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1.
Acta Pharm ; 74(3): 525-537, 2024 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-39279522

RESUMEN

Polyurethane/hydroxyapatite (PU/HA) composites are well-known for various biomedical applications. This study reports a chemical approach to improve the interaction between HA and PU matrix. HA was surface-modified with 1,6-hexamethylene diisocyanate (HMDI). First, an isocyanate-modified HA (IHA) was synthesized by hydro-thermal method. Second, IHA was incorporated into a separately synthesized thermoplastic PU by a solvent casting technique. A series of PU/IHA composites was prepared by varying PU᾿s soft and hard segments. The IHA was added to PU (5 and 10 %). The FTIR spectra exhibited characteristic bands of urethane and HA, confirming the synthesis of the composites. XRD study showed the crystallite size of IHA (20 Å) with hexagonal geometry and an amorphous to semicrystalline nature of composites. SEM showed that composites displayed porous and granular morphology. The TGA thermograms of the composites revealed the thermal stability up to 400 °C. The IHA addition considerably improved hydrophilicity and degradation of the composites in simulated body fluid (SBF). MTT assay revealed improved cytocompatibility (> 80 %) of the composites. These results demonstrated an appreciable improvement in structure, morphology, hydrophilicity, degradation, and cytocompatibility of PU/IHA composites by chemical modification of HA. Hence, these composites possess remarkable potential for biomedical applications such as tissue regeneration.


Asunto(s)
Materiales Biocompatibles , Durapatita , Poliuretanos , Poliuretanos/química , Durapatita/química , Materiales Biocompatibles/química , Animales , Ratones , Ensayo de Materiales/métodos , Espectroscopía Infrarroja por Transformada de Fourier/métodos , Propiedades de Superficie , Cianatos/química , Ingeniería de Tejidos/métodos , Supervivencia Celular/efectos de los fármacos , Porosidad , Difracción de Rayos X , Isocianatos/química , Interacciones Hidrofóbicas e Hidrofílicas
2.
Int J Biol Macromol ; 278(Pt 2): 134657, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-39147346

RESUMEN

This research addresses the need for enhanced biomaterials by investigating the influence of the NCO/OH ratio on sodium alginate-based polyurethane elastomers(Al-PUEs), offering novel insights into their structural, thermal, mechanical and swelling behavior. Al-PUEs were prepared by blending the chain extenders with key ingredients in a specific molar ratio using aliphatic HMDI and HTPB monomers. The chemical linkages, crystalline behavior, homogeneity, and surface morphology of PUEs were evaluated by FT-IR, XRD, SEM, and EDX analysis. Thermo-mechanical studies were performed using TGA, DSC and tensile testing. Swelling behavior and absorption analysis were analyzed in DMSO and water. The analysis indicated that the hydrophilicity and swelling behavior of the prepared PUEs were affected by the addition of sodium alginate content. The results exhibit the tailor-made network structure of Al-PUEs, resulting in better thermal stability, elasticity of materials via stress-strain behavior and marvelous characteristic features than traditional high-tech yields. Furthermore, the resulting Al-PUEs are potential candidates for biomedical implants.


Asunto(s)
Alginatos , Elastómeros , Isocianatos , Poliuretanos , Poliuretanos/química , Alginatos/química , Elastómeros/química , Isocianatos/química , Materiales Biocompatibles/química , Resistencia a la Tracción , Espectroscopía Infrarroja por Transformada de Fourier , Ensayo de Materiales , Interacciones Hidrofóbicas e Hidrofílicas , Temperatura
3.
Int J Biol Macromol ; 276(Pt 1): 133617, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38960219

RESUMEN

Non-isocyanate polyurethanes (NIPUs) have attracted increasing attention as a sustainable alternative to conventional isocyanate-based polyurethanes. This study synthesized non-isocyanate hydroxyurethanes (NIHUs) through an addition reaction between propylene carbonate (PC) and 1,2-ethylenediamine (EDA). The resulting NIHU was then hybridized with carboxymethyl cellulose (CMC) to investigate its hybridization potential. Structural analysis through FTIR, NMR, and XRD confirmed the crystalline nature of NIHU, featuring urethane bonds and abundant hydroxyl groups. It was found that NIHU and CMC interacted by forming hydrogen bonds between hydroxyl groups of NIHU and carboxyl groups of CMC, resulting in a dense CMC/NIHU hybrid structure. NMR and XRD analyses revealed changes in the hybrids' chain mobility, the Young's modulus of the hybrid with 30 % NIHU content decreased from 1627 MPa to 502 MPa relative to CMC, and the elongation at break increased from 4.44 % to 17.2 %. Increasing the concentration of NIHU in CMC reduced the hydrophobicity, in terms of water contact angle, from 70° to 41.7°. The simplicity of the synthesis method for NIHU, coupled with the desirable structure, strength, and balanced flexibility of CMC/NIHU hybrids, is expected to facilitate the production of NIHU-rich hybrids and increase their application in packaging.


Asunto(s)
Carboximetilcelulosa de Sodio , Tecnología Química Verde , Poliuretanos , Carboximetilcelulosa de Sodio/química , Poliuretanos/química , Poliuretanos/síntesis química , Interacciones Hidrofóbicas e Hidrofílicas , Isocianatos/química
4.
Environ Sci Process Impacts ; 26(8): 1373-1379, 2024 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-38963002

RESUMEN

Environmental fate and toxicity testing typically requires knowledge of the water solubility of the test substances. Determining the solubility of aromatic diisocyanates in water poses great challenges because of their hydrophobic nature and water-reactivity. The reactive dissolution process is dynamic and the establishment of a steady-state equilibrium cannot readily be observed. In preparation of experimental work, computer simulation was used to derive and evaluate criteria that enable distinguishing homogeneous (i.e., substances would be fully dissolved in water) from heterogeneous (i.e., a separate organic phase would be present) conditions. The simulation utilized available kinetic information and models representing the main physical and chemical processes taking place. It was found that the transition to heterogeneous conditions (i.e., the exceedance of the solubility limit with increasing loading) can be identified by observing either a rapid decline in ultimate yield of the diamine hydrolysis product from near-stoichiometric to much lower values, or a decrease in rate of formation of the diamine hydrolysis product relative to its ultimate yield. The latter criterion is expected to be the more powerful indicator. These criteria can be used in future work to define and interpret an experimental program for determining solubility limits for aromatic diisocyanates or other poorly-soluble, water-reactive substances.


Asunto(s)
Isocianatos , Contaminantes Químicos del Agua , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/química , Isocianatos/química , Isocianatos/análisis , Modelos Químicos , Solubilidad , Agua/química , Simulación por Computador , Cinética
5.
Contact Dermatitis ; 91(3): 212-221, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38956835

RESUMEN

BACKGROUND: Isocyanates are used as starting materials of polyurethane (PU) products. They are relatively important occupational skin sensitizers. OBJECTIVES: To analyse results of a large isocyanate patch test series of 19 isocyanate test substances and 4,4'-diaminodiphenylmethane (MDA), a marker of 4,4'-diphenylmethane diisocyanate (MDI) hypersensitivity. METHODS: Test files were screened for positive reactions in the isocyanate series. Patients with positive reactions were analysed for occupation, exposure and diagnosis. RESULTS: In 2010-2019, 53 patients had positive reactions in the series (16% of 338 patients tested). MDA, the well-established screening substance for MDI allergy, was positive in 30 patients, an in-house monomeric MDI test substance in 23 patients and 3 different polymeric MDI test substances in 19-21 patients. We diagnosed 16 cases of occupational allergic contact dermatitis (OACD) from MDI including 3 pipe reliners. Hexamethylene-1,6-diisocyanate (HDI) oligomers in paint hardeners caused 5 cases of OACD, more cases than 2,4-toluene diisocyanate (TDI; n = 3) and isophorone diisocyanate (IPDI; n = 1) put together. CONCLUSIONS: In contrast to previous studies, polymeric MDI test substances were not superior to a monomeric MDI. Pipe reliners may get sensitised not only by epoxy products and acrylates but also by MDI in hardeners of PU pipe coatings. HDI oligomers were the second most important causes of OACD after MDI.


Asunto(s)
Dermatitis Alérgica por Contacto , Dermatitis Profesional , Isocianatos , Pruebas del Parche , Humanos , Isocianatos/efectos adversos , Pruebas del Parche/métodos , Dermatitis Profesional/diagnóstico , Dermatitis Profesional/etiología , Dermatitis Alérgica por Contacto/diagnóstico , Dermatitis Alérgica por Contacto/etiología , Femenino , Masculino , Adulto , Poliuretanos/efectos adversos , Persona de Mediana Edad , Compuestos de Anilina
6.
J Adhes Dent ; 26: 171-178, 2024 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-38966001

RESUMEN

PURPOSE: To evaluate the effect of urethane methacrylate precursor (UMP) on the enzymatic resistance of demineralized dentin (DD) matrices. MATERIALS AND METHODS: Experimental treatments containing 0 (control), 1, and 5 mmol/L UMP dissolved in an acetone (Ace) solution were formulated. Dentin matrix specimens were demineralized in vitro and immersed in the experimental treatments for 1 h. The treated specimens were then stored in 0.1 mg/mL collagenase solution for 24 h, after which their dry mass loss and hydroxyproline (HYP) release were assessed. The swelling ratios of specimens in each group were also evaluated. The interaction between UMP and the dentin matrix was observed using field-emission scanning electron microscopy (FE-SEM). Endogenous enzyme activity in dentin was evaluated using confocal laser scanning microscopy (CLSM). RESULTS: Compared with the other treatment groups, treatment with 1 mM and 5 mM UMP-Ace significantly decreased the dry mass loss, HYP release and swelling ratio of the DD matrix (p < 0.05). FE-SEM and CLSM observations showed that treatment with UMP-Ace protected the structure of the dentin matrix and decreased porosity within the dentin-collagen network. CONCLUSION: Treatment with 1 mM and 5 mM UMP-Ace protects DD matrix against collagenase degradation and may be clinically useful for improving the durability of the hybrid layer.


Asunto(s)
Dentina , Metacrilatos , Microscopía Confocal , Microscopía Electrónica de Rastreo , Dentina/efectos de los fármacos , Humanos , Metacrilatos/química , Isocianatos/química , Recubrimiento Dental Adhesivo , Recubrimientos Dentinarios/química , Ensayo de Materiales , Colagenasas , Hidroxiprolina , Colágeno , Cementos de Resina/química
7.
Int J Mol Sci ; 25(14)2024 Jul 22.
Artículo en Inglés | MEDLINE | ID: mdl-39063233

RESUMEN

Carbodiimides are important crosslinkers in organic synthesis and are used in the isocyanate industry as modifier additives. Therefore, the understanding of their formation is of high importance. In this work, we present a theoretical B3LYP/6-31G(d) and SMD solvent model and experimental investigation of the formation of diphenylcarbodiimide (CDI) from phenyl isocyanate using a phosphorus-based catalyst (MPPO) in ortho-dichlorobenzene (ODCB) solvent. Kinetic experiments were based on the volumetric quantitation of CO2 evolved, at different temperatures between 40 and 80 °C. Based on DFT calculations, we managed to construct a more detailed reaction mechanism compared to previous studies which is supported by experimental results. DFT calculations revealed that the mechanism is composed of two main parts, and the rate determining step of the first part, controlling the CO2 formation, is the first transition state with a 52.9 kJ mol-1 enthalpy barrier. The experimental activation energy was obtained from the Arrhenius plot (ln k vs. 1/T) using the observed second-order kinetics, and the obtained 55.8 ± 2.1 kJ mol-1 was in excellent agreement with the computational one, validating the complete mechanism, giving a better understanding of carbodiimide production from isocyanates.


Asunto(s)
Carbodiimidas , Isocianatos , Carbodiimidas/química , Isocianatos/química , Cinética , Termodinámica , Catálisis , Dióxido de Carbono/química , Solventes/química , Temperatura
8.
Int J Mol Sci ; 25(13)2024 Jul 02.
Artículo en Inglés | MEDLINE | ID: mdl-39000407

RESUMEN

This work focused on the preparation and investigation of polyurethane (SO-PU)-containing sunflower oil glycerides. By transesterification of sunflower oil with glycerol, we synthesized a glyceride mixture with an equilibrium composition, which was used as a new diol component in polyurethanes in addition to poly(ε-caprolactone)diol (PCLD2000). The structure of the glyceride mixture was characterized by physicochemical methods, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), nuclear magnetic resonance spectroscopy (NMR), and size exclusion chromatography (SEC) measurements. The synthesis of polyurethanes was performed in two steps: first the prepolymer with the isocyanate end was synthesized, followed by crosslinking with an additional amount of diisocyanate. For the synthesis of the prepolymer, 4,4'-methylene diphenyl diisocyanate (MDI) or 1,6-hexamethylene diisocyanate (HDI) were used as isocyanate components, while the crosslinking was carried out using an additional amount of MDI or HDI. The obtained SO-PU flexible polymer films were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The so-obtained flexible SO-PU films were proved to be suitable for the preparation of potentially biocompatible and/or biodegradable scaffolds. In addition, the stress versus strain curves for the SO-PU polymers were interpreted in terms of a mechanical model, taking into account the yield and the strain hardening.


Asunto(s)
Polímeros , Poliuretanos , Aceite de Girasol , Poliuretanos/química , Polímeros/química , Aceite de Girasol/química , Materiales Biocompatibles/química , Isocianatos/química , Poliésteres/química , Espectroscopía de Resonancia Magnética , Espectroscopía Infrarroja por Transformada de Fourier
9.
Toxicol Ind Health ; 40(8): 441-464, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38748851

RESUMEN

The water extractability and acute aquatic toxicity of seven aliphatic diisocyanate-based prepolymer substances were investigated to determine if lesser reactivity of the aliphatic isocyanate groups, as well as increased ionization potential of the expected (aliphatic amine-terminated) polymeric hydrolysis products, would influence their aquatic behavior compared to that of previously investigated aromatic diisocyanate-based prepolymers. At loading rates of 100 and 1,000 mg/L, only the substances having log Kow ≤9 exhibited more than 1% extractability in water, and a maximum of 66% water extractability was determined for a prepolymer having log Kow = 2.2. For the more hydrophobic prepolymer substances (log Kow values from 18-37), water extractability was negligible. High-resolution mass spectrometric analyses were performed on the water-accommodated fractions (WAF) of the prepolymers, which indicated the occurrence of primary aliphatic amine-terminated polymer species having backbones and functional group equivalent weights aligned to those of the parent prepolymers. Measurements of reduced surface tension and presence of suspended micelles in the WAFs further supported the occurrence of these surface-active cationic polymer species as hydrolysis products of the prepolymers. Despite these characteristics, the water-extractable hydrolysis products were practically non-toxic to Daphnia magna. All of the substances tested exhibited 48-h EL50 values of >1,000 mg/L, with one exception of EL50 = 157 mg/L. The results from this investigation support a grouping of the aliphatic diisocyanate-based prepolymers as a class of water-reactive polymer substances having predictable aquatic exposure and a uniformly low hazard potential, consistent with that previously demonstrated for the aromatic diisocyanate-based prepolymers.


Asunto(s)
Isocianatos , Contaminantes Químicos del Agua , Animales , Contaminantes Químicos del Agua/toxicidad , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/análisis , Isocianatos/química , Isocianatos/toxicidad , Polímeros/química , Polímeros/toxicidad , Daphnia/efectos de los fármacos , Relación Estructura-Actividad , Poliuretanos/química , Poliuretanos/toxicidad
10.
Sci Total Environ ; 934: 173250, 2024 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-38761928

RESUMEN

Isocyanides and isocyanates are some of the most reactive compounds in organic chemistry, making them perceived as compounds with high potential for use in both the laboratory and industry. With their high reactivity also comes several disadvantages, most notably their potentially high toxicity. The following article is a collection of information on the toxic effects of the isocyanide group on the human body and the environment. Information on the mechanism of how these harmful substances affect living tissues and the environment, worldwide information on how to protect against these chemicals, current regulations, and exposure limits for specific countries is compiled. The latest research on the application uses of isocyanates and isocyanides is also outlined, as well as the latest safer and greener methods and techniques to work with these compounds. Additionally, the presented article can serve as a brief guide to the organic toxicity of a group of isocyanates and isocyanates.


Asunto(s)
Cianuros , Isocianatos , Isocianatos/toxicidad , Cianuros/química , Humanos , Contaminantes Ambientales/toxicidad , Exposición a Riesgos Ambientales
11.
Clin Toxicol (Phila) ; 62(3): 197-199, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38587093

RESUMEN

INTRODUCTION: Acute intoxication rarely produces conditions that require urgent surgical care. CASE SUMMARY: A 45-year-old man presented to the emergency department with severe abdominal pain after the deliberate ingestion of 200 cm3 of polyurethane mixed with methylene diphenyl diisocyanate and urethane primers. On an initial laparoscopic examination, foreign material was observed in the peritoneal space with haemoperitoneum. Emergency exploration was then undertaken for suspected gastric perforation. Full-thickness damage was identified on the stomach wall during the operation. The material in the gastrointestinal tract and peritoneal space was gently removed. Moulded casts of the entire stomach and distal oesophagus were extracted successfully. The patient was discharged 14 days after surgery. IMAGES: Computed tomography revealed foreign material occupying the entire gastric chamber, as well as diffuse gastric perforation. CONCLUSIONS: Life-threatening gastric perforation can occur after polyurethane foam ingestion. Clinical/medical toxicologists and emergency physicians need to be aware of the highly expandable nature of this agent.


Asunto(s)
Poliuretanos , Humanos , Masculino , Persona de Mediana Edad , Tomografía Computarizada por Rayos X , Estómago/lesiones , Cuerpos Extraños/cirugía , Cuerpos Extraños/complicaciones , Dolor Abdominal/etiología , Isocianatos , Intento de Suicidio
12.
Trans R Soc Trop Med Hyg ; 118(7): 436-439, 2024 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-38586989

RESUMEN

Leakage of methyl isocyanate from the Union Carbide plant in Bhopal, India, killed thousands and left deleterious trans-generational effects. Gas-exposed populations experience higher rates of lung and metabolic diseases, and immune dysregulation, all associated with adverse outcomes in coronavirus disease 2019 (COVID-19). We used publicly available, official data from government sources to estimate COVID-19-associated crude mortality in populations with and without a history of gas exposure. Overall, there were 1240 deaths among patients hospitalized with known COVID-19 in Bhopal, of which 453 (36.53%) were in gas-exposed individuals, 726 (58.55%) were in gas-unexposed individuals and the exposure status of 61 (4.92%) individuals could not be determined. There were 351 and 375 deaths in gas-unexposed people in the first (April 2020-February 2021) and second (March 2021-July 2021) waves, respectively; in the gas-exposed population, there were 300 and 153 deaths in the two respective waves. The overall annualized crude mortality of COVID-19 was 3.84 (95% CI 3.41 to 4.33) times higher in the gas-exposed population at 83.6 (95% CI 76.1 to 91.7) per 100 000 compared with the gas-unexposed population, at 21.8 (95% CI 20.2 to 23.4) per 100,000. When stratified by age, compared with unexposed people, the gas-exposed individuals experienced 1.88 (95% CI 1.61 to 2.21) and 1.24 (95% CI 1.02 to 1.50) times the mortality rates in the age groups of 35-65 and >65 y, respectively. These findings indicate that gas-exposed individuals are likely to have a higher risk of severe COVID-19 and death and need to be specifically targeted and recognized for preventive and promotive efforts.


Asunto(s)
COVID-19 , SARS-CoV-2 , Humanos , COVID-19/mortalidad , COVID-19/epidemiología , India/epidemiología , Adulto , Masculino , Femenino , Persona de Mediana Edad , Isocianatos/efectos adversos , Sobrevivientes/estadística & datos numéricos , Anciano , Liberación Accidental de Bhopal , Exposición a Riesgos Ambientales/efectos adversos , Adolescente , Adulto Joven , Niño , Preescolar
13.
Int J Mol Sci ; 25(7)2024 Mar 23.
Artículo en Inglés | MEDLINE | ID: mdl-38612435

RESUMEN

This study presents the synthesis of four series of novel hybrid chalcones (20,21)a-g and (23,24)a-g and six series of 1,3,5-triazine-based pyrimido[4,5-b][1,4]diazepines (28-33)a-g and the evaluation of their anticancer, antibacterial, antifungal, and cytotoxic properties. Chalcones 20b,d, 21a,b,d, 23a,d-g, 24a-g and the pyrimido[4,5-b][1,4]diazepines 29e,g, 30g, 31a,b,e-g, 33a,b,e-g exhibited outstanding anticancer activity against a panel of 60 cancer cell lines with GI50 values between 0.01 and 100 µM and LC50 values in the range of 4.09 µM to >100 µM, several of such derivatives showing higher activity than the standard drug 5-fluorouracil (5-FU). On the other hand, among the synthesized compounds, the best antibacterial properties against N. gonorrhoeae, S. aureus (ATCC 43300), and M. tuberculosis were exhibited by the pyrimido[4,5-b][1,4]diazepines (MICs: 0.25-62.5 µg/mL). The antifungal activity studies showed that triazinylamino-chalcone 29e and triazinyloxy-chalcone 31g were the most active compounds against T. rubrum and T. mentagrophytes and A. fumigatus, respectively (MICs = 62.5 µg/mL). Hemolytic activity studies and in silico toxicity analysis demonstrated that most of the compounds are safe.


Asunto(s)
Chalconas , Isocianatos , Mycobacterium tuberculosis , Chalconas/farmacología , Antifúngicos/farmacología , Staphylococcus aureus , Antibacterianos/farmacología , Azepinas/farmacología , Fluorouracilo , Neisseria gonorrhoeae , Triazinas/farmacología
14.
Chem Commun (Camb) ; 60(27): 3657-3660, 2024 Mar 28.
Artículo en Inglés | MEDLINE | ID: mdl-38451232

RESUMEN

In this article, we report the synthesis of sydnonimines from sydnones and their use as dipoles for fast click-and-release reactions. The process relies on nucleophilic aromatic substitution of aliphatic and aromatic amines with triflated sydnones. This new methodology allowed the preparation of functionalised sydnonimine probes that are otherwise difficult to prepare. These probes were then used to release a drug and a fluorescent aromatic isocyanate inside living cells.


Asunto(s)
Sidnonas , Isocianatos
15.
Chem Res Toxicol ; 37(3): 476-485, 2024 03 18.
Artículo en Inglés | MEDLINE | ID: mdl-38494904

RESUMEN

Mechanisms underlying methylene diphenyl diisocyanate (MDI) and other low molecular weight chemical-induced asthma are unclear and appear distinct from those of high molecular weight (HMW) allergen-induced asthma. We sought to elucidate molecular pathways that differentiate asthma-like pathogenic vs nonpathogenic responses to respiratory tract MDI exposure in a murine model. Lung gene expression differences in MDI exposed immune-sensitized and nonsensitized mice vs unexposed controls were measured by microarrays, and associated molecular pathways were identified through bioinformatic analyses and further compared with published studies of a prototypic HMW asthmagen (ovalbumin). Respiratory tract MDI exposure significantly altered lung gene expression in both nonsensitized and immune-sensitized mice, vs controls. Fifty-three gene transcripts were altered in all MDI exposed lung tissue vs controls, with levels up to 10-fold higher in immune-sensitized vs nonsensitized mice. Gene transcripts selectively increased in MDI exposed immune-sensitized animals were dominated by chitinases and chemokines and showed substantial overlap with those increased in ovalbumin-induced asthma. In contrast, MDI exposure of nonsensitized mice increased type I interferon stimulated genes (ISGs) in a pattern reflecting deficiency in adenosine deaminase acting against RNA (ADAR-1), an important regulator of innate, as well as "sterile" or autoimmunity triggered by tissue damage. Thus, MDI-induced changes in lung gene expression were identified that differentiate nonpathogenic innate responses in nonsensitized hosts from pathologic adaptive responses in immune-sensitized hosts. The data suggest that MDI alters unique biological pathways involving ISGs and ADAR-1, potentially explaining its unique immunogenicity/allergenicity.


Asunto(s)
Asma , Interferones , Animales , Ratones , Adenosina Desaminasa/genética , Adenosina Desaminasa/metabolismo , Alérgenos/inmunología , Alérgenos/toxicidad , Asma/inducido químicamente , Asma/genética , Expresión Génica , Interferones/inmunología , Interferones/metabolismo , Isocianatos , Pulmón/metabolismo , Ovalbúmina
16.
Biomater Sci ; 12(8): 2149-2164, 2024 Apr 16.
Artículo en Inglés | MEDLINE | ID: mdl-38487997

RESUMEN

The sole effective treatment for most patients with heart valve disease is valve replacement by implantation of mechanical or biological prostheses. However, mechanical valves represent high risk of thromboembolism, and biological prostheses are prone to early degeneration. In this work, we aim to determine the potential of novel environmentally-friendly non-isocyanate polyurethanes (NIPUs) for manufacturing synthetic prosthetic heart valves. Polyhydroxyurethane (PHU) NIPUs are synthesized via an isocyanate-free route, tested in vitro, and used to produce aortic valves. PHU elastomers reinforced with a polyester mesh show mechanical properties similar to native valve leaflets. These NIPUs do not cause hemolysis. Interestingly, both platelet adhesion and contact activation-induced coagulation are strongly reduced on NIPU surfaces, indicating low thrombogenicity. Fibroblasts and endothelial cells maintain normal growth and shape after indirect contact with NIPUs. Fluid-structure interaction (FSI) allows modeling of the ideal valve design, with minimal shear stress on the leaflets. Injection-molded valves are tested in a pulse duplicator and show ISO-compliant hydrodynamic performance, comparable to clinically-used bioprostheses. Poly(tetrahydrofuran) (PTHF)-NIPU patches do not show any evidence of calcification over a period of 8 weeks. NIPUs are promising sustainable biomaterials for the manufacturing of improved prosthetic valves with low thrombogenicity.


Asunto(s)
Prótesis Valvulares Cardíacas , Poliuretanos , Humanos , Poliuretanos/química , Isocianatos , Células Endoteliales , Válvula Aórtica/cirugía
17.
Chemistry ; 30(28): e202400581, 2024 May 17.
Artículo en Inglés | MEDLINE | ID: mdl-38470445

RESUMEN

α,ß-aromatic lactams are highly abundant in biologically active molecules, yet so far they cannot be radiolabeled with short-lived (t1/2=20.3 min), ß+-decaying carbon-11, which has prevented their application as positron emission tomography tracers. Herein, we developed, optimized, and applied a widely applicable, one-pot, quick, robust and automatable radiolabeling method for α,ß-aromatic lactams starting from [11C]CO2 using the reagent POCl3⋅AlCl3. This method proceeds via intramolecular Friedel-Crafts acylation of in situ formed [11C]isocyanates and shows a broad substrate scope for the formation of five- and six-membered rings. We implemented our developed labeling method for the radiosynthesis of the potential PARP1 PET tracer [carbonyl-11C]DPQ in a clinical radiotracer production facility following the standards of the European Pharmacopoeia.


Asunto(s)
Radioisótopos de Carbono , Isocianatos , Tomografía de Emisión de Positrones , Radiofármacos , Radioisótopos de Carbono/química , Acilación , Radiofármacos/química , Radiofármacos/síntesis química , Isocianatos/química , Tomografía de Emisión de Positrones/métodos , Marcaje Isotópico/métodos , Lactamas/química
18.
Rev Mal Respir ; 41(3): 227-236, 2024 Mar.
Artículo en Francés | MEDLINE | ID: mdl-38429194

RESUMEN

INTRODUCTION: This study aims to identify the epidemiological and occupational characteristics of patients with occupational asthma (OA) and to assess their clinical evolution and occupational outcomes. METHODS: We carried out a descriptive epidemiological study over a period of five years (from 2012 to 2016) about the OA cases in the private sector reported in the Tunisian region of Zaghouan. RESULTS: All in all, 165 OA cases were reported during the study period, representing an annual incidence of 733.3 cases per 1,000,000 workers in the private sector. Our study population was composed predominantly (85.5%) of women, whose mean age was 41.5±6.8years. More than three quarters of the affected persons were working in the automobile industry, and most illnesses (77%) were attributable to isocyanates. The mean time to onset of the respiratory symptoms was longer for low molecular weight agents (13.6±3.1years) compared to high molecular weight agents (12.0±3.9years) (P=0.0006). The majority of OA cases (66.7%) lost their jobs. Job loss was significantly more frequent among asthmatic women and workers with OA due to isocyanates. Among the 62 cases of OA for whom risk factors were eliminated, 45 nonetheless remained symptomatic. CONCLUSION: Effective prevention strategies involving the various actors need to be implemented in work environments so as to reduce the frequency and the medico-legal repercussions of a disabling condition.


Asunto(s)
Asma Ocupacional , Enfermedades Profesionales , Exposición Profesional , Humanos , Femenino , Adulto , Persona de Mediana Edad , Asma Ocupacional/diagnóstico , Asma Ocupacional/epidemiología , Asma Ocupacional/etiología , Ocupaciones , Isocianatos , Incidencia , Factores de Riesgo , Enfermedades Profesionales/epidemiología , Enfermedades Profesionales/etiología , Exposición Profesional/efectos adversos
19.
J Agric Food Chem ; 72(12): 6444-6453, 2024 Mar 27.
Artículo en Inglés | MEDLINE | ID: mdl-38502525

RESUMEN

The development of efficient, biobased polyurethane controlled-release fertilizers from sustainable and eco-friendly biomaterials has received increased research attention, owing to concerns regarding global food security and environmental sustainability. Most previous studies focused on replacing petroleum-based polyols with biopolyols; however, the other main raw material, isocyanate, remained a petrochemical product. Herein, all-natural, plant-derived polyurethane-coated urea was successfully developed using castor oil and biobased isocyanate, and the performance of the coating shell before and after modification was compared. The results showed that the incorporation of a low dose of lauric acid copper into the coating material simultaneously enhanced the hydrophobicity and elasticity of the all-biobased polyurethane membrane, which prolonged the nitrogen release longevity from 3 to 112 days. In addition, the modified membrane showed excellent biodegradability in a soil environment. The novel all-biobased polyurethane coating material and modification technique provide insight for developing sustainable and eco-friendly controlled-release fertilizers.


Asunto(s)
Fertilizantes , Poliuretanos , Preparaciones de Acción Retardada , Polímeros , Isocianatos
20.
J Biomed Mater Res B Appl Biomater ; 112(2): e35381, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38348489

RESUMEN

Recent studies show good osteoinductive properties of polyurethanes modified with polyhedral oligomeric silsesquioxanes (POSS). In this work, three types of POSS; propanediolisobutyl-POSS (PHI-POSS), disilanolisobutyl-POSS (DSI-POSS), and octahydroxybutyl-POSS (OCTA-POSS) were chemically incorporated into linear polyurethane based on an aliphatic isocyanate, hexamethylene diisocyanate (HDI), to obtain new nanohybrid PU-POSS materials. The full conversion of POSS was confirmed by Fourier transform infrared spectroscopy (FTIR-ATR) spectra of the model reactions with pure HDI. The materials obtained were investigated by FTIR, SEM-EDS, and DSC. The DSC studies showed the thermoplasticity of the obtained materials and apparently good recovery. 30-day immersion in SBF (simulated body fluid) revealed an increase in the rate of deposition of hydroxyapatite (HAp) for the highest POSS loadings, resulting in thick layers of hydroxyapatite (~60-40 µm), and the Ca/P ratio 1.67 (even 1.785). The structure and properties of the inorganic layer depend on the type of POSS, the number of hard segments, and those containing POSS, which can be tailored by changing the HDI/poly(tetramethylene glycol) (PTMG) ratio. Furthermore, the obtained composites revealed good biocompatibility, as confirmed by cytotoxicity tests conducted on two cell lines; normal human dermal fibroblasts (NHDF) and primary human osteoblasts (HOB). Adherent cells seeded on the tested materials showed viability even after a 48-h incubation. After this time, the population of viable, and proliferating cells exceeded 90%. Bioimaging studies have shown the fibroblast and osteoblast cells were well attached to the surface of the tested materials.


Asunto(s)
Durapatita , Isocianatos , Poliuretanos , Humanos , Poliuretanos/farmacología , Poliuretanos/química , Espectroscopía Infrarroja por Transformada de Fourier , Osteoblastos , Línea Celular
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