Prolonged Reaction Research Articles

A New Insight Into The Huisgen Reaction: Heterogeneous Copper Catalyzed Azide-Alkyne Cycloaddition for the Synthesis of 1,4-Disubstituted Triazole (From 2018-2023).

The Huisgen cycloaddition, often referred to as 1,3-Dipolar cycloaddition, is a well-established method for synthesizing 1,4-disubstituted triazoles. Originally conducted under thermal conditions [3+2] cycloaddition reactions were limited by temperature, prolonged reaction time, and regioselectivity. The introduction of copper catalyzed azide-alkyne cycloaddition (CuAAC) revitalized interest, giving rise to the concept of "click chemistry". The CuAAC has emerged as a prominent method for producing 1,2,3-triazole with excellent yields and exceptional regioselectivity even in unfavorable conditions. Copper catalysts conventionally facilitate azide-alkyne cycloadditions, but challenges include instability and recycling issues. In recent years, there has been a growing demand for heterogeneous and porous catalysts in various chemical reactions. Chemists have been more interested in heterogenous catalysts as a result of the difficulties in separating homogenous catalysts from reaction products. These catalysts are favored for their abundant active sites, extensive surface area, easy separation from reaction mixtures, and the ability to be reused. Heterogeneous catalysts have garnered significant attention due to their broad industrial utility, characterized by cost-effectiveness, stability, resistance to thermal degradation, and ease of removal compared to their homogeneous counterparts. The present review covers recent advancements from year 2018 to 2023 in the field of click reactions for obtaining 1,2,3-triazoles through Cu catalyzed 1,3-dipolar azide-alkyne cycloaddition and the properties of the catalyst, reaction conditions such as solvent, temperature, reaction time, and the impact of different heterogeneous copper catalysts on product yield.

Peripheral GFAP and NfL as early biomarkers for dementia: longitudinal insights from the UK Biobank

BackgroundPeripheral glial fibrillary acidic protein (GFAP) and neurofilament light chain (NfL) are sensitive markers of neuroinflammation and neuronal damage. Previous studies with highly selected participants have shown that peripheral GFAP and NfL levels are elevated in the pre-clinical phase of Alzheimer’s disease (AD) and dementia. However, the predictive value of GFAP and NfL for dementia requires more evidence from population-based cohorts.MethodsThis was a prospective cohort study to evaluate UK Biobank participants enrolled from 2006 to 2010 using plasma GFAP and NfL measurements measured by Olink Target Platform and prospectively followed up for dementia diagnosis. Primary outcome was the risk of clinical diagnosed dementia. Secondary outcomes were cognition. Linear regression was used to assess the associations between peripheral GFAP and NfL with cognition. Cox proportional hazard models with cross-validations were used to estimate associations between elevated GFAP and NfL with risk of dementia. All models were adjusted for covariates.ResultsA subsample of 48,542 participants in the UK Biobank with peripheral GFAP and NfL measurements were evaluated. With an average follow-up of 13.18 ± 2.42 years, 1312 new all-cause dementia cases were identified. Peripheral GFAP and NfL increased up to 15 years before dementia diagnosis was made. After strictly adjusting for confounders, increment in NfL was found to be associated with decreased numeric memory and prolonged reaction time. A greater annualized rate of change in GFAP was significantly associated with faster global cognitive decline. Elevation of GFAP (hazard ratio (HR) ranges from 2.25 to 3.15) and NfL (HR ranges from 1.98 to 4.23) increased the risk for several types of dementia. GFAP and NfL significantly improved the predictive values for dementia using previous models (area under the curve (AUC) ranges from 0.80 to 0.89, C-index ranges from 0.86 to 0.91). The AD genetic risk score and number of APOE*E4 alleles strongly correlated with GFAP and NfL levels.ConclusionsThese results suggest that peripheral GFAP and NfL are potential biomarkers for the early diagnosis of dementia. In addition, anti-inflammatory therapies in the initial stages of dementia may have potential benefits.

Kinetic Resolution of Cyclic Tertiary Alcohols with Lipase A from Candida Antarctica

AbstractEnzyme‐catalyzed acylative kinetic resolution (KR) and dynamic kinetic resolution (DKR) of racemic primary and secondary alcohols have been widely reported to produce esters with high enantiomeric purity. In contrast, similar KRs of tertiary alcohols have been reported for only a limited range of substrates and require prolonged reaction times of several days. To gain deeper insight into the substrate scope and increase the process efficiency, we examined the reaction conditions using commercially available immobilized lipase A from Candida antarctica and found that the addition of the heterogeneous, inorganic base sodium carbonate significantly increased the reaction rate while maintaining high enantioselectivity. The use of vinyl hexanoate as the acyl donor provided esters that were stable during chromatography purification. The optimized reaction conditions were then successfully applied to a range of cyclic tertiary alcohols containing tetralin, dihydroindene, chromane, and thiochromane skeletons having, in part, a substituent on the aromatic ring. In this study on the structure–reactivity relationship of enzymatic KR‐type reactions, we achieved >30 % conversion for various tertiary alcohols in 24 h at 25 °C, producing optically active esters with 88–99 % ee.

Comprehensive assessment and treatment strategies for dysphagia in the elderly population: Current status and prospects.

As the population ages, the prevalence of dysphagia among older adults is a growing concern. Age-related declines in physiological function, coupled with neurological disorders and structural changes in the pharynx associated with aging, can result in weakened tongue propulsion, a prolonged reaction time of the submental muscles, delayed closure of the laryngeal vestibule, and delayed opening of the upper esophageal sphincter (UES), increasing the risk of dysphagia. Dysphagia impacts the physical health of the elderly, leading to serious complications such as dehydration, aspiration pneumonia, malnutrition, and even life-threatening conditions, and it also detrimentally affects their psychological and social well-being. There is a significant correlation between frailty, sarcopenia, and dysphagia in the elderly population. Therefore, older adults should be screened for dysphagia to identify both frailty and sarcopenia. A reasonable diagnostic approach for dysphagia involves screening, clinical assessment, and instrumental diagnosis. In terms of treatment, multidisciplinary collaboration, rehabilitation training, and the utilization of new technologies are essential. Future research will continue to concentrate on these areas to enhance the diagnosis and treatment of dysphagia, with the ultimate aim of enhancing the quality of life of the elderly population.

Walker’s Appeal... is the main manifesto of radical African-American abolitionism

This work is about one of the key episodes of African-American history and the history of American abolitionism associated with the publication in September 1829 in Boston of Walker’s Appeal, in Four Articles; Together with a Preamble, to the Coloured Citizens of the World. The appearance of this “revolutionary appeal” undoubtedly marked a new milestone in the development of the anti-slavery movement and the actual emergence of such a trend as radical African-American abolitionism. The reaction to the release of this document by the authorities of the Southern States can be called unprecedented in its scale and consequences. It found expression in the adoption of a number of repressive laws, which, in turn, marked the beginning of a period of prolonged reaction in the American South, which would end only after the end of the Civil War of 1861–1865. The significance of this event is difficult to overestimate. After almost two centuries, the figure of David Walker and his Appeal still arouse increased interest from Western researchers and not only. However, no serious works on this topic have been published in Russian historiography up to the present moment. This study aims to identify and examine the causes and circumstances of the writing of the Walker’s Appeal…, to analyze the main provisions of this document and the consequences caused by its dissemination. In addition, the author pays special attention to the review of the historiography of this issue. The source base is newspaper publications, letters and bills of the period under review, as well as the text of the Appeal. The methodological basis of the research consists of causal, historical-descriptive, historical-genetic, historical-typological, retrospective, and comparative-historical methods. The materialistic dialectic plays the main role, showing the development of the abolitionist movement in dynamics and the influence of related factors. The author concludes that Walker’s Appeal… became an expression of the most important trend in the development of American abolitionism at the end of the first third of the nineteenth century. The appearance of this document clearly demonstrated the radicalization of the African-American community itself and its willingness to join the struggle for the abolition of slavery and its rights.

Understanding Relations Between Product Icon Type, Feature Type, and Abstraction: Evidence From ERPs and Eye-Tracking Studys

The representation and recognition of icons play a crucial role in interface interaction efficiency and user experience within human–computer interaction. However, the intricate relationship between product icon types, feature types, and abstraction in cognitive contexts has yet to be clarified. This study aimed to delve into the cognitive mechanisms concerning practical and hedonic product icons across varying abstraction levels using EEG analysis. Moreover, it investigated how the explicitness and implicitness of these icons and their abstraction levels influence recognition efficiency via eye-tracking studies. In Experiment A, a high abstraction level led to prolonged reaction times (RTs), reduced accuracy rate (ACC), more negative N400, and decreased late positive potential (LPP) amplitudes. These outcomes suggested increased effort, heightened semantic conflict, and negative emotional engagement. Moreover, at middle abstraction levels, RTs were consistently longer for hedonic product icons compared to practical ones. Additionally, both N400 and LPP amplitudes were notably larger for hedonic product icons. In Experiment B, eye-tracking results revealed that compared with implicit features, the change of abstraction degree of explicit features is more likely to increase the number of fixation points and RTs of users. Specifically, functional explicit features wielded the greatest impact on overall icon cognitive efficiency. Synthesizing both experiments revealed significant differences in abstraction requirements for practical vs. hedonic product icons. A practical implication arises: moderate overall abstraction suits practical product icons, while higher abstraction suits hedonic ones. Among features, it’s essential to avoid excessive abstraction in functional and symbolic aspects, while simplifying or removing area line features and chamfered elements can be beneficial. This study contributes to Internet of Things (IoT) icon research, offering potential guidance for graphic designers in crafting user-friendly icons.

Organocatalytic ring-opening polymerization of lactide by bis(thiourea) H-bonding donating cocatalysts with binaphthyl-amine framework

Development of H-bonding organo-catalysts with high catalytic activity and high degree of control is significantly important for the metal-free polyesters that are potentially suitable for biomedical usage. The concomitant use of base and commercially available thiourea generally suffered from prolonged reaction time and resulted in incomplete monomer conversion in some cases. Introducing one or more (thio)urea H-bonding donating arms to the parent thiourea has been proved to be an effective method for substantially increasing the activity of thiourea H-bonding donors. Consequently, we synthesized bis-thioureas derived from binaphthyl-amine bearing different substituents and investigated their catalytic performance in ROPs of lactide in this work. The density functional theory (DFT) calculations suggested that the “activated-thiourea” mode is more preferred for the bis(thiourea) containing binaphthyl-amine framework. The bis(thiourea)/base binary systems could effectively promote the LA polymerization using benzyl alcohol as initiator. The polymerization rates and the degree of control over the polymerization are highly dependent on the structures of the bis(thiourea) and base. Bis(thiourea)/1,5,7-triazabicyclo[4.4.0]dec‑5-ene pairs exhibited highest catalytic activity compared to other bis(thiourea)/base pairs, and the turnover frequency is high up to 1980 h–1 at 75 °C. In addition, the bulky hindrance and axial chirality of the binaphthyl-amine framework could enable stereoselective ROP of rac-LA to produce isotactic-rich and crystalline PLAs at relatively low temperature (0 °C). Mechanistic studies indicated that both enantiomorphic site control (ESC) and chain end control (CEC) concurrently occurred in the rac-LA polymerization catalyzed by bis(thiourea)/base binary systems. This work will inspire future design of H-bonding donors with high catalytic performance.

Electronic Structure Modulation Via Iron-Incorporated NiO to Boost Urea Oxidation/Oxygen Evolution Reaction.

The urea-assisted water splitting not only enables a reduction in energy consumption during hydrogen production but also addresses the issue of environmental pollution caused by urea. Doping heterogeneous atoms in Ni-based electrocatalysts is considered an efficient means for regulating the electronic structure of Ni sites in catalytic processes. However, the current methodologies for synthesizing heteroatom-doped Ni-based electrocatalysts exhibit certain limitations, including intricate experimental procedures, prolonged reaction durations, and low product yield. Herein, Fe-doped NiO electrocatalysts were successfully synthesized using a rapid and facile solution combustion method, enabling the synthesis of 1.1107 g within a mere 5 min. The incorporation of iron atoms facilitates the modulation of the electronic environment around Ni atoms, generating a substantial decrease in the Gibbs free energy of intermediate species for the Fe-NiO catalyst. This modification promotes efficient cleavage of C-N bonds and consequently enhances the catalytic performance of UOR. Benefiting from the tunability of the electronic environment around the active sites and its efficient electron transfer, Fe-NiO electrocatalysts only needs 1.334 V to achieve 50 mA cm-2 during UOR. Moreover, Fe-NiO catalysts were integrated into a dual electrode urea electrolytic system, requiring only 1.43 V of cell voltage at 10 mA cm-2.

Surface coordination induced a quasi p-n junction for efficient visible light driven degradation of tetracycline over hydroxyapatite

The removal of antibiotics from aquatic solutions remains a global environmental challenge. In this work, the photocatalytic removal of a typical antibiotic-tetracycline (TC) using hydroxyapatite (HAp) as a catalyst was investigated. It was impressive that TC could be efficiently degraded by HAp under visible light irradiation, even though both HAp and TC exhibited poor harvesting in visible light region. The experimental and theoretical explorations were undertaken to thoroughly investigate the underlying mechanism of visible light degradation of TC over HAp. The results indicated that the formed TC-HAp complexes via surface coordination played an important role as photosensitizers for the visible light response. Together with the formation of a quasi p-n junction via band alignment, the photogenerated electrons in the highest unoccupied molecular orbital (HOMO) of TC-HAp were excited to the lowest unoccupied molecular orbital (LUMO) and subsequently migrated to the conduction band of HAp to achieve the efficient charge separation. Superoxide radicals and holes were found to be the major active species for TC degradation. The toxicity evaluation showed that TC could be transferred to the lower toxic intermediates, and deep oxidation with prolonged reaction time was necessary to eliminate the toxicity of TC. This work demonstrates the surface coordination with subsequent quasi p-n junction mechanism of TC degradation over HAp under visible light, which will stimulate us to explore new efficient photocatalytic systems for the degradation of various contaminants.

Zur Dekarbonisierung N‐Heterocyclischer Carbene (NHCs): Die einfachen Alan‐Addukte (NHC) ⋅ AlR3 (R=H, Me, Et)

AbstractDie Reaktion des Amin‐stabilisierten Alans (NMe3) ⋅ AlH3 1 mit dem Rückgrat‐gesättigten N‐heterocyclischen Carben (NHC) SIDipp (SIDipp=1,3‐Bis‐{2,6‐di‐iso‐propyl‐phenyl}‐imidazolidin‐2‐yliden) bei 0 °C ergab das NHC‐stabilisierte Alan‐Addukt (SIDipp) ⋅ AlH3 2. Erhöhte Temperaturen oder verlängerte Reaktionszeiten bei Raumtemperatur führten zum Produkt einer Ringerweiterungs‐Reaktion (RER) des NHCs, (NMe3) ⋅ AlH(RER‐SIDippH2), 3 ⋅ (NMe3). Die anschließende Reaktionen mit den sterisch weniger anspruchsvollen NHCs (IMeMe {=1,3,4,5‐Tetramethyl‐imidazolin‐2‐yliden}, IiPrMe {=1,3‐Di‐iso‐propyl‐4,5‐dimethyl‐imidazolin‐2‐yliden} und IiPr {=1,3‐Di‐iso‐propyl‐imidazolin‐2‐yliden}) lieferten die NHC‐stabilisierten RER‐Produkte (NHC) ⋅ AlH(RER‐SIDippH2) 3 ⋅ (NHC) (NHC=IMeMe, IiPrMe, IiPr), während mit den sterisch anspruchsvolleren NHCs IDipp (=1,3‐Bis‐{2,6‐di‐iso‐propyl‐phenyl}‐imidazolin‐2‐yliden), SIDipp und ItBu (=1,3‐Di‐tert‐butyl‐imidazolin‐2‐yliden) keine Reaktion beobachtet wurde. Die Verbindungen 3 ⋅ (NHC) wurden ebenfalls ausgehend von (SIDipp) ⋅ AlH3 2 und NHC bei Raumtemperatur erhalten. Das Erhitzen von Lösungen von (SIDipp) ⋅ AlH3 2 ohne zusätzliche Base auf 95 °C führte unter Verlust von Ethen zu einer Dekarbonisierung des NHCs und somit zur Substitution des Carben‐Kohlenstoffatoms durch Aluminiumhydrid. Die anschließende Dimerisierung ergab cis‐[AlH{μ‐N(Dipp)CH2CH2N(Dipp)}]2 4_dimer. Das Erhitzen von Lösungen der NHC‐stabilisierten Aluminiumalkyle (SIDipp) ⋅ AlR3 2R (R=Me, Et) auf 145 °C führte stattdessen unter Freisetzung von Ethen zur vollständigen Spaltung des NHC‐Grundgerüstes und Isolierung der Dialkylaluminium(III)‐Amidinate {DippNC(R)NDipp}AlR2 5R (R=Me, Et).

How to Decarbonize N-Heterocyclic Carbenes (NHCs): The simple Alane Adducts (NHC) ⋅ AlR3 (R=H, Me, Et).

The reaction of the amine-stabilized alane (NMe3) ⋅ AlH3 1 with the backbone-saturated N-heterocyclic carbene (NHC) SIDipp (SIDipp=1,3-bis-{2,6-di-iso-propyl-phenyl}-imidazolidin-2-ylidene) at 0 °C yielded the NHC alane adduct (SIDipp) ⋅ AlH3 2. Reaction at elevated temperatures or prolonged reaction at room temperature gave the product of a ring expansion reaction (RER) of the NHC, (NMe3) ⋅ AlH(RER-SIDippH2) 3 ⋅ (NMe3). Subsequent reaction of the latter with sterically less hindered NHCs (IMeMe {=1,3,4,5-tetramethyl-imidazolin-2-ylidene}, IiPrMe {=1,3-di-iso-propyl-4,5-dimethyl-imidazolin-2-ylidene}, and IiPr {=1,3-di-iso-propyl-imidazolin-2-ylidene}) afforded the NHC-stabilized RER-products (NHC) ⋅ AlH(RER-SIDippH2) 3 ⋅ (NHC) (NHC=IMeMe, IiPrMe, IiPr), while no reaction was observed with the sterically more demanding NHCs IDipp (=1,3-bis-{2,6-di-iso-propyl-phenyl}-imidazolin-2-ylidene), SIDipp and ItBu (=1,3-di-tert-butyl-imidazolin-2-ylidene). The compounds 3 ⋅ (NHC) were also obtained starting from (SIDipp) ⋅ AlH3 2 and NHC at room temperature. Heating solutions of (SIDipp) ⋅ AlH3 2 without additional base to 95 °C resulted in decarbonization of the NHC and substitution of the carbene carbon atom with aluminum hydride under loss of ethene. Subsequent dimerization afforded cis-[AlH{μ-N(Dipp)CH2CH2N(Dipp)}]2 4_dimer. Heating solutions of the NHC-ligated aluminum alkyls (SIDipp) ⋅ AlR3 2R (R=Me, Et) to 145 °C instead led to complete scission of the NHC backbone with evolution of ethene and isolation of the dialkylaluminium(III) amidinates {DippNC(R)NDipp}AlR2 5R (R=Me, Et).

Cotton fabrics modified with tannic acid/1-eicosanamine grafting layer for oil/water separation

The wettability of the surface of hydrophilic cotton fabrics was modified using a one-step protocol with tannic acid (TA) to provide its excess catechol groups to be grafted with 1-eicosanamine at pH 8.5 and room temperature with catalysts CuSO4/H2O2. The modification over the synthesis conditions revised the contact angles of water and diiodomethane droplets from 132.68 ± 0.49° to 143.95 ± 0.80° and from 100.08°±1.42° to 82.96 ± 1.38°, respectively. The corresponding dispersive of the so-yielded cotton surface ranged from 8.6 to 16.0 mJ/m2, and the polar components ranged from 0.08 to 2.7 mJ/m2, much lower than polytetrafluoroethylene. The modified cotton fabrics are omniphobic and can repel water and commercial oil products. The absorption tests revealed that the modified cotton fabrics absorbed 1.10 g hexane/g cotton by contacting hexane (top)-water (bottom) layers and absorbed 1.26 g hexane/g cotton by contacting water first for 30 s, then hexane for another 30 s. The modified fabrics reveal good absorption reusability as hexane absorbent is even pre-saturated with water. This conclusion is also valid for commercial unleaded gasoline #95 and diesel. A parametric study revealed that the added catalysts and prolonged reaction time would enhance the hydrophobicity of the surface. These modified cotton fabrics can absorb oil from water and oil spills. Mechanisms corresponding to this observation are discussed.

Transglutaminase cross-linking ovalbumin-flaxseed oil emulsion gels: Properties, microstructure, and performance in oxidative stability

This study prepared emulsion gels by modifying ovalbumin (OVA)-flaxseed oil (FSO) emulsions with transglutaminase (TGase) and investigated their properties, structure and oxidative stability under different enzyme reaction times. Here, we found prolonged reaction times led to the transformation of α-helix and β-turn into β-sheet and random coil. The elasticity, hardness and water retention of the emulsion gels increased significantly, but the water-holding capacity decreased when the reaction time exceeded 4 h. Confocal laser scanning microscope (CLSM) indicated extended enzyme reaction time fostered oil droplet aggregation with proteins. Emulsion gel reduced FSO oxidation, especially after 4 h of the enzyme reaction, the peroxide value (PV) of the emulsion gel was reduced by 29.16% compared to the control. In summary, the enzyme reaction time of 4 h resulted in the formation of a dense gel structure and enhanced oxidative stability. This study provides the potential applications in functional foods and biomedical fields.

In Vivo Osteogenic and Angiogenic Properties of a 3D-Printed Isosorbide-Based Gyroid Scaffold Manufactured via Digital Light Processing.

Osteogenic and angiogenic properties of synthetic bone grafts play a crucial role in the restoration of bone defects. Angiogenesis is recognised for its support in bone regeneration, particularly in larger defects. The objective of this study is to evaluate the new bone formation and neovascularisation of a 3D-printed isosorbide-based novel CSMA-2 polymer in biomimetic gyroid structures. The gyroid scaffolds were fabricated by 3D printing CSMA-2 polymers with different hydroxyapatite (HA) filler concentrations using the digital light processing (DLP) method. A small animal subcutaneous model and a rat calvaria critical-size defect model were performed to analyse tissue compatibility, angiogenesis, and new bone formation. The in vivo results showed good biocompatibility of the 3D-printed gyroid scaffolds with no visible prolonged inflammatory reaction. Blood vessels were found to infiltrate the pores from day 7 of the implantation. New bone formation was confirmed with positive MT staining and BMP-2 expression, particularly on scaffolds with 10% HA. Bone volume was significantly higher in the CSMA-2 10HA group compared to the sham control group. The results of the subcutaneous model demonstrated a favourable tissue response, including angiogenesis and fibrous tissue, indicative of the early wound healing process. The results from the critical-size defect model showcased new bone formation, as confirmed by micro-CT imaging and immunohistochemistry. The combination of CSMA-2 as the 3D printing material and the gyroid as the 3D structure was found to support essential events in bone healing, specifically angiogenesis and osteogenesis.

Low blood concentration of alcohol enhances activity related to stopping failure in the right inferior frontal cortex.

This study investigated the effects of low doses of alcohol, which are acceptable for driving a car, on inhibitory control and neural processing using the stop-signal task (SST) in 17 healthy right-handed social drinkers. The study employed simultaneous functional magnetic resonance imaging and electromyography (EMG) recordings to assess behavioral and neural responses under conditions of low-dose alcohol (breath-alcohol concentration of 0.15mg/L) and placebo. The results demonstrated that even a small amount of alcohol consumption prolonged Go reaction times in the SST and modified stopping behavior, as evidenced by a decrease in the frequency and magnitude of partial response EMG that did not result in button pressing during successful inhibitory control. Furthermore, alcohol intake enhanced neural activity during failed inhibitory responses in the right inferior frontal cortex, suggesting its potential role in behavioral adaptation following stop-signal failure. These findings suggest that even low levels of alcohol consumption within legal driving limits can greatly impact both the cognitive performance and brain activity involved in inhibiting responses. This research provides important evidence on the neurobehavioral effects of low-dose alcohol consumption, with implications for understanding the biological basis of impaired motor control and decision-making and potentially informing legal guidelines on alcohol consumption.

CO2-Driven N-Formylation/N-Methylation of Amines Using C-Scorpionate Metal Complexes.

C-scorpionate metal complexes, specifically, [NiCl2(tpm)]·3H2O, [CoCl2(tpm)]·3H2O and [PdCl2(tpm)] [tpm = hydrotris(1H-pyrazol-1-yl)methane], were effective in the N-formylation and N-methylation of amines using carbon dioxide, as carbon source, in the presence of sodium borohydride. Various parameters were studied, including reaction time, temperature, solvent volume, presence of additives, and catalyst amount. These parameters were found to have a significant impact on the selectivity of the product. [NiCl2(tpm)]·3H2O exhibited good conversion at 80 °C, but its selectivity towards formamide decreased with prolonged reaction time. Increasing the amount of [NiCl2(tpm)]·3H2O, the selectivity changed. [PdCl2(tpm)] showed different selectivity compared to [NiCl2(tpm)]·3H2O, while [CoCl2(tpm)]·3H2O presented poor results. Monitoring the reaction course by 1H NMR revealed the presence of an intermediate species that influenced product formation. These results highlight the versatility and catalytic potential of C-scorpionate metal complexes in the N-formylation/N-methylation of amines in the catalytic system (NaBH4/MeCN/CO2).

Healthy aging alters the oscillatory dynamics and fronto-parietal connectivity serving fluid intelligence.

Fluid intelligence (Gf) involves logical reasoning and novel problem-solving abilities. Often, abstract reasoning tasks like Raven's progressive matrices are used to assess Gf. Prior work has shown an age-related decline in fluid intelligence capabilities, and although many studies have sought to identify the underlying mechanisms, our understanding of the critical brain regions and dynamics remains largely incomplete. In this study, we utilized magnetoencephalography (MEG) to investigate 78 individuals, ages 20-65 years, as they completed an abstract reasoning task. MEG data was co-registered with structural MRI data, transformed into the time-frequency domain, and the resulting neural oscillations were imaged using a beamformer. We found worsening behavioral performance with age, including prolonged reaction times and reduced accuracy. MEG analyses indicated robust oscillations in the theta, alpha/beta, and gamma range during the task. Whole brain correlation analyses with age revealed relationships in the theta and alpha/beta frequency bands, such that theta oscillations became stronger with increasing age in a right prefrontal region and alpha/beta oscillations became stronger with increasing age in parietal and right motor cortices. Follow-up connectivity analyses revealed increasing parieto-frontal connectivity with increasing age in the alpha/beta frequency range. Importantly, our findings are consistent with the parieto-frontal integration theory of intelligence (P-FIT). These results further suggest that as people age, there may be alterations in neural responses that are spectrally specific, such that older people exhibit stronger alpha/beta oscillations across the parieto-frontal network during abstract reasoning tasks.

Demodicosis in a Kunekune pig and molecular characterisation of porcine demodectic mites involved: a case report

BackgroundIn January 2021, a female 1-year-old Kunekune was presented at the University Clinic for Swine with severe reduction of the field of vision resulting in prolonged reaction time when targeting barriers, due to moderate to severe thickening of the skin around both orbits also affecting the eyelids. MethodsClinical examination revealed skin hyperplasia, nodular enlargement of the skin pores of the axillar and inguinal region. Ophthalmologists decided to remove parts of the thickened periocular skin, followed by histopathological examination.ResultsOnce large amounts of demodectic mites were detected by histopathology, demodicosis could be diagnosed and treatment of the pig was started using sarolaner. Morphological and molecular analyses were performed. Histopathological and parasitological exams led to the aetiological diagnosis of demodicosis in the affected Kunekune pig. Severe skin lesions were revealed to be the consequence of an infestation with Demodex sp. Morphological analyses confirmed the involvement of D. phylloides. Molecular characterization indicated a Demodex species closely related to mites documented in wild boar - most probably D. phylloides for which no explicit sequences are available in GenBank yet. Treatment with sarolaner (2.6 mg/kg) resulted in a substantial regression of skin lesions, already detectable 1 month after first treatment.ConclusionsDemodicosis is a very rare disease in pigs that is most probably related to an impaired immune response to the mites. Demodectic mange should be included in the list of differential diagnoses in cases of periocular alterations of the skin of pigs.Graphical

Isochoric pressure-temperature behavior of lactalbumin+water reactive mixtures under subcritical conditions

This study examines the pressure-temperature (P-T) behavior of reactive mixtures composed of lactalbumin and water under subcritical and isochoric conditions. The impact of density on the P-T behavior was investigated for an initial lactalbumin composition of 5%, covering a density range of 0.7597 g/mL to 0.85620 g/mL. Additionally, the effect of varying lactalbumin concentrations, ranging from 3% to 15% (w/w), at a constant initial density of 0.831 g/mL, was also studied. Isochoric lines and density values of the reactive mixtures were compared to those of pure water under identical pressure and temperature conditions in all experiments. Furthermore, the total soluble solids (TSS) content was analyzed after each experiment, along with the thermal stability of amino acids subjected to prolonged reaction periods and high temperatures.

Overcoming Product Inhibition in a Nucleophilic Aromatic Substitution Reaction.

The development of a nucleophilic aromatic substitution (SNAr) reaction for the synthesis of belzutifan and related analogues is disclosed. This classical transformation suffered from reaction stalling, despite prolonged reaction times. Through experimental and mechanistic studies, product inhibition was revealed and rationalized. Herein, we describe our efforts to overcome this synthetic challenge and demonstrate the importance of the judicious choice of the solvent to achieve reactivity.