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1.
Polymers (Basel) ; 16(5)2024 Feb 29.
Artigo em Inglês | MEDLINE | ID: mdl-38475352

RESUMO

Soft tissue defects, such as incisional hernia or pelvic organ prolapse, are prevalent pathologies characterized by a tissue microenvironment rich in fragile and dysfunctional fibroblasts. Precision medicine could improve their surgical repair, currently based on polymeric materials. Nonetheless, biomaterial-triggered interventions need first a better understanding of the cell-material interfaces that truly consider the patients' biology. Few tools are available to study the interactions between polymers and dysfunctional soft tissue cells in vitro. Here, we propose polypropylene (PP) as a matrix to create microscale surfaces w/wo functionalization with an HBII-RGD molecule, a fibronectin fragment modified to include an RGD sequence for promoting cell attachment and differentiation. Metal mold surfaces were roughened by shot blasting with aluminum oxide, and polypropylene plates were obtained by injection molding. HBII-RGD was covalently attached by silanization. As a proof of concept, primary abdominal and vaginal wall fasciae fibroblasts from control patients were grown on the new surfaces. Tissue-specific significant differences in cell morphology, early adhesion and cytoskeletal structure were observed. Roughness and biofunctionalization parameters exerted unique and combinatorial effects that need further investigation. We conclude that the proposed model is effective and provides a new framework to inform the design of smart materials for the treatment of clinically compromised tissues.

2.
Int J Sports Med ; 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38346702

RESUMO

Groin problems are common in multidirectional sports. The aim of the present study is to assess seasonal, current, and trends for groin problems in rink hockey players, irrespective of their playing position, age, or gender. Rink hockey players from three countries [n=446 (162 female, 284 male)] were invited to participate in an online questionnaire. This form evaluated the prevalence of groin problems (time-loss and non-time-loss) for the 2022-2023 season, as well as monthly prevalence of groin problems (time-loss and non-time-loss). All groin problems were compared between playing position, gender, and age to assess between-group differences. Senior males reported the highest time-loss (25%) and non-time-loss (51%) for seasonal prevalence; while U-17 males reported the lowest in both categories of groin problems (time-loss 9%, non-time-loss 27%). No significant differences between playing position or gender were found for any of the groin problems analyzed. In-season prevalence (9-15.7%) of groin problems was significantly higher than pre-season (7.4%) prevalence (p<0.01). Seasonal prevalence of groin problems is common in rink hockey, regardless of gender, playing position, or age. Preventive efforts should be directed towards all players, regardless of their individual characteristics.

3.
Chem Sci ; 15(2): 431-441, 2024 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-38179527

RESUMO

Humankind's manipulation of platinum dates back more than two millennia to burial objects. Since then, its use has evolved from purely decorative purposes in jewelry to more functional applications such as in catalysts, pharmaceuticals, and bioimaging agents. Platinum offers a range of properties arguably unmatched by any other metal, including electroactivity, photoluminescence, chromic behaviour, catalysis, redox reactivity, photoreactivity, and stimuli-controlled intermetallic interactions. The vast body of knowledge generated by the exploration of these and other properties of platinum has recently merged with other areas of chemistry such as supramolecular and host-guest chemistry. This has shown us that platinum can incorporate its responsive character into supramolecular assemblies (e.g., macrocycles and polymers) to produce materials with tailorable functions and responses. In this Perspective Article, we cover some platinum-powered supramolecular structures reported by us and others, hoping to inspire new and exciting discoveries in the field.

4.
Dalton Trans ; 52(36): 12968-12977, 2023 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-37650238

RESUMO

The quest for advanced water purification technologies has been vigorous over recent decades, motivated by the promise of ever more efficient, greener, and affordable tools. Halloysite nanotubes (HNTs) are naturally-occurring materials that have shown potential as dye sorbents. Unfortunately, these nanoclays suffer from low permeation during water treatment, which limits their widespread application. Here, we use cellulose nanocrystals (CNCs) as structural scaffolds to support HNTs and fabricate permeable aerogel sorbent materials with mechanical stability. Aerogels containing 40 wt% HNTs showed a maximum dye adsorption capacity of 60 mg g-1 towards methylene blue, with only 15% decay in efficiency after 5 cycles. The good mechanical properties of these materials allowed for their incorporation into free-flowing purification columns that displayed excellent dye removal ability. Overall, this work provides a new strategy to fabricate green, renewable, and low-cost sorbent materials for the removal of dyes and shows potential for the sorption of other ionic pollutants.

5.
Dalton Trans ; 52(21): 7136-7142, 2023 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-37159279

RESUMO

Films of cellulose nanocrystals (CNCs) with chiral nematic organization can show vivid iridescence that arises from their hierarchical structure. Unfortunately, the brittleness of the films limits their potential applications. In this paper, we investigate the incorporation of halloysite nanotubes (HNTs) into CNC films to prepare organic-inorganic composite films with enhanced mechanical properties, while preserving the chiral nematic structure and brilliant iridescence. The hybrid composite films containing 10 wt% HNTs are more elastic than pristine CNC films, with a 1.3-fold increase in tensile strength and a 1.6-fold increase in maximum strain. As well, the incorporation of HNTs slightly improves the thermal stability of the composite films. These materials mimic the hybrid composite structures of crab shells, leading to enhanced mechanical properties and thermal stability of CNC films while maintaining iridescence.

6.
Angew Chem Int Ed Engl ; 62(30): e202305525, 2023 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-37208297

RESUMO

Metal-metal bonds have rarely been explored as active elements in supramolecular assemblies despite their unique potential to introduce responsive behavior. In this report, a dynamic molecular container composed of two cyclometalated Pt units is constructed using Pt-Pt bonds. This molecule-the flytrap-has a flexible jaw composed of two [18]crown-6 ethers that can adapt their shape to bind large inorganic cations with sub-micromolar affinity. Along with the spectroscopic and crystallographic characterization of the flytrap, we report its photochemical assembly, which allows the capture of ions and their transport from solution to the solid state. In addition, we have been able to recycle the flytrap to regenerate its starting material due to the reversible nature of the Pt-Pt bond. We believe that other molecular containers and materials for harvesting valuable substrates from solution could be assembled using the advances presented here.

7.
Adv Mater ; 35(29): e2301060, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37019850

RESUMO

Stimulus-responsive materials that display circularly polarized luminescence (CPL) have attracted great attention for application in chiral sensors and smart displays. However, due to difficulties in the regulation of chiral structures, fine control of CPL remains a challenge. Here, it is demonstrated that cellulose nanocrystal shape-memory polymers (CNC-SMPs) with luminescent components enable mechanically responsive CPL. The chiral nematic organization of CNCs in the material gives rise to a photonic bandgap. By manipulating the photonic bandgap or luminescence wavelengths of the luminescent CNC-SMPs, precise control of CPL emission with varied wavelengths and high dissymmetry factors (glum ) is achieved. Specifically, CPL emission can be switched reversibly by treating the luminescent CNC-SMPs with hot-pressing and recovery by heating. Pressure-responsive CPL with tunable glum values is ascribed to the pressure-responsive photonic bandgaps. Moreover, colorimetric and CPL-active patterns are created by imprinting desired forms into SMP samples. This study demonstrates a novel way to fabricate smart CPL systems using biomaterials.

8.
Microorganisms ; 11(4)2023 Mar 31.
Artigo em Inglês | MEDLINE | ID: mdl-37110339

RESUMO

Microorganisms responsible for genitourinary infections increasingly include species other than conventional etiological agents that are of clinical and pathogenic relevance and therapeutic interest. This cross-sectional descriptive study selected samples from clinical genitourinary episodes between January 2016 and December 2019 in which emerging microbiological agents were detected. The patients' epidemiological characteristics, clinical presentation, antibiotic treatment, and outcome were studied to identify their pathogenic role. The emerging microorganisms most frequently detected in urinary tract infections were Streptococcus bovis (58.5%) and Gardnerella spp. (23.6%) in females and S. bovis (32.3%), Aerococcus urinae (18.6%), and Corynebacterium spp. (16.9%) in males, while the most frequently detected in genital infections were S. viridans (36.4%) in females and C. glucuronolyticum (32.2%) and Gardnerella spp. (35.6%) in males. All cases in female children were produced by S. bovis. Symptomatic episodes were more frequent with Aerococcus spp. and S. bovis and the presence of leukocytosis more frequent with Aerococcus spp. Quinolones and doxycycline were most often prescribed antibiotics for genital infections and quinolones and amoxicillin-clavulanic acid for urinary infections. Urinary infection by Aerococcus spp. was more frequent in males of advanced age, Corynebacterium spp. was more frequent in permanent vesical catheter carriers, and episodes of asymptomatic bacteriuria by Gardnerella spp. were more frequent in patients with kidney transplant and chronic consumers of corticosteroid therapy. Lactobacillus spp. should be considered in urinary infections of patients of advanced age and with a previous antibiotic load. Genital infection by Gardnerella spp. was significantly associated with a history of risky sexual relations.

9.
J. oral res. (Impresa) ; 12(1): 119-126, abr. 4, 2023. ilus
Artigo em Inglês | LILACS | ID: biblio-1451421

RESUMO

Introduction: The present report describes the case of a 12-year-old patient with 17-year follow-up who was previously diagnosed with Papillon-Lefèvre Syndrome (PLS), which is a rare autosomal recessive irregularity in the cathepsin C gene (CTSC) characterized by palmoplantar hyperkeratosis and premature loss of primary and permanent teeth. Case Report: A specific mutation in the c.203 T > G gene inducing loss of function leading to PLS was detected, as was a mutation in the HLA-DRB1*11 allele, which is associated with this syndrome. There is no consanguinity of the parents, and the siblings are entirely healthy. Early identification of the main characteristics of this syndrome is imperative. Accurate diagnosis by genetic analysis allows differential diagnoses and timely comprehensive dental treatment. Conclusions: Additionally, it allows consultation with a dermatologist to maintain or improve the quality of life of patients with this condition due to progressive worsening and severity of the main physical manifestations. Keywords: Papillon-Lefevre Disease; Keratoderma, Palmo-plantar; Cathepsin C; Periodontitis; Skin Diseases, Genetic; Case reports


Introducción: El presente reporte describe el caso de un paciente de 12 años de edad con 17 años de seguimiento a quien previamente se le diagnosticó Síndrome de Papillon-Lefèvre (PLS), el cual es una rara irregularidad autosómica recesiva en el gen de la catepsina C (CTSC) caracterizada por hiperqueratosis palmoplantar y pérdida prematura de dientes primarios y permanentes. Reporte de Caso: Se detectó una mutación específica en el gen c.203 T > G que induce pérdida de función que conduce a PLS, así como una mutación en el alelo HLA-DRB1*11, que se asocia a este síndrome. No presenta consanguinidad de los padres, padres y hermanos totalmente sanos. La identificación temprana de las principales características de este síndrome es imperativa. El diagnóstico certero por análisis genético permite diagnósticos diferenciales y tratamientos odontológicos integrales oportunos. Conclusiones: Adicionalmente, permite la consulta con un dermatólogo para mantener o mejorar la calidad de vida de los pacientes con esta condición debido al progresivo empeoramiento y severidad de las principales manifestaciones físicas.


Assuntos
Humanos , Masculino , Criança , Doença de Papillon-Lefevre/diagnóstico por imagem , Ceratodermia Palmar e Plantar , Catepsina C/genética , Doença de Papillon-Lefevre/terapia
10.
Front Genet ; 14: 1022912, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36968598

RESUMO

Background: MicroRNAs (miRNAs) are important regulators in a variety of biological processes, and their dysregulation is associated with multiple human diseases. Single nucleotide variants (SNVs) in genes involved in the processing of microRNAs may alter miRNA regulation and could present high allele heterogeneity in populations from different ethnic groups. Thus, the aim of this study was to genotype 15 SNVs in eight genes involved in the miRNA processing pathway in Mexican individuals and compare their frequencies across 21 populations from five continental groups. Methods: Genomic DNA was obtained from 399 healthy Mexican individuals. SNVs in AGO2 (rs2293939 and rs4961280), DGCR8 (rs720012), DICER (rs3742330 and rs13078), DROSHA (rs10719 and rs6877842), GEMIN3 (rs197388 and rs197414), GEMIN4 (rs7813, rs2740349, and rs4968104), TNRC6B (rs9611280), and XP05 (rs11077 and rs34324334) were genotyped using TaqMan probes. The minor allele frequency of each SNV was compared to those reported in the 1,000 Genomes database using chi-squared. Sankey plot was created in the SankeyMATIC package to visualize the frequency range of each variant in the different countries analyzed. Results: In Mexican individuals, all 15 SNVs were found in Hardy-Weinberg equilibrium, with frequencies ranging from 0.04 to 0.45. The SNVs rs4961280, rs2740349, rs34324334, and rs720012 in Mexican individuals had the highest minor allele frequencies worldwide, whereas the minor allele frequencies of rs197388, rs10719, rs197414, and rs1107 were among the lowest in Mexican individuals. The variants had high allele heterogeneity among the sub-continental populations, ranging from monomorphic, as was the case for rs9611280 and rs34324334 in African groups, to >0.50, which was the case for variants rs11077 and rs10719 in most of the populations. Importantly, the variants rs197388, rs720012, and rs197414 had FST values > 0.18, indicating a directional selective process. Finally, the SNVs rs13078 and rs10719 significantly correlated with both latitude and longitude. Conclusion: These data indicate the presence of high allelic heterogeneity in the worldwide distribution of the frequency of SNVs located in components of the miRNA processing pathway, which could modify the genetic susceptibility associated with human diseases in populations with different ancestry.

11.
Bioengineering (Basel) ; 10(2)2023 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-36829626

RESUMO

Exercise capacity is limited by environmental heat stress because thermoregulatory systems are altered and cannot prevent the elevation of body temperature due to a complex interplay of physiological, physical, and perceptual alterations. Cooling is an effective strategy to attenuate the temperature rise. Based on the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines and the PEDro scale for assessing methodological quality, we systematically reviewed studies indexed in Medline, Web of Science, EMBASE, Science Direct, Sportdiscus, and Scopus, to evaluate the effects of the cooling vest (CVs) on perceptual response, physiological behavior, and sports performance in adult physical activity practitioners under heat stress conditions. Among the 711 studies identified in the search, 10 studies for the systematic review and eight for the meta-analysis met the inclusion and exclusion criteria. Overall, the use of CVs showed improvements in certain sports performance indicators, being significant (p < 0.05) in test time and substantial in peak power that could be influenced directly by the significant reduction (p < 0.05) in skin temperature and indirectly by the significant improvement (p < 0.05) in thermal and exertional perceptual responses, without the involvement of core temperature. In conclusion, the use of CVs is a cooling technique that influences perceptual response, thermo-physiological behavior, and sports performance. However, further studies are needed to elucidate the relevance of its application to CVs.

12.
ACS Appl Mater Interfaces ; 15(6): 8406-8414, 2023 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-36719931

RESUMO

Gels are useful materials for drug delivery, wound dressings, tissue engineering, and 3D printing. These various applications require gels with different mechanical properties that can be easily tuned, also preferably excluding the use of chemical additives, which can be toxic or harmful to the body or environment. Here, we report a novel strategy to synthesize cellulose nanocrystal (CNC) gels with tunable mechanical properties. Sequential freeze-thaw cycling and hydrothermal treatments were applied to CNC suspensions in different orders to give a series of pristine CNC hydrogels. Freeze-drying of the hydrogels also afforded a series of lightweight CNC aerogels. The mechanical properties of the hydrogels and aerogels were studied by rheological measurements and compression strength tests, respectively. Specifically, the complex modulus of CNC hydrogels ranged from 160 to 32,000 Pa among eight different hydrogels, while Young's modulus of CNC aerogels was tuned from 0.114 to 3.98 MPa across five different aerogels. The microstructures of aerogels were also investigated by scanning electron microscopy and X-ray microtomography, which revealed remarkable differences between the materials. Solvent sorption-desorption tests showed that the reinforced networks have excellent stability over the basic CNC aerogels in ethanol, demonstrating a material enhancement from the preparation strategies we developed. Thermal conductivity and thermal stability for these materials were also investigated, and it was found that the lowest thermal conductivity was 0.030 W/m K, and all of the aerogels are generally stable below 280 °C. These characteristics also expand the potential applications of this family of CNC gels to lightweight supporting materials and thermal insulators.

13.
Acta Radiol ; 64(3): 1078-1085, 2023 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-35607260

RESUMO

BACKGROUND: Meniscal ramp lesions have gained much prominence in recent years due to a significant increase in their diagnosis and their important biomechanical involvement in the knee. A new proposed classification of these lesions has recently been published. PURPOSE: To evaluate the reproducibility of the new classification of meniscal ramp lesions recently published using magnetic resonance imaging (MRI). MATERIAL AND METHODS: A total of 249 post-traumatic knee MRI studies were evaluated by three musculoskeletal radiologists independently. Patients with an anterior cruciate ligament (ACL) tear on MRI in addition to a recent history of trauma to the knee for <12 months were included in the study, for a total of 95. We carried out an inter-observer concordance study to analyze whether the new classification is reproducible to detect meniscal ramp lesions and to classify them into their different types. RESULTS: Among our study cohort of 95 patients, we found 47 (49.5%) ramp lesions. In the inter-observer study, we obtained a good concordance (k = 0.733) in the detection of these lesions and an excellent one (k = 0.843) when the type of lesion is described. CONCLUSION: This study demonstrates that the new classification of meniscal ramp lesions has good reproducibility on MRI.


Assuntos
Lesões do Ligamento Cruzado Anterior , Reconstrução do Ligamento Cruzado Anterior , Humanos , Reprodutibilidade dos Testes , Reconstrução do Ligamento Cruzado Anterior/métodos , Articulação do Joelho/cirurgia , Lesões do Ligamento Cruzado Anterior/diagnóstico por imagem , Imageamento por Ressonância Magnética , Meniscos Tibiais
14.
Angew Chem Int Ed Engl ; 62(4): e202216029, 2023 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-36426408

RESUMO

Macrocycle engineering is a key topic in supramolecular chemistry. When synthesizing a ring, one can obtain either complex mixtures of macrocycles of different sizes or a single ring if a template is utilized. Here, we unite these approaches along with post-synthetic modifications to transform a single tether into multiple rings-up to five per tether. The macrocycles contain two bridged phenylpyridine ligands that are connected through a Pt atom, which defines the rings' shape, size, and host activity. All rings undergo redox reactions (between PtII and PtIV ) that allow for large conformational changes. Their reactivity, together with their host performance, is a convenient way to control the capture and release of guests, to mediate ring transformations, and to control pseudorotaxane-to-pseudorotaxane conversions. This novel approach could serve to assemble other libraries of small ring molecules, create cyclic polymers bridged by responsive-at-metal nodes, and produce processable mechanically interlocked molecules.

15.
Artigo em Inglês | MEDLINE | ID: mdl-36498228

RESUMO

Tribulus terrestris L. (TT) ingredients have anti-inflammatory and antioxidant activities, but their effects on exercise-induced muscle damage (EIMD) in trained athletes are uncertain. The purpose of this single-blind placebo-controlled trial, in accordance with CONSORT guidelines, was to examine the effect of 6 weeks of TT supplementation on muscle metabolism, inflammation biomarkers, and oxidant status. Thirty trained male CrossFit® athletes were randomly assigned to be supplemented with 770 mg/day of TT (intervention group (IG)) or receive a placebo daily (control group (CG)) for 6 weeks. Muscle damage enzymes, inflammation biomarkers, and Total Antioxidant Status (TAS) were assessed at baseline (T1), 21 days after baseline (T2), and after 42 days (T3). Grace, a Workout of the Day, was measured in T1 and T3. Statistical significance (p < 0.05) was found between IG and CG in Lactate Dehydrogenase (LDH), C-reactive protein (CRP), and TAS levels at the end of the follow-up. Furthermore, TAS levels were significantly (p < 0.05) lower at T2 and T3 relative to baseline in the IG, also LDH and CRP increased significantly (p < 0.05) at T2 and T3 relative to baseline in the CG. No significant (p > 0.05) decreases in muscle damage or inflammation biomarkers were observed, although a slight downward trend was observed after 6 weeks for supplemented athletes. TT supplementation could attenuate the CrossFit® training program-induced oxidative stress, muscle damage, and inflammation which could be due to the natural antioxidant and anti-inflammatory properties of TT.


Assuntos
Suplementos Nutricionais , Músculos , Preparações de Plantas , Tribulus , Humanos , Masculino , Anti-Inflamatórios/farmacologia , Antioxidantes/farmacologia , Biomarcadores , Inflamação/tratamento farmacológico , L-Lactato Desidrogenase , Músculos/metabolismo , Estresse Oxidativo , Método Simples-Cego , Atletas
16.
Heliyon ; 8(11): e11238, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-36387577

RESUMO

Wildfires in the urban-forest interface constitute a civil protection emergency, causing considerable personal injury and damage to properties. The potential impacts of wildfires on buildings can be minimized by reducing the surrounding fuel and the use of structural materials with low flammability. However, the costs associated with implementing these actions and the responsibility for maintenance usually present conflicts with the property owners. This study aimed to identify minimum safety distances in wildland-urban interfaces within priority areas. The priority areas were identified based on the integration of fire risk and fuel hazard. Radiant heat is a variable in the behavior of fire that directly influences the definition of safety distances. In this research the radiant heat transfer was calculated based on the potential fire behavior for each study area. A comparative study of the horizontal heat transfer method and the radiant heat flux model was carried out. The horizontal heat transfer method indicated the highest vegetation-free distances, ranging from 23 m to 32 m. Some safety distances were validated using experimental fires and wildfires. The findings from the experimental fires and wildfires emphasize the need for a progressive fuel load reduction to mitigate radiant heat transfer. This may include both the removal of surface fuel and removal of trees to mitigate against crown fires. Our findings provide relevant information for decision-making on the effectiveness and efficiency of safety distances at the wildland-urban interface.

17.
Int Orthod ; 20(4): 100692, 2022 12.
Artigo em Inglês | MEDLINE | ID: mdl-36410930

RESUMO

INTRODUCTION: To compare the root morphology of the maxillary lateral incisors (MLIs) adjacent to an impacted (IMC) versus non-impacted maxillary canine (non-IMC). MATERIALS AND METHODS: This cross-sectional study included cone beam computed tomography (CBCT) images derived from 154 subjects (with unilateral/bilateral impacted maxillary canines or without canine impaction). Each MLI was considered as a unit of analysis. Thus, the study group included 122 MLIs adjacent to impacted maxillary canine (IMCG) and the control group included 122 MLIs adjacent to a non-impacted maxillary canine (CG). Groups were matched by age, sex and evaluation side. Root length, root dilaceration angle and root convergence angle were evaluated in both the coronal and sagittal planes. Comparisons between groups were made with Student's t-test and the chi-square test with Bonferroni correction (P<0.008, P<0.01, respectively). RESULTS: The root measurements of the MLIs showed some significant differences between the groups. The coronal root length was 0.52mm shorter but not highly significant (P=0.032), the coronal root dilaceration angle was 7.51° smaller (P<0.001), and the coronal root convergence angle was 1.28° greater (P<0.001) in the IMCG compared to the CG. The orientation of root dilaceration in the MLIs showed significant differences between the groups: it was mostly distopalatal in the GC (87.5%), to a lesser extent in the IMCG (58.9%) and also mesiopalatal in the IMCG (22.3%), (P=0.001). CONCLUSIONS: The root morphology of MLIs adjacent to an IMC showed a tendency of shorter length, smaller root dilaceration and greater root convergence in the coronal section than MLIs adjacent to a non-IMC.


Assuntos
Incisivo , Dente Impactado , Humanos , Incisivo/diagnóstico por imagem , Estudos Transversais , Estudos Retrospectivos , Maxila/diagnóstico por imagem , Dente Impactado/diagnóstico por imagem , Tomografia Computadorizada de Feixe Cônico/métodos
20.
Chemistry ; 28(54): e202200862, 2022 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-35920581

RESUMO

Ring-opening metathesis polymerization (ROMP) of strained macrocycles is a key method to prepare diverse polymers. However, lack of ring strain in most macrocycles is an impediment to polymerization. In this paper, the polymerization/oligomerization of unstrained macrocycles was achieved using a supramolecular approach, leading selectively to cyclic products. Diphenyl thiourea and other guest molecules were used as additives to the ROMP reaction of unstrained macrocycles. An intermediate host-guest complex leads to the stabilization of the open form of the macrocycle after treatment with Grubbs catalysts, thereby favoring polymerization by inhibiting the ring-closing reaction back to the monomer. This proof-of-concept enables ring-expansion polymerization of unstrained macrocycles leading to cyclic polymers with molecular weights up to 6700 Da.

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