RESUMEN

N-heterocyclic compounds are important molecular scaffolds in the search for new drugs, since most drugs contain heterocyclic moieties in their molecular structure, and some of these classes of heterocycles are able to provide ligands for two or more biological targets. Ketene dithioacetals are important building blocks in organic synthesis and are widely used in the synthesis of N-heterocyclic compounds. In this work, we used double vinylic substitution reactions on ketene dithioacetals to synthesize a small library of heterocyclic derivatives and evaluated their cytotoxic activity in breast and ovarian cancer cells, identifying two benzoxazoles with good potency and selectivity. In silico predictions indicate that the two most active derivatives exhibit physicochemical properties within the range of drug-like compounds and showed potential to interact with HDAC8 and ERK1 cancer-related targets.

Asunto(s)

Antineoplásicos , Etilenos , Compuestos Heterocíclicos , Cetonas , Humanos , Línea Celular Tumoral , Etilenos/química , Etilenos/farmacología , Compuestos Heterocíclicos/química , Compuestos Heterocíclicos/farmacología , Compuestos Heterocíclicos/síntesis química , Antineoplásicos/farmacología , Antineoplásicos/síntesis química , Antineoplásicos/química , Cetonas/química , Cetonas/farmacología , Cetonas/síntesis química , Relación Estructura-Actividad , Histona Desacetilasas/metabolismo , Simulación del Acoplamiento Molecular , Ensayos de Selección de Medicamentos Antitumorales , Acetales/química , Acetales/farmacología , Acetales/síntesis química , Proteínas Represoras

RESUMEN

The (S)-norcoclaurine synthase from Thalictrum flavum (TfNCS) stereoselectively catalyzes the Pictet-Spengler reaction between dopamine and 4-hydroxyphenylacetaldehyde to give (S)-norcoclaurine. TfNCS can catalyze the Pictet-Spengler reaction with various aldehydes and ketones, leading to diverse tetrahydroisoquinolines. This substrate promiscuity positions TfNCS as a highly promising enzyme for synthesizing fine chemicals. Understanding carbonyl-containing substrates' structural and electronic signatures that influence TfNCS activity can help expand its applications in the synthesis of different compounds and aid in protein optimization strategies. In this study, we investigated the influence of the molecular properties of aldehydes and ketones on their reactivity in the TfNCS-catalyzed Pictet-Spengler reaction. Initially, we compiled a library of reactive and unreactive compounds from previous publications. We also performed enzymatic assays using nuclear magnetic resonance to identify some reactive and unreactive carbonyl compounds, which were then included in the library. Subsequently, we employed QSAR and DFT calculations to establish correlations between substrate-candidate structures and reactivity. Our findings highlight correlations of structural and stereoelectronic features, including the electrophilicity of the carbonyl group, to the reactivity of aldehydes and ketones toward the TfNCS-catalyzed Pictet-Spengler reaction. Interestingly, experimental data of seven compounds out of fifty-three did not correlate with the electrophilicity of the carbonyl group. For these seven compounds, we identified unfavorable interactions between them and the TfNCS. Our results demonstrate the applications of in silico techniques in understanding enzyme promiscuity and specificity, with a particular emphasis on machine learning methodologies, DFT electronic structure calculations, and molecular dynamic (MD) simulations.

Asunto(s)

Aldehídos , Cetonas , Aldehídos/química , Aldehídos/metabolismo , Cetonas/química , Cetonas/metabolismo , Especificidad por Sustrato , Ligasas de Carbono-Nitrógeno/metabolismo , Ligasas de Carbono-Nitrógeno/química , Thalictrum/enzimología , Thalictrum/metabolismo , Thalictrum/química , Simulación de Dinámica Molecular , Biocatálisis

RESUMEN

OBJECTIVE: Stress distribution assessment by finite elements analysis in poly(etheretherketone) (PEEK) implant and abutment as retainers of single crowns in the anterior region. MATERIALS AND METHODS: Five 3D models were created, varying implant/abutment manufacturing materials: titanium (Ti), zirconia (Zr), pure PEEK (PEEKp), carbon fiber-reinforced PEEK (PEEKc), glass fiber-reinforced PEEK (PEEKg). A 50 N load was applied 30o off-axis at the incisal edge of the upper central incisor. The Von Mises stress (σvM) was evaluated on abutment, implant/screw, and minimum principal stress (σmin) and maximum shear stress (τmax) for cortical and cancellous bone. RESULTS: The abutment σvM lowest stress was observed in PEEKp group, being 70% lower than Ti and 74% than Zr. On the implant, PEEKp reduced 68% compared to Ti and a 71% to Zr. In the abutment screws, an increase of at least 33% was found in PEEKc compared to Ti, and of at least 81% to Zr. For cortical bone, the highest τmax values were in the PEEKp group, and a slight increase in stress was observed compared to all PEEK groups with Ti and Zr. For σmin, the highest stress was found in the PEEKc. Stress increased at least 7% in cancellous bone for all PEEK groups. CONCLUSION: Abutments and implants made by PEEKc concentrate less σvM stress, transmitting greater stress to the cortical and medullary bone. CLINICAL RELEVANCE: The best stress distribution in PEEKc components may contribute to decreased stress shielding; in vitro and in vivo research is recommended to investigate this.

Asunto(s)

Benzofenonas , Coronas , Pilares Dentales , Análisis del Estrés Dental , Análisis de Elementos Finitos , Cetonas , Ensayo de Materiales , Polietilenglicoles , Polímeros , Titanio , Circonio , Cetonas/química , Polietilenglicoles/química , Humanos , Circonio/química , Titanio/química , Fibra de Carbono/química , Diseño de Implante Dental-Pilar , Incisivo , Materiales Dentales/química , Implantes Dentales de Diente Único , Hueso Cortical , Vidrio/química , Diseño de Prótesis Dental

RESUMEN

STATEMENT OF PROBLEM: Additive (AM) and subtractive (SM) manufacturing have become popular for fabricating occlusal devices with materials of different chemical compositions. However, knowledge on the effect of material and antagonist type on the wear characteristics of occlusal devices fabricated by using different methods is limited. PURPOSE: The purpose of this in vitro study was to evaluate the effect of material and antagonist type on the wear of occlusal devices fabricated by using conventional manufacturing, AM, and SM. MATERIAL AND METHODS: Two-hundred and forty Ø10×2-mm disk-shaped specimens were fabricated by using heat-polymerized polymethylmethacrylate (control, CM), AM clear device resin fabricated in 3 different orientations (horizontal [AMH], diagonal [AMD], and vertical [AMV]), SM polymethylmethacrylate (SMP), and SM ceramic-reinforced polyetheretherketone (SMB) (n=40). Specimens were then divided into 4 groups based on the antagonists: steatite ceramic (SC); multilayered zirconia (ZR); lithium disilicate (EX); and zirconia-reinforced lithium silicate (ZLS) used for thermomechanical aging (n=10). After aging, the volume loss (mm3) and maximum wear depth (µm) were digitally evaluated. Data were analyzed with 2-way analysis of variance and Tukey honestly significant difference tests (α=.05). RESULTS: The interaction between the device material and the antagonist affected volume loss and maximum depth of wear (P<.001). AMH had volume loss and depth of wear that was either similar to or higher than those of other materials (P≤.044). When SC was used, CM had higher volume loss and depth of wear than AMV, and, when EX was used, AMD had higher volume loss and depth of wear than SMP (P≤.013). SC and ZR led to higher volume loss of CM and AMH than EX and led to the highest depth of wear for these materials, while ZR also led to the highest volume loss and depth of wear of AMD and AMV (P≤.019). EX led to the lowest volume loss and depth of wear of AMV and SMP and to the lowest depth of wear of AMH (P≤.021). Regardless of the antagonist, SMB had the lowest volume loss and depth of wear (P≤.005). CONCLUSIONS: AMH mostly had higher volume loss and depth of wear, while SMB had the lowest volume loss, and its depth of wear was not affected by the tested antagonists. ZR mostly led to higher volume loss and maximum depth of wear, while EX mostly led to lower volume loss and maximum depth of wear of the tested occlusal device materials.

Asunto(s)

Materiales Dentales , Ensayo de Materiales , Polimetil Metacrilato , Circonio , Materiales Dentales/química , Polimetil Metacrilato/química , Circonio/química , Cerámica/química , Humanos , Técnicas In Vitro , Ferulas Oclusales , Alisadura de la Restauración Dental , Diseño de Prótesis Dental , Benzofenonas , Porcelana Dental/química , Polímeros/química , Propiedades de Superficie , Polietilenglicoles/química , Cetonas/química

RESUMEN

Steroids that take part in the pathways of human steroidogenesis are involved in many biological mechanisms where they interact with calcium. In the present work, the binding selectivities and affinities for calcium of progestagens, mineralocorticoids, androstagens, and estrogens were studied by Electrospray Ionization-Mass Spectrometry (ESI-MS). The adduct profile of each steroid was characterized by high resolution and tandem mass spectrometry. The relative stability of the most important adducts was studied by threshold collision induced dissociation, E1/2. Doubly-charged steroid-calcium complexes [nM + Ca]2+ with n = 1-6 were predominant in the mass spectra. The adduct [5M + Ca]2+ was the base peak for most 3-keto-steroids, while ligands bearing hindered ketones or α-hydroxy-ketones also yielded [nM + Ca + mH2O]2+ with n = 3-4 and m = 0-1. Principal component analysis allowed us to spot the main differences and similarities in the binding behavior of these steroids. The isomers testosterone and dehydroepiandrosterone, androstanolone and epiandrosterone, and 17-α-hydroxyprogesterone and 11-deoxycorticosterone showed remarkable differences in their adduct profiles. Computational modeling of representative adducts was performed by density functional theory methods. The possible binding modes at low and high numbers of steroid ligands were determined by calcium Gas Phase Affinity, and through modeling of the complexes and comparison of their relative stabilities, in agreement with the experimental results.

Asunto(s)

Calcio , Espectrometría de Masa por Ionización de Electrospray , Humanos , Calcio/química , Espectrometría de Masa por Ionización de Electrospray/métodos , Espectrometría de Masas en Tándem/métodos , Esteroides , Cetonas

RESUMEN

The development of inexpensive and portable point-of-care devices for measuring nutritional physiological parameters from blood (e.g., glucose, ketones) has accelerated our understanding and assessment of real-time variation in human health, but these have infrequently been tested or implemented in wild animals, especially in relation to other key biological or fitness-related traits. Here we used point-of-care devices to measure blood levels of glucose, ketones, uric acid, and triglycerides in free-ranging house finches (Haemorhous mexicanus)-a common songbird in North America that has been well-studied in the context of urbanization, nutrition, health, and sexual selection-during winter and examined (1) repeatability of these methods for evaluating blood levels in these wild passerines, (2) intercorrelations among these measurements within individuals, (3) how blood nutritional-physiology metrics related to a bird's body condition, habitat of origin (urban vs. suburban), poxvirus infection, and sex; and (4) if the expression of male sexually selected plumage coloration was linked to any of the nutritional-physiological metrics. All blood-nutritional parameters were repeatable. Also, there was significant positive covariation between concentrations of circulating triglycerides and glucose and triglycerides and uric acid. Urban finches had higher blood glucose concentrations than suburban finches, and pox-infected individuals had lower blood triglyceride concentrations than uninfected ones. Last, redder males had higher blood glucose, but lower uric acid levels. These results demonstrate that point-of-care devices can be useful, inexpensive ways of measuring real-time variation in the nutritional physiology of wild birds.

Asunto(s)

Pinzones , Passeriformes , Infecciones por Poxviridae , Humanos , Masculino , Animales , Pinzones/fisiología , Urbanización , Ácido Úrico/metabolismo , Glucemia , Sistemas de Atención de Punto , Animales Salvajes , Ecosistema , Fenómenos Fisiológicos de la Nutrición , Cetonas/metabolismo , Triglicéridos

RESUMEN

Aim: In recent years, great advances have been made in the use of CAD/CAM to prepare fixed restorations. The marginal and internal fit of these restorations is a principal determinant for their clinical success. In addition, the nature of the oral environment affects the mechanical properties of these restorations. Therefore, this study aimed to investigate the effect of aging process under conditions that simulate the oral environment on the marginal adaptation, and, fracture resistance of crowns fabricated from polyether ether ketone (PEEK) using CAD/CAM methods. Methods: Twenty identical crown restorations were fabricated by using CAD/CAM methods to mill polyether ether ketone (PEEK) material. These crowns were produced by using a software design of an epoxy resin replica of the prepared maxillary first premolar tooth. All PEEK crowns were cemented and randomly divided into two equal groups (A, B). Each group was divided into subgroups (A1, A2 and B1, B2). Group A1 and A2 were used to measure marginal adaptation and fracture resistance, respectively, before aging, while group (B1 and B2) were measured after aging. The cemented crowns were mounted in resin molds to facilitate the sectioning process. The measurements of the marginal gap were performed after sectioning at four points using a stereomicroscope. The fracture resistance of the crowns was investigated using a universal testing machine. A statistical analysis was performed using the GraphPad Prism® software version and unpaired Student's t-test. Results: The results revealed that aging affected the marginal gap, and the fracture resistance of the PEEK crowns. While aging, negatively affected the conditions under investigation, however the least significant difference of marginal gap was found in the margin region. Conclusions: PEEK-CAD/CAM is considered as a good alternative prosthodontic material for fixed prostheses. The CAD/CAM technique used to make PEEK crown restorations in our study offers the advantages of high marginal accuracy and fracture resistance for long-term performance in the oral environment

Asunto(s)

Polímeros , Envejecimiento , Diseño Asistido por Computadora , Adaptación Marginal Dental , Coronas , Resistencia Flexional , Cetonas

RESUMEN

Recent studies have demonstrated the antiproliferative and cytotoxic effects of aza-steroids and steroidal sapogenins on human cancer cell lines. The scientific community has shown a growing interest in these compounds as drug candidates for cancer treatment. In the current work, we report the synthesis of new diosgenin oxime derivatives as potential antiproliferative agents. From (25 R)-5α-spirost-3,5,6-triol (1), a diosgenin derivative, ketones 2, 3, 4, and 9 were obtained and used as precursors of the new oximes. A condensation reaction was carried out between the steroidal ketones (2, 3, 4, and 9) with hydroxylamine hydrochloride in 2,4,6-trimethylpyridine to produce five spirostanic oximes (four of them are not reported before) with a 42-96% yield. Also, a new spirostanic α, ß-unsaturated cyanoketone was synthesized via Beckmann fragmentation using thionyl chloride with a 62% yield. Furthermore, we proposed a reaction mechanism with the aim of explaining such transformation.

Asunto(s)

Antineoplásicos , Diosgenina , Humanos , Cianocetona , Diosgenina/farmacología , Esteroides/farmacología , Antineoplásicos/farmacología , Oximas/farmacología , Cetonas/farmacología

RESUMEN

Based on its mechanical properties, PEEK (polyether-ether-ketone) might be useful in restorative procedures. In oral rehabilitation, its viability has been studied mainly for prostheses and dental implants. AIM: The aim of this study was to evaluate the fit accuracy of dental implant bars made of either PEEK or cobalt-chrome submitted to cycling mechanics. MATERIALS AND METHOD: This was an experimental in vitro study, where units were treated with two implants and mini-abutments, joined by cobalt-chrome or polyether-ether-ketone PEEK bars. A total 20 bars were prepared (n=10 per group) and subjected to mechanical cycling tests (1 million cycles on the distal cantilever of the bar in the vertical direction, 120N and sinusoidal loading, at a frequency of 2Hz). The fit at the abutment/implant interface was measured before and after cycling, and the counter-torque of the vertical screw of the mini abutments was measured after cycling, using a digital torquemeter. Data were analyzed by three-way ANOVA and Tukey's test at 5% significance level. RESULTS: No statistically significant interaction was found among the three factors considered (bar material, implant positioning and mechanical cycling) (p = 0.592). No significant difference was identified in the interaction between bar material and implant positioning (p = 0.321), or between implant positioning and mechanical cycling (p = 0.503). The association between bar material and mechanical cycling was statistically significant (p = 0.007), with the cobalt-chrome bar resulting in greater misfit with mechanical cycling. There was no difference in counter-torque values between groups. CONCLUSIONS: The PEEK bar provided better fit of the mini abutments to the implants, even after mechanical cycling. The counter-torque of the screws was similar in all scenarios considered.

---

O PEEK (Poli-éter-éter-cetona) é um material considerado para uso em procedimentos restauradores devido às suas propriedades mecânicas. Na reabilitação oral, sua viabilidade tem sido estudada principalmente para uso em próteses e implantes dentários. Objetivos: O objetivo deste estudo foi avaliar a precisão da adaptação de duas barras diferentes do tipo protocolo confeccionadas em PEEK ou Cobalto-Cromo, após serem submetidas à mecânica ciclística. Materiais e Método: As unidades experimentais foram constituídas por barras confeccionadas em Poli-ether-ether-Ketone (PEEK) e em Cobalto-Cromo (Co-Cr). Trata-se de um estudo experimental, in vitro, onde verificou-se unidades constituídas por dois implantes e mini pilares unidos com barras de Cobalto-Cromo ou PEEK. Foram confeccionados um total de 20 barras (n=10 em cada grupo) e as barras foram submetidas a ensaios de ciclagem mecânica (1 milhão de ciclos no cantilever distal da barra no sentido vertical, 120N e carregamento senoidal, a uma frequência de 2Hz). Antes e após a ciclagem realizou-se a mensuração da desadaptação na interface pilar/implante e após a ciclagem foi medido o contra-torque do parafuso vertical dos mini-pilares através de torquímetro digital TQ 8800 (LT Lutron, Taiwan). Os dados foram submetidos a ANOVA a três critérios e teste de Tukey ao nível de significância a 5%. Resultados: Constatou-se que não houve interação estatisticamente significativa entre os três fatores estudados, ou seja, entre o material da barra, o posicionamento do implante e a ciclagem mecânica (p = 0,592). Também não se identificou diferença estatística significativa da interação entre o material da barra e o posicionamento do implante (p = 0,321), nem entre o posicionamento do implante e a ciclagem mecânica (p = 0,503). Já a associação entre o material da barra e a ciclagem mecânica foi estatisticamente significativa (p = 0,007), onde a barra de Cobalto-Cromo resultou em maior desadaptação com a ciclagem mecânica. Não houve diferença nos valores dos contra-torques entre os grupos. Conclusões: Conclui-se que a barra de protocolo fabricada em PEEK proporcionou melhor adaptação dos mini pilares aos implantes mesmo após a ciclagem mecânica. Por fim, o contra-torque dos parafusos foi semelhante em todos os cenários avaliados.

Asunto(s)

Implantes Dentales , Pilares Dentales , Polietilenglicoles , Cetonas , Cobalto , Éteres , Análisis del Estrés Dental/métodos , Ensayo de Materiales

RESUMEN

The potential of ketogenic approaches to regulate energy balance has recently gained attention since ketones may influence both energy expenditure and energy intake. In this narrative review, we summarized the most relevant evidence about the role of ketosis on energy expenditure, substrate utilization, and energy intake in humans. We considered different strategies to induce ketosis, such as fasting, dietary manipulation, and exogenous ketone sources. In general, ketosis does not have a major influence on energy expenditure but promotes a shift in substrate utilization towards ketone body oxidation. The strategies to induce ketosis by reduction of dietary carbohydrate availability (e.g., ketogenic diets) do not independently influence energy intake, being thus equally effective for weight loss as diets with higher carbohydrate content. In contrast, the intake of medium-chain triglycerides and ketone esters induces ketosis and appears to increase energy expenditure and reduce energy intake in the context of high carbohydrate availability. These latter strategies lead to slightly enhanced weight loss. Unfortunately, distinguishing the effects of the various ketogenic strategies per se from the effects of other physiological responses is not possible with the available human data. Highly controlled, inpatient studies using targeted strategies to isolate the independent effects of ketones are required to adequately address this knowledge gap.

Asunto(s)

Dieta Cetogénica , Cetosis , Humanos , Cuerpos Cetónicos , Cetonas , Metabolismo Energético , Ingestión de Energía , Carbohidratos de la Dieta , Pérdida de Peso

RESUMEN

Polyether ether ketone (PEEK) is a biocompatible polymer used in maxillofacial and orthopedic applications because of its mechanical properties and chemical stability. However, this biomaterial is inert and requires surface modification to make it bioactive, enhancing implant-tissue integration and giving the material the ability to interact with the surrounding microenvironment. In this paper, surface of PEEK was activated by oxygen plasma treatment and this resulted in increasing reactivity and surface hydrophilicity. Then, a polydopamine (PDA) coating was deposited over the surface followed by biofunctionalization with an RGD peptide. The plasma effect was studied by contact angle measurements and scanning electron microscopy. X-ray photoelectron spectroscopy confirmed the presence of PDA coating and RGD peptide. Crystallinity and phase identification were carried out through X-ray diffraction. Quantification of the immobilized peptide over the PEEK surface was reached through UV-vis spectroscopy. In addition, in vitro tests with fibroblast cell line (NIH/3T3) determined the viability, attachment, spreading, and proliferation of these cells over the modified PEEK surfaces. According to the results, PEEK surfaces functionalized with peptides demonstrated an increased cellular response with each successive surface modification.

Asunto(s)

Cetonas , Polietilenglicoles , Polietilenglicoles/farmacología , Cetonas/farmacología , Éteres

RESUMEN

STUDY DESIGN: A laboratory study comparing polyether ether ketone (PEEK)-zeolite and PEEK spinal implants in an ovine model. OBJECTIVE: This study challenges a conventional spinal implant material, PEEK, to PEEK-zeolite using a nonplated cervical ovine model. SUMMARY OF BACKGROUND DATA: Although widely used for spinal implants due to its material properties, PEEK is hydrophobic, resulting in poor osseointegration, and elicits a mild nonspecific foreign body response. Zeolites are negatively charged aluminosilicate materials that are hypothesized to reduce this pro-inflammatory response when used as a compounding material with PEEK. MATERIALS AND METHODS: Fourteen skeletally mature sheep were, each, implanted with one PEEK-zeolite interbody device and one PEEK interbody device. Both devices were packed with autograft and allograft material and randomly assigned to one of 2 cervical disc levels. The study involved 2 survival time points (12 and 26 weeks) and biomechanical, radiographic, and immunologic endpoints. One sheep expired from complications not related to the device or procedure. A biomechanical evaluation was based on measures of segmental flexibility, using 6 degrees of freedom pneumatic spine tester. Radiographic evaluation was performed using microcomputed tomography scans in a blinded manner by 3 physicians. Levels of the pro-inflammatory cytokines, interleukin (IL)-1ß, IL-6, and tumor necrosis factor-alpha at the implant, were quantified using immunohistochemistry. RESULTS: PEEK-zeolite and PEEK exhibited an equivalent range of motion in flexion extension, lateral bending, and axial torsion. A motion was significantly reduced for implanted devices at both time points as compared with native segments. Radiographic assessments of fusion and bone formation were similar for both devices. PEEK-zeolite exhibited lower levels of IL-1ß ( P = 0.0003) and IL-6 ( P = 0.03). CONCLUSION: PEEK-zeolite interbody fusion devices provide initial fixation substantially equivalent to PEEK implants but exhibit a reduced pro-inflammatory response. PEEK-zeolite devices may reduce the chronic inflammation and fibrosis previously observed with PEEK devices.

Asunto(s)

Fusión Vertebral , Zeolitas , Animales , Ovinos , Microtomografía por Rayos X/métodos , Interleucina-6 , Polietilenglicoles/química , Cetonas/química , Éteres , Fusión Vertebral/métodos , Fenómenos Biomecánicos

RESUMEN

We report a strategy for the direct synthesis of 3-organylselanylthiochromones and 3-organylselanylchromones via the radical cyclization reaction between alkynyl aryl ketones containing an ortho-thiopropyl/methoxy group and diorganyl diselenides promoted by Oxone®. This method allows the construction and seleno-functionalization of thiochromones and chromones using Oxone® as a stable and non-hazardous oxidizing agent in the presence of CH3CN at 82 °C. These reactions tolerate a variety of substituents, and allowed the synthesis of twenty-one new 3-organylselanylthiochromones and selanylchromones in good to excellent yields (55-95%). Additionally, the developed method proved to be suitable for scale up (3.0 mmol, 80%), and the synthetic usefulness of the prepared compounds was demonstrated in the oxidation of 2-phenyl-3-(phenylselanyl)-4H-thiochromen-4-one.

Asunto(s)

Cromonas , Cetonas , Ciclización , Catálisis

RESUMEN

In this study, two different feeds were treated to produce hydrocarbons: (1) reagent-grade acetone, and (2) mixed ketones obtained from lignocellulosic biomass via the carboxylate platform. Acetone and mixed ketones underwent catalytic self-condensation over HZSM-5. For acetone, HZSM-5(80) was used, and the experiments were conducted in two sets: (1) vary temperature (305-415°C) at P = 101 kPa (abs) and weight hourly space velocity (WHSV) = 1.3 h-1; (2) vary WHSV (1.3-7.9 h-1) at T = 350 and 415°C, and P = 101 kPa (abs). For acetone over HZSM-5(280), the experiments were conducted in two sets: (1) vary WHSV (1.3-6.5 h-1) at T = 415°C, and P = 101 kPa (abs); and (2) vary WHSV (1.3-11.8 h-1) at P = 790 kPa (abs) and T = 415°C. For mixed ketones, HZSM-5(280) was used at WHSV = 1.9 h-1, T = 430-590°C, and P = 101 kPa (abs). For acetone at higher temperatures, the conversion was 100% and the liquid products were aromatics centered on C8. At low temperatures, conversion was less and the carbon liquid distribution was centered on C9 (mainly mesitylene). For mixed ketones, catalyst deactivation was higher causing product concentrations to change over time, and the highest conversion reached was 40%.

Asunto(s)

Acetona , Cetonas , Hidrocarburos , Catálisis , Biomasa

RESUMEN

Plants have profound therapeutic benefits, more economical treatments, fewer side effects, and a relatively cheap cost, making them a source of drugs for protective, preventative, curative, or conducive purposes and creating novel phytomedicines. Plant derived medicines are relatively safe compared to synthetic medicines. Many plants have proved to successfully aid in the treatment of diabetes including Filago hurdwarica (Wall. ex DC.) Wagenitz. The current investigations were therefore designed to assess the phytochemical, antioxidant, antidiabetic, and antihyperlipidemic activities of F. hurdwarica. The phytochemical investigations and antioxidant activities of different extracts were carried out using standard chemical tests, DPPH, and H2O2 scavenging assays. F. hurdwarica plant extract in Hydromethanolic solution were prepared by Soxhletation method and stored in refrigerator at 4°C for two days before use. Swiss Albino mice were made diabetic by a single dose of alloxan (150 mg/kg). Hydromethanolic plant extract and fractions of F. hurdwarica were screened for antidiabetic activity and given to the alloxan-induced diabetic mice at a concentration of 150-250 mg/kg of body weight in different groups of 6 diabetic mice each orally once a day for 15 days. Glibenclamide is also given to another group to as a standard drug to support the result at a dose of 10 mg/kg of body weight orally once a day for 15 days. Blood glucose levels and body weights of mice were measured on 0, 4, 7, 11 and 15th days. The study found that the extract was safe up to the dose level of 2000 mg/kg and the dose response effect of chloroform extract (150-250 mg/kg) of F. hurdwarica showed expressive antihyperglycemic effects and also improved other altered biochemical parameters associated with diabetes. The FTIR and XRD spectra demonstrated the occurrence of phenols, alcohols, alkenes, alkyl halides, ketones, and aromatic compounds and confirmed the amorphous nature of the extract. GC-MS spectral analysis showed the tentative presence of 31 phytochemical constituents in the chloroform extract of F. hurdwarica with different retention time. To conclude, the chloroform extract (250 mg/kg) of F. hurdwarica revealed considerable antioxidant, antihyperglycemic, and antihyperlipidemic potential and is safe for treating diabetes and related complications.

Asunto(s)

Asteraceae , Diabetes Mellitus Experimental , Alquenos/uso terapéutico , Aloxano/uso terapéutico , Animales , Antioxidantes/farmacología , Glucemia , Peso Corporal , Cloroformo/uso terapéutico , Diabetes Mellitus Experimental/inducido químicamente , Diabetes Mellitus Experimental/tratamiento farmacológico , Gliburida/uso terapéutico , Peróxido de Hidrógeno/uso terapéutico , Hipoglucemiantes/química , Hipoglucemiantes/farmacología , Hipoglucemiantes/uso terapéutico , Hipolipemiantes/química , Hipolipemiantes/farmacología , Hipolipemiantes/uso terapéutico , Cetonas/uso terapéutico , Ratones , Fenoles/análisis , Fitoquímicos/análisis , Fitoquímicos/farmacología , Fitoquímicos/uso terapéutico , Extractos Vegetales/química , Extractos Vegetales/farmacología , Extractos Vegetales/uso terapéutico

RESUMEN

For the synthesis of polymeric resins, it is of great importance to review the raw materials and the equipment to be used to avoid the presence of compounds that may affect the effectiveness of the polymerization and the characteristics of the plastic to be obtained. Iron oxide is a compound that can be present in reactors after maintenance due to the techniques used and the cleaning of this equipment, and it can affect the characteristics of the resins, reducing their quality. In this study, the presence of FeO in different concentrations was evaluated to determine its effects on the properties and pyrolysis of polypropylene resins by using X-ray refraction to determine the elements of the samples, evaluating thermal degradation by TGA, the variation in molecular weight by measuring the MFI, and the compounds obtained from pyrolysis by chromatography. The results showed that the thermal degradation decreased as the FeO concentration increased, while for the MFI, the relationship was directly proportional. The evaluation of the compounds obtained from pyrolysis showed an increase in the production of alcohols, alkynes, ketones, and acids, and a decrease in alkanes and alkenes, showing that FeO affects the properties of polypropylene and the compounds that are produced during pyrolysis.

Asunto(s)

Polipropilenos , Pirólisis , Alcanos , Alquenos , Alquinos , Catálisis , Compuestos Férricos , Residuos Industriales , Cetonas , Plásticos , Polvos , Resinas de Plantas

RESUMEN

This study describes the reaction of 2-amino arylalkynyl ketones with organoselenolates to form (Z)-vinyl selenides, which lead to 4-organoselenyl quinolines via an intramolecular condensation. Using the optimized reaction conditions, the generality of this cyclization was studied with various arylalkynyl ketones and diorganyl diselenides. The study of the reaction mechanisms led to the isolation and identification of a vinyl selenide, which was the key intermediate for this cyclization. To expand the structural diversity and to demonstrate the applicability of the 4-organoselenyl quinolines prepared, we studied their application as substrates in the cleavage of the carbon-selenium bond using n-butyllithium followed by the capture of the lithium intermediate by electrophiles and Suzuki and Sonogashira cross-coupling reactions.

Asunto(s)

Quinolinas , Selenio , Alquinos/química , Carbono , Catálisis , Ciclización , Cetonas/química , Litio , Estructura Molecular , Quinolinas/química , Estereoisomerismo

RESUMEN

BACKGROUND: Based on the current need for new drugs against malaria, our study evaluated eight beta amino ketones in silico and in vitro for potential antimalarial activity. METHODS: Using the Brazilian Malaria Molecular Targets (BraMMT) and OCTOPUS® software programs, the pattern of interactions of beta-amino ketones was described against different proteins of P. falciparum and screened to evaluate their physicochemical properties. The in vitro antiplasmodial activities of the compounds were evaluated using a SYBR Green-based assay. In parallel, in vitro cytotoxic data were obtained using the MTT assay. RESULTS: Among the eight compounds, compound 1 was the most active and selective against P. falciparum (IC50 = 0.98 µM; SI > 60). Six targets were identified in BraMMT that interact with compounds exhibiting a stronger binding energy than the crystallographic ligand: P. falciparum triophosphate phosphoglycolate complex (1LYX), P. falciparum reductase (2OK8), PfPK7 (2PML), P. falciparum glutaredoxin (4N0Z), PfATP6, and PfHT. CONCLUSIONS: The physicochemical properties of compound 1 were compatible with the set of criteria established by the Lipinski rule and demonstrated its potential as a drug prototype for antiplasmodial activity.

Asunto(s)

Antimaláricos , Malaria Falciparum , Malaria , Antimaláricos/farmacología , Antimaláricos/uso terapéutico , Glutarredoxinas/uso terapéutico , Humanos , Cetonas/farmacología , Cetonas/uso terapéutico , Ligandos , Malaria Falciparum/tratamiento farmacológico , Extractos Vegetales/uso terapéutico , Plasmodium falciparum

RESUMEN

STUDY DESIGN: Prospective, randomized, blinded clinical trial. OBJECTIVE: To examine clinical and radiological outcomes in patients undergoing anterior cervical discectomy and fusion (ACDF) surgeries randomized to receive either polyether-ether-ketone (PEEK) or structural bone allografts. SUMMARY OF BACKGROUND DATA: The biomechanical qualities as well as osteoconductive, osteogenic, and osteoinductive properties of various graft materials have been previously evaluated. There remain questions, however, as to whether there are any clinical and/or radiographic outcome differences in the selection of interbody graft types for ACDF. METHODS: Patients undergoing one- to three-level ACDF with single anterior plate fixation were randomized (1:1 ratio) to receive either cortical allograft or PEEK interbody spacers. Radiographic and clinical outcomes were assessed at 3, 6, 12, and 24 months with an additional postoperative radiographic assessment. RESULTS: A total of 120 patients were enrolled and randomized. Comparing clinical outcomes, no differences in arm or neck pain scores were noted; however, there was a statistically significant (≤0.041) improvement in SF-36 PCS scores for the allograft group at all follow-up time points and a tendency toward lower disability scores. Overall, evidence of radiographic fusion was achieved in 87 (91.6%) patients: five (10.2%) and three (6.5%) patients had pseudoarthrosis (P = 0.72) in the PEEK and allograft groups, respectively. At 24 months' follow-up time, any cervical or segmental alignment restoration achieved with surgery was lost and no statistically significant changes were detected when all levels of surgery were included. Likewise, there were no statistically significant differences between the groups for anterior or posterior body height measurements at the 24 months' follow-up. Approximately 20% of patients had anterior and posterior subsidence, all grade 0 regardless of the group assignment. CONCLUSION: Comparable radiographic outcomes were observed for patients undergoing one- to three-level PEEK versus allograft-assisted ACDF surgeries. Although MCID comparisons suggest that allograft and PEEK-treated patients have similar clinical outcomes, testing that incorporates the magnitude of the change suggests that there may be a statistically significant greater magnitude of improvement for the allograft group patients, but further studies with a larger sample size would be helpful to determine if a true effect exists.

Asunto(s)

Vértebras Cervicales , Fusión Vertebral , Aloinjertos , Benzofenonas , Vértebras Cervicales/diagnóstico por imagen , Vértebras Cervicales/cirugía , Discectomía , Humanos , Cetonas/uso terapéutico , Polietilenglicoles/uso terapéutico , Polímeros , Estudios Prospectivos , Resultado del Tratamiento

RESUMEN

OBJECTIVES: To evaluate the bond strength of four types of posts (pre-fabricated fiberglass post, fiberglass post anatomized with composite resin, milled fiberglass post, and milled polyetheretherketone (PEEK) post), and two types of resin cements (conventional and self-adhesive) by assessing immediate bond strength and post-mechanical aging at each root third. MATERIALS AND METHODS: Bovine endodontically treated roots (16 groups, n = 8) were prepared and the posts were produced and luted; the specimens of aging groups were cycled (300,000 cycles under 50 N load at 1.2 Hz frequency); six slices of each root were obtained; push-out test was performed by using a universal testing machine (500 N load at 1 mm/min cross speed); fracture pattern was classified into five levels. The statistical analyses used were three-way ANOVA, Tukey's test (for bond strength), and Fisher's test (for fracture pattern) (α < 0.05). RESULTS: Differences were found between the cements for posts (conventional: p < 0.001; self-adhesive: p = 0.002), whereas no difference was found for root region (p = 0.941; p = 0.056, respectively); analysis of each root showed significant differences for cements (p < 0.001), posts (p < 0.001), and mechanical cycling (p = 0.001); in terms of double interaction, differences were found for posts and mechanical cycling (p = 0.005); no other interactions were observed (double or triple); the fracture pattern showed difference between the groups for both cements. CONCLUSIONS: Milled PEEK posts seem to be a good clinical option, but they require improvement of CAD-CAM technology and advances towards their adhesion. CLINICAL RELEVANCE: Milled posts are promising and can reduce clinical time for rehabilitation of extensively destroyed teeth.

Asunto(s)

Recubrimiento Dental Adhesivo , Técnica de Perno Muñón , Bovinos , Animales , Cementos de Resina/química , Análisis del Estrés Dental , Cavidad Pulpar , Ensayo de Materiales , Vidrio/química , Resinas Compuestas/química , Cetonas , Polietilenglicoles/química , Dentina