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As nitrogen analogues of iron-oxo species, high-valent iron-imido species have attracted great interest in the past decades. FeV-alkylimido species are generally considered to be key reaction intermediates in Fe(III)-catalyzed C(sp3)âH bond aminations of alkyl azides but remain underexplored. Here, it is reported that iron-corrole (Cor) complexes can catalyze a wide range of intramolecular CâH amination reactions of alkyl azides to afford a variety of 5-, 6- and 7-membered N-heterocycles, including alkaloids and natural product derivatives, with up to 3880 turnover numbers (TONs) and excellent diastereoselectivity (>99:1 d.r.). Mechanistic studies including density functional theory (DFT) calculations and intermolecular hydrogen atom abstraction (HAA) reactions reveal key reactive FeV-alkylimido intermediates. The [FeV(Cor)(NAd)] (Ad = adamantyl) complex is independently prepared and characterized through electron paramagnetic resonance (EPR), resonance Raman (rR) measurement, and X-ray photoelectron spectroscopy (XPS). This complex is reactive toward HAA reactions with kinetic isotope effects (KIEs) similar to [Fe(Cor)]-catalyzed intramolecular CâH amination of alkyl azides.
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A series of sterically congested quinone methides (QMs) exhibit photoinduced antiproliferative activity against some human cancer cell lines. To elucidate the structure-reactivity relationship and details of mechanisms of the photogeneration of sterically congested QMs, we chose phenylphenol derivatives 1-3 as QM precursors and investigated their photodehydration processes in aqueous solutions using ultrafast spectroscopy and theoretical computations. We found that meta derivatives 1 and 2 undergo water-mediated excited-state proton transfer (ESPT) from the phenol OH, followed by expulsion of the OH- to form QMs. By comparison, para derivative 3 proceeds via water-mediated ESPT from H2O to benzyl alcohol coupled with dehydration as the first step, delivering a cation intermediate, which further deprotonates to yield QM. Such results would help chemists understand more about the meta effects in photochemistry and about ESPT and would help synthetic chemists design sterically congested QM precursors with extraordinary reactivities and expand applications of QMs in biological and medical systems.
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Halophenols are toxic and persistent pollutants in water environments which poses harm to various organisms. Due to their high stability and long residence time, ultraviolet radiation, heavy metals and oxidizing agents have been largely adopted on treating these compounds. However, these treatment methods could pose toxicity or hazardous risks to the marine environment and plant operators. In this study, a water-soluble porphyrin photocatalyst was synthesized and introduced for halophenol treatment using UV-free LED white light. The porphyrin catalyst is a macrocyclic ring consisting of pyrroles linked with methine bridges, the highly conjugated ring provided the superior functionality of visible light absorption. Surprisingly, over 99 % degradation of halophenols and over 90 % dehalogenation have been achieved without metal chelation, even higher than those of transition metal porphyrins with inclusion of Fe3+, Zn2+, Cu2+, Co2+, Ni2+, and Mn2+. Ring-opening reactions were confirmed with the formation of carboxylic acids; dicarboxylic acids like acrylic acid, and malonic acid; while fumaric acid was the main product. Total organic carbon results indicated no CO2 produced during the reaction. Triplet absorbance and scavenger studies also indicated that singlet oxygen and conduction band electrons are the main radical species for halophenol degradation. The 100-fold singlet emission quenching over triplet absorption quenching indicated that the excited electrons tend to be transferred via singlet state. This concept brings along new approaches detoxifying halophenol-related wastewater without UV, metals and other additives, which is more environmentally-friendly and sheds light to the conversion of toxic materials into useful chemical precursors.
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The case study explores bilingualism and neurodegenerative disorders, specifically progressive supranuclear palsy (PSP) with speech and language disorder (PSP-SL). It features a 78-year-old Mexican American woman who exhibits echolalia only in response to Spanish. This selective impairment suggests unevenly affected language control mechanisms despite her proficiency in both languages. Cognitive function is evaluated with neuropsychological tests; she's diagnosed with PSP-SL, depression, and anxiety. Echolalia in response to one language implies complex phonological retrieval mechanisms. Such observations prompt further inquiry into bilingual language control and processing mechanisms. The case supports evidence that bilingualism may attenuate neurodegeneration effects, suggesting better inhibitory control over disinhibited speech through enhanced executive functioning benefits.
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Ultrasmall copper nanoclusters have recently emerged as promising photocatalysts for organic synthesis, owing to their exceptional light absorption ability and large surface areas for efficient interactions with substrates. Despite significant advances in cluster-based visible-light photocatalysis, the types of organic transformations that copper nanoclusters can catalyze remain limited to date. Herein, we report a structurally well-defined anionic Cu40 nanocluster that emits in the second near-infrared region (NIR-II, 1000-1700 nm) after photoexcitation and can conduct single-electron transfer with fluoroalkyl iodides without the need for external ligand activation. This photoredox-active copper nanocluster efficiently catalyzes the three-component radical couplings of alkenes, fluoroalkyl iodides, and trimethylsilyl cyanide under blue-LED irradiation at room temperature. A variety of fluorine-containing electrophiles and a cyanide nucleophile can be added onto an array of alkenes, including styrenes and aliphatic olefins. Our current work demonstrates the viability of using readily accessible metal nanoclusters to establish photocatalytic systems with a high degree of practicality and reaction complexity.
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Thermally activated delayed fluorescence (TADF) has been widely applied to electroluminescent materials to take the best advantage of triplet excitons. For some materials, the TADF originates from high-level reverse intersystem crossing (hRISC), and has attracted much attention due to its high efficiency for utilizing the triplet excitons. However, reports concerning the mechanistic studies on the hRISC-TADF process and structure-property correlation are sparse. In this study, we prepared three compounds containing triphenylamine and benzophenone with different substitution positions, o-TPA-BP, m-TPA-BP, and p-TPA-BP, in which only p-TPA-BP displays strong luminescence and hRISC-TADF features. To investigate the mechanism of the substituent-position-dependent hRISC-TADF, ultrafast time-resolved spectroscopy was utilized to observe the deactivation pathways with the assistance of theoretical calculations. The results show that o-TPA-BP will not generate triplet species, and the triplet species for m-TPA-BP will rapidly deactivate. Only p-TPA-BP can transition back to the singlet state from the T2 state effectively and exhibit a large gap between T1 and T2 to favor the hRISC route. These results illustrate how the substitution position affects the ISC and further influences the luminescence properties, which can provide new insights for developing new high-efficiency luminescent materials.
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A calcaneal tuberosity avulsion fracture occurring simultaneously with a rupture of the Achilles tendon, although occurring through similar mechanisms, is a rare injury pattern to see in combination and presents a unique challenge to the surgeon. The patient we present was initially found to have a type II fracture of the calcaneal tuberosity. However, during surgical fixation of the fracture, a complete rupture of the Achilles tendon was noticed. The technique used in this case was the fixation of the fracture fragment with two 5 mm fully threaded screws. The tendon was then reattached to the calcaneus using two Mitek anchors (DePuy Mitek Inc., MA, USA) with a modified Bunnell technique. There are a number of techniques suggested in the literature, including, among others, K-wires (DePuy Mitek Inc., MA, USA) and screw fixation. Our patient recovered well and has now been discharged from further orthopaedic follow-up.
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Photosynthesis of H2O2 from earth-abundant O2 and H2O molecules offers an eco-friendly route for solar-to-chemical conversion. The persistent challenge is to tune the photo-/thermo- dynamics of a photocatalyst toward efficient electron-hole separation while maintaining an effective driving force for charge transfer. Such a case is achieved here by way of a synergetic strategy of sub-band-assisted Z-Scheme for effective H2O2 photosynthesis via direct O2 reduction and H2O oxidation without a sacrificial agent. The optimized SnS2/g-C3N4 heterojunction shows a high reactivity of 623.0 µmol g-1 h-1 for H2O2 production under visible-light irradiation (λ > 400 nm) in pure water, ≈6 times higher than pristine g-C3N4 (100.5 µmol g-1 h-1). Photodynamic characterizations and theoretical calculations reveal that the enhanced photoactivity is due to a markedly promoted lifetime of trapped active electrons (204.9 ps in the sub-band and >2.0 ns in a shallow band) and highly improved O2 activation, as a result of the formation of a suitable sub-band and catalytic sites along with a low Gibbs-free energy for charge transfer. Moreover, the Z-Scheme heterojunction creates and sustains a large driving force for O2 and H2O conversion to high value-added H2O2.
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Nitrenium ions are important reactive intermediates participating in the synthetic chemistry and biological processes. Little is known about triplet phenyl nitrenium ions regarding their reactivity, lifetimes, spectroscopic features, and electronic configurations, and no ground state triplet nitrenium ion has been directly detected. In this work, m-pyrrolidinyl-phenyl hydrazine hydrochloride (1) is synthesized as the photoprecursor to photochemically generate the corresponding m-pyrrolidinyl-phenyl nitrenium ion (2), which is computed to adopt a π, π* triplet ground state. A combination of femtosecond (fs) and nanosecond (ns) transient absorption (TA) spectroscopy, cryogenic continuous-wave electronic paramagnetic resonance (CW-EPR) spectroscopy, computational analysis, and photoproduct studies was performed to elucidate the photolysis pathway of 1 and offers the first direct experimental detection of a ground state triplet phenyl nitrenium ion. Upon photoexcitation, 1 forms S1, where bond heterolysis occurs and the NH3 leaving group is extruded in 1.8 ps, generating a vibrationally hot, spin-conserving closed-shell singlet phenyl nitrenium ion (12) that undergoes vibrational cooling in 19 ps. Subsequent intersystem crossing takes place in 0.5 ns, yielding the ground state triplet phenyl nitrenium ion (32), with a lifetime of 0.8 µs. Unlike electrophilic singlet phenyl nitrenium ions, which react rapidly with nucleophiles, this triplet phenyl nitrenium reacts through sequential H atom abstractions, resulting in the eventual formation of the reduced m-pyrrolidinyl-aniline as the predominant stable photoproduct. Supporting the triplet ground state, continuous irradiation of 1 in a glassy matrix at 80 K in an EPR spectrometer forms a paramagnetic triplet species, consistent with a triplet nitrenium ion.
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Cocrystal engineering is an efficient and simple strategy to construct functional materials, especially for the exploitation of novel and multifunctional materials. Herein, we report two kinds of nucleic-acid-base cocrystal systems that imitate the strong hydrogen bond interactions constructed in the form of complementary base pairing. The two cocrystals studied exhibit different colors of phosphorescence from their monomeric counterparts and show the feature of rare high-temperature phosphorescence. Mechanistic studies reveal that the strong hydrogen bond network stabilizes the triplet state and suppresses non-radiative transitions, resulting in phosphorescence even at 425 K. Moreover, the isolation effects of the hydrogen bond network regulate the interactions between the phosphor groups, realizing the manipulation from aggregation to single-molecule phosphorescence. Benefiting from the long-lived triplet state with a high quantum yield, the generation of reactive oxygen species by energy transfer is also available to utilize for some applications such as in photodynamic therapy and broad-spectrum microbicidal effects. In vitro experiments show that the cocrystals efficiently kill bacteria on a tooth surface and significantly help prevent dental caries. This work not only provides deep insight into the relationship of the structure-properties of cocrystal systems, but also facilitates the design of multifunctional cocrystal materials and enriches their potential applications.
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Anti-Infecciosos , Cárie Dentária , Ácidos Nucleicos , Humanos , Cristalização , Anti-Infecciosos/farmacologiaRESUMO
This research article uses density functional theory (DFT) to study photoinduced borylation. This work examined the electron donor-acceptor complex (EDA) of bis(catecholato)diboron with different redox-active leaving groups and bis(pinacol)diboron with aryl N-hydroxyphthalimide. The results of these DFT studies show the complex ratio of B2cat2 and N, N-dimethylacetamide (DMA) should be 1 : 2 which is consistent with the experimental results in the literature. We further proposed a reaction mechanism and calculated the energies associated with each step.
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Mercury (Hg) is a ubiquitous environmental contaminant known to bioaccumulate in biota and biomagnify in food webs. Parasites occur in nearly every ecosystem and often interact in complex ways with other stressors that their hosts experience. Hepatozoon spp. are intraerythrocytic parasites common in snakes. The Florida green watersnake (Nerodia floridana) and the banded watersnake (Nerodia fasciata) occur syntopically in certain aquatic habitats in the Southeastern United States. The purpose of this study was to investigate relationships among total mercury (THg) concentrations, body size, species, habitat type and prevalence and parasitemia of Hepatozoon spp. infections in snakes. In the present study, we sampled N. floridana and N. fasciata from former nuclear cooling reservoirs and isolated wetlands of the Savannah River Site in South Carolina. We used snake tail clips to quantify THg and collected blood samples for hemoparasite counts. Our results indicate a significant, positive relationship between THg and snake body size in N. floridana and N. fasciata in both habitats. Average THg was significantly higher for N. fasciata compared to N. floridana in bays (0.22 ± 0.02 and 0.08 ± 0.006 mg/kg, respectively; p < 0.01), but not in reservoirs (0.17 ± 0.02 and 0.17 ± 0.03 mg/kg, respectively; p = 0.29). Sex did not appear to be related to THg concentration or Hepatozoon spp. infections in either species. We found no association between Hg and Hepatozoon spp. prevalence or parasitemia; however, our results suggest that species and habitat type play a role in susceptibility to Hepatozoon spp. infection.
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Eucoccidiida , Mercúrio , Poluentes Químicos da Água , Animais , South Carolina , Mercúrio/análise , Ecossistema , Parasitemia/parasitologia , Bioacumulação , Serpentes/parasitologia , Monitoramento Ambiental/métodos , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/análiseRESUMO
The 3',5'-dimethoxybenzoin (DMB) system has been widely investigated as a photoremovable protecting group (PRPG) for the elimination of various functional groups and has been applied in many fields. The photolysis of DMB fluoride leads to a highly efficient photocyclization-deprotection reaction, resulting in a high yield of 3',5'-dimethoxybenzofuran (DMBF) in a MeCN solution, while there is a competitive reaction that produces DMB in an aqueous solution. The yield of DMB increased as the volume ratio of water increased. To understand the solvent effect of the photolysis of selected DMB-based compounds, a combination of femtosecond to nanosecond transient absorption spectroscopies (fs-TA and ns-TA), nanosecond time-resolved resonance Raman spectroscopy (ns-TR3) and quantum chemical calculation was employed to study the photophysical and photochemical reaction mechanisms of DMB fluoride in different solutions. Facilitated by the bichromophoric nature of DMB fluoride with electron-donating and -withdrawing chromophores, the cyclized intermediates could be found in a pure MeCN solution. The deprotection of a cyclic biradical intermediate results in the simultaneous formation of DMBF and a cyclic cation species. On the other hand, in aqueous solution, fs-TA experiments revealed that α-keto cations could be observed after excitation directly, which could easily produce the DMB through the addition of a hydroxyl within 8.7 ps. This work provides comprehensive photo-deactivation mechanisms of DMB fluoride in MeCN and aqueous conditions and provides critical insights regarding the biomedical application of DMB-based PRPG compounds.
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INTRODUCTION: Nurses working within Emergency Departments are frequently required to care for individuals impacted by suicidal behaviour. LITERATURE REVIEW: Published research into the experience of such individuals in emergency care, is limited. Studies identified do not distinguish between self-harming and suicidal behaviour and do not reveal the lived experience in depth. AIM AND METHODOLOGY: This research reveals the lived experience of being in emergency care following an overdose with suicidal intent, through the collection of data while patients are still in hospital. Sixteen semi-structured interviews were conducted with patients on a medical admission ward. The research uses an interpretive hermeneutic phenomenological approach. ANALYSIS: A thematic analysis indicated six key themes: The fear of death and dying, The hospital - a place of safety, Loved ones a reason to live, Feelings of hopelessness, Eclipsed as a suicidal patient, and the Impact of human relationships. DISCUSSION: The findings are discussed and contextualized within wider literature: The fear of death, hopelessness, the role of stigma and shame, including anticipatory stigma, and the impact of kindness and relationships. Implications for practice are outlined, informing how care can be enhanced by nursing staff.
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Serviços Médicos de Emergência , Transtornos Fóbicos , Comportamento Autodestrutivo , Humanos , Hermenêutica , Ideação SuicidaRESUMO
Adult-onset egg allergy is rare compared to child-onset egg allergy, and the component-resolved diagnosis test is effective in evaluating food allergy. We herein report a 24-year-old woman with late-onset egg-yolk allergy diagnosed as bird-egg syndrome. The prolonged exposure to pet parrots' dander or dropping through the respiratory system caused sensitization to the Gal d 5 component and resulted in a cross-reaction to egg yolk. Since the patient was suspected of the syndrome by her history, the skin prick test, ISAC ImmunoCAP, and serum ImmunoCAP test were performed. By confirming Gal d 5 component by ISAC ImmunoCAP, the patient was diagnosed with the syndrome. In patients with newly adult-onset food allergy, the clinician must identify the environmental conditions which can cause cross-sensitization and perform the causative component test.
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The present work aimed to evaluate the degradability of the chitosan polymer by soil microorganisms.This evaluation was accomplished using the Most Probable Number (MPN) method by plating in drops so that soil microorganisms capable of degrading the polymeric material could be quantified. Soil samples diluted in three specific culture media for each typeof microorganism were plated bacteria, fungi and actinobacteriaand they were maintained at 28°C for seven days to determine the growth rate of fungi and actinobacteria, and for 48hoursfor the development of bacteria. Significant differences in the MPN of actinobacteriarelative to the other groups analyzed were observed. Thus, the method used was effective for determining the degradability of the chitosan biopolymer when observing the development of microorganisms subjected to the replacement of thecarbonsource by the addition of 2% w v-1of the chitosan biopolymer to the culture medium. The formation of clear regions around the microbial colonies was a strong indicator of biodegradation.
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Análise do Solo , Biodegradação Ambiental , Quitosana/análise , Quitosana/químicaRESUMO
In the case of a patient with a small number of unilateral remaining teeth in the mandible, a restoration with conventional removable partial denture cannot provide sufficient retention and resistance. A harmful stress from the poor stability of denture on remaining teeth occurs due to alveolar bone resorption in edentulous area. Although implant fixed prosthesis can provide multiple benefits over conventional removable partial denture, there are limitations come from anatomic structures and costs. In this case, an implant-assisted removable partial denture (IARPD) with a couple of implants placed in strategic positions can be a treatment modality. The objective of this article is to present a case report of two patients showed satisfactory clinical outcomes during three-year follow-up period describing the fabrication and advantages of removable partial denture assisted by teeth and implants (IARPD) for a patient with a small number of unilateral remaining teeth in mandible using Locator as an implant attachment.
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Humanos , Reabsorção Óssea , Prótese Parcial Removível , Dentaduras , Seguimentos , Mandíbula , Próteses e Implantes , Reabilitação , DenteRESUMO
The mangaba (Hancornia speciosa) stands out and has a great potential for economic exploitation and researches have suggested relevant results regarding the nutritional and functional value of this food. Therefore, the objective of this study was to chemically and physicochemically characterize the mangaba fruit harvested in the Middle Araguaia region. It was evaluated the chemical composition, antioxidant activity, volatile compounds, preliminary photochemical studies of phenolic components and the cytotoxic potential of ethanolic extract fruits against Artemia salina. The mean pH, the total titratable acidity and the value for reducing sugars conclude that the mangaba possesses the characteristics appropriate for both fresh consumption and for processing. Between the mean values measured, the fruits presented high fiber content and a low caloric value. The analysis of the antioxidant potential revealed a significant activity and in the volatile compounds analysis, esters were the major class presents. The result of the phytochemical screening revealed that phenols, flavonoids and tannins were present in the ethanolic extract of mangaba and a significant activity in the cytotoxicity assay was observed.
A mangaba (Hancornia speciosa) destaca-se pelo ótimo potencial de exploração econômica e pesquisas têm sugerido resultados relevantes em relação ao valor nutricional e funcional deste alimento. Portanto, o objetivo deste estudo foi caracterizar química e físico-quimicamente os frutos de mangaba colhidos na região do Médio Araguaia. Foi avaliada a composição química, atividade antioxidante, compostos voláteis, estudo fitoquímico preliminar de compostos fenólicos e o potencial citotóxico de extratos etanólicos do frutos contra Artemia salina. O pH, a acidez total titulável e o valor de açúcares redutores concluem que a mangaba possui características apropriadas tanto para consumo in natura quanto para processamento. Entre os valores médios obtidos, os frutos apresentaram alto teor de fibra e um baixo valor calórico. A análise de potencial antioxidante revelou uma atividade significativa e, na análise de compostos voláteis, ésteres representaram a classe predominante. O resultado do ensaio fitoquímico revelou que fenois, flavonoides e taninos estavam presentes no extrato etanólico de mangaba e uma atividade significativa no ensaio citotóxico foi observada.
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The compositions of the essential oils from the leaves of three domestic varieties of the guava tree Psidium guajava L. (Paluma, Século XXI and Pedro Sato) and of one wild variety were compared. Essential oils were extracted by steam distillation, the components were identified by gas chromatography coupled to mass spectrometry GC-MS, and the apparent concentrations were determined by gas chromatography with a flame ionization detector. The results demonstrated that the three essential oils contained many common substances with a prevalence of 1,8-cineole, whereas the essential oil of the Paluma variety contained 1,8-cineole (42.68 percent) as the major constituent, as well as α-terpineol (38.68 percent). The principal components of the essential oil of the Século XXI variety were 1,8-cineole (18.83 percent), trans-caryophyllene (12.08 percent), and selin-11-en-4-αol (20.98 percent), while those of the Pedro Sato variety and of the wild plant were 1,8-cineole (17.68 percent) and (12.83 percent), caryophyllene oxide (9.34 percent) and (9.09 percent), and selin-11-en-4-α-ol (21.46 percent) and (22.19 percent), respectively.
Os óleos essenciais de folhas de goiabeira Psidium guajava L. de três diferentes cultivares (Paluma, Século XXI e Pedro Sato) e da planta silvestre foram analisados a fim de comparar os seus constituintes. O óleo essencial foi obtido por hidrodestilação em aparelho de Clevenger modificado. Para a caracterização e quantificação dos compostos presentes por CG-EM e CG respectivamente. Os resultados mostraram que os três óleos essenciais analisados apresentam inúmeras substâncias em comum com a predominância do 1,8-cineol. O óleo essencial da cultivar Paluma se difere dos demais devido a alta concentração de 1,8-cineol (42,68 por cento) e do α-terpineol (38,68 por cento). No óleo essencial da cultivar Século XXI observase a presença do 1,8 cineol (18,83 por cento), trans-carifileno (12,08 por cento) e o selin-11-en-4-α-ol (20,98 por cento) como majoritários, enquanto que a cultivar Pedro Sato e a planta silvestre apresentaram com o 1,8 cineol com (17,68 por cento) e (12,83 por cento), oxido de cariofileno (9,34 por cento) e (9,09 por cento) e o selin-11-en-4-α-ol com (21,46 por cento) e (22,19 por cento), respectivamente.
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Twenty-four Holstein steer calves (88 ± 3kg) with abomasal catheters were randomly assigned within blocks to one of four treatments. The treatments consisted of four abomasal infusions: water (control), 4 g/kg BW.d-1 of partially hydrolyzed starch (SH), 0.6 g/kg BW.d-1 of casein, and a mix of SH + casein. The small intestine was collected and five equidistan, 1m sites were identified (duodenum, jejunum 1, jejunum 2 jejunum 3 and ileum). Maltase specific activity in mucosal homogenate and brush border membrane vesicles, SGLT1 protein abundance, and sodium-dependent glucose uptake in brush border membrane vesicles did not differ between the calves receiving different abomasal infusion treatments. However, maltase specific activity in homogenates and brush border membrane vesicles increased four-fold from the duodenum to the first jejunal site before declining steadily towards the ileum (p=0.0145 p=0.0020, respectively). The SGLT1 abundance differed by intestinal sampling site (p=0.0162). These data indicated that cattle might not have the ability to alter the capacity for glucose uptake when challenged with different substrates and that the regulation of SGLT1 expression could differ between bovine and other species.