenolic constituent of olive mill wastewater, is studied in the pH range 5.0-7.0 by using hydrogen peroxide and an amorphous iron oxide as catalyst.

Label-free detection of DNA hybridization based on a novel functionalized conducting polymer.

A new functionalized pyrrole monomer, 3-pyrrolylacrylic acid (PAA) was synthesized. It was used to prepare a copolymer with pyrrole, poly(Py-co-PAA), which was investigated by reflective FT-IR, UV-vis spectroscopy and cyclic voltammetry. A label-free DNA sensor was prepared based on a poly(Py-co-PAA) film.

Batch salicylic acid nitration by nitric acid/acetic acid mixture under isothermal, isoperibolic and adiabatic conditions.

Runaway phenomena and thermal explosions can originate during the nitration of salicylic acid by means of a nitric acid/acetic acid mixture when the thermal control is lost, mainly as a result of the formation and thermal decomposition of picric acid. The prediction of the behaviour of this system is thus of great importance in view of possible industrial applications and the need to avoid the occurrence of unwanted dangerous events. During a previous investigation a model was developed to simulate its behaviour when the starting concentration of the substrate is too low, thus, preventing the precipitation of poor soluble intermediates.

Kinetic and safety assessment for salicylic acid nitration by nitric acid/acetic acid system.

The nitration process of salicylic acid for the production of the important intermediate 5-nitrosalicylic acid is studied from thermokinetic and safety points of view. Investigations carried out by considering, as process deviations, the loss of the thermal control point out the possibility of runaway phenomena due to the occurrence of polynitration reactions. Isothermal experiments are carried out in various conditions to assess the involved reaction network and reaction kinetics.

Antibiotics in the environment: occurrence in Italian STPs, fate, and preliminary assessment on algal toxicity of amoxicillin.

Amoxicillin is a widely used penicillin-like antibiotic, and due to its presence in several effluents of Italian STPs, its environmental fate along with its toxicity toward simple organisms have been investigated in model conditions. The present study shows that under abiotic conditions both hydrolysis and direct photolysis could be responsible for the transformation and removal of amoxicillin in aquatic environment, especially in slightly basic media. Quantum yields for the solar direct photolysis have been calculated along with kinetic constants and half-life times.

(S)-Nitroxycarnitine nitrate production from (S)-carnitine by using acetic anhydride/nitric acid/acetic acid mixtures: safety assessment.

The present work aims at assessing both thermodynamic and kinetic parameters of the esterification process of the (S)-carnitine, using calorimetric techniques. The use of the system acetic anhydride/nitric acid/acetic acid as esterifying agent and the explosive behaviour of nitric esters lead to safety considerations that have been investigated by hypothesizing some common process deviations. In particular, it has been investigated in adiabatic conditions both the batch addition of acetic anhydride and the effect of an initial temperature higher than those required by the process.