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Patients with Down syndrome (DS) are commonly affected by a pre-leukemic disorder known as transient abnormal myelopoiesis (TAM). This condition usually undergoes spontaneous remission within the first 2 months after birth; however, in children under 5, 20%-30% of cases evolve to myeloid leukemia of Down syndrome (ML-DS). TAM and ML-DS are caused by co-operation between trisomy 21 and acquired mutations in the GATA1 gene. Currently, only next-generation sequencing (NGS)-based methodologies are sufficiently sensitive for diagnosis in samples with small GATA1 mutant clones (≤10% blasts). Alternatively, this study presents research on a new, fast, sensitive, and inexpensive high-resolution melting (HRM)-based diagnostic approach that allows the detection of most cases of GATA1 mutations, including silent TAM. The algorithm first uses flow cytometry for blast count, followed by HRM and Sanger sequencing to search for mutations on exons 2 and 3 of GATA1. We analyzed 138 samples of DS patients: 110 of asymptomatic neonates, 10 suspected of having TAM, and 18 suspected of having ML-DS. Our algorithm enabled the identification of 33 mutant samples, among them five cases of silent TAM (5/110) and seven cases of ML-DS (7/18) with blast count ≤10%, in which GATA1 alterations were easily detected by HRM. Depending on the type of genetic variation and its location, our methodology reached sensitivity similar to that obtained by NGS (0.3%) at a considerably reduced time and cost, thus making it accessible worldwide.
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Síndrome de Down , Leucemia Mieloide , Reação Leucemoide , Algoritmos , Criança , Síndrome de Down/complicações , Síndrome de Down/diagnóstico , Síndrome de Down/genética , Fator de Transcrição GATA1/genética , Humanos , Recém-Nascido , Leucemia Mieloide/genética , Reação Leucemoide/diagnóstico , Reação Leucemoide/genética , MutaçãoRESUMO
Biomedical applications of polymers require precise control of the solid-state structure, which is of particular interest for biodegradable copolymers. In this work, we evaluated the influence of crystallization conditions on the comonomer exclusion/inclusion balance of biodegradable poly(butylene succinate-ran-butylene adipate) (PBSA) isodimorphic random copolymers. Regardless of the crystallization conditions, the copolymers retain their isodimorphic character, displaying a pseudo-eutectic behavior with crystallization in the entire composition range. This illustrates the thermodynamic nature of the isodimorphic behavior for PBSA random copolymers. However, depending on the composition, the crystallization conditions affect the exclusion/inclusion balance of the comonomers. Fast cooling favors butylene adipate (BA) inclusion inside the poly(butylene succinate) (PBS) crystals, whereas isothermal crystallization strongly limits it. PBA-rich compositions behave differently. Both fast and slow crystallization formed the ß-phase, whereas BS unit inclusion is favored independently of the cooling conditions. During successive self-nucleation and annealing, the BA inclusion is intermediate between non-isothermal and isothermal conditions, while the crystalline structure of the PBA phase changes from the ß-phase to the more stable α-phase. We propose a simple crystallographic model to explain the changes in the unit cell dimension of the copolymers.
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Adipatos , Polímeros , Alcenos , Butileno Glicóis , Cristalização , SuccinatosRESUMO
The acute phase of Chagas disease (CD) is characterized by high parasitic proliferation and intense inflammation, exacerbating the generation of reactive oxygen species (ROS) and reactive nitrogen species (RNS). These reactive molecules are also increased by the metabolism of the nitroheterocyclic compounds benznidazole (BZ) and nifurtimox, the only drugs available for the treatment of CD. This oxidative environment, associated with the intracellular multiplication of Trypanosoma cruzi, leads to tissue destruction, triggering the pathogenic process. Both drugs have limited efficacy and serious side effects, which demonstrates the need to seek alternative therapies. Due to the difficulty in developing new drugs, reviewing therapeutic regimens appears advantageous, and the use of BZ in low doses associated with antioxidants, such as ascorbic acid (AA), would be a valid alternative to attenuate oxidative stress. In our in vivo studies, mice receiving the combination of 7.14 mg/kg of body weight/day AA and 10 mg/kg/day BZ10 (AA+BZ10) showed a reduction in parasitemia that was more effective than that with those receiving BZ or AA alone. The combined treatment was effective in decreasing intracellular ROS and lipid peroxidation in cardiac tissue. Histological and PCR analyzes showed that AA also reduced the cardiac parasitism. However, the greatest benefit was seen in AA+BZ10 group, since cardiac inflammation was significantly reduced. In addition, the combined therapy prevented the hepatic damage induced by the infection. Our findings suggest that AA combined with a low dose of BZ may improve the trypanocidal activity and attenuate the toxic effects of BZ. The decrease in oxidative damage and inflammation observed in mice treated with AA+BZ10 could result in increased cardioprotection.
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Ácido Ascórbico/farmacologia , Doença de Chagas/tratamento farmacológico , Nitroimidazóis/farmacologia , Animais , Antioxidantes/metabolismo , Doença de Chagas/parasitologia , Quimioterapia Combinada/métodos , Inflamação/tratamento farmacológico , Inflamação/parasitologia , Peroxidação de Lipídeos/efeitos dos fármacos , Masculino , Camundongos , Oxirredução/efeitos dos fármacos , Espécies Reativas de Oxigênio/metabolismo , Tripanossomicidas/farmacologia , Trypanosoma cruzi/efeitos dos fármacosRESUMO
The purpose of this study was to evaluate the effects of FSH and PI3K on the nuclear maturation, viability, steroidogenesis and embryo development of bovine cumulus-oocyte complexes (COCs). Oocyte maturation was achieved with MIV B, MIV B+100 µM LY294002, MIV B+10 ng/mL follicle stimulating hormone (FSH), or MIV B+10 ng/mL FSH+100 µM LY294002 treatments for 22-24 h. After the cultured COCs were denuded, oocytes were separated into those that extruded polar bodies (mature) and those that did not, and real-time polymerase chain reaction (PCR) for BAX, BCL2, LHR, FSHR, CYP11A1, CYP19A1 and HSD17B1 genes was performed. The culture medium was collected to determine the levels of 17ß-estradiol (E2) and progesterone (P4). The trypan blue test was used to study COC viability, and embryo development was evaluated. FSH increased nuclear maturation and PI3K blocked the maturation but did not influence oocyte viability. BAX and BCL2 expression levels in the cumulus cells were only affected by FSH, and the BAX levels decreased after treatment with LY294002. FSH increased the levels of E2 and P4, however inhibition of PI3K decreased E2 levels. MIV B enhanced levels of LHR, FSHR, CYP11A1, CYP19A1 and HSD17B1, whereas LY294002 inhibited the expression levels of all genes. MIV B+FSH decreased the expression levels of all genes except CYP11A1. LY294002 did not demonstrate any effects in the presence of FSH. Embryo development was significantly decreased when the MIV B+FSH medium was used. In conclusion, FSH controls the steroidogenesis, viability and gene expression in COCs. PI3K plays essential roles in nuclear maturation, steroidogenesis and embryo development.
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Células do Cúmulo/fisiologia , Hormônio Foliculoestimulante/metabolismo , Oócitos/fisiologia , Fosfatidilinositol 3-Quinases/metabolismo , Esteroides/metabolismo , Animais , Blastocisto/fisiologia , Bovinos , Cromonas/farmacologia , Células do Cúmulo/citologia , Estradiol/metabolismo , Feminino , Fertilização in vitro , Hormônio Foliculoestimulante/farmacologia , Regulação da Expressão Gênica no Desenvolvimento , Técnicas de Maturação in Vitro de Oócitos/métodos , Morfolinas/farmacologia , Oócitos/efeitos dos fármacos , Inibidores de Fosfoinositídeo-3 Quinase , Progesterona/metabolismo , Proteína X Associada a bcl-2/genéticaRESUMO
Following Foucault's work on disciplinary power and biopolitics, this article maps an initial cartography of the research areas to be traced by a genealogy of pharmacological practice. Pharmacology, as a practical activity, refers to the creation, production and sale of drugs/medication. This work identifies five lines of research that, although often disconnected from each other, may be observed in the specialized literature: (1) pharmaceuticalization; (2) regulation of the pharmaceutical industry; (3) the political-economic structure of the pharmaceutical industry; (4) consumption/consumerism of medications; (5) and bio-knowledge. The article suggests that a systematic analysis of these areas leads one to consider pharmacological practice a sui generis apparatus of power, which reaches beyond the purely disciplinary and biopolitical levels to encompass molecular configurations, thereby giving rise not only to new types of government over life, but also to new struggles for life, extending from molecular to population-wide levels.
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Indústria Farmacêutica/ética , Indústria Farmacêutica/organização & administração , Política , Indústria Farmacêutica/economia , Humanos , Legislação de Medicamentos/ética , Legislação de Medicamentos/organização & administraçãoRESUMO
The aim of this study was to identify common factors relating to the academic success of medical students who were distinguished with honors at the Buenos Aires University. In 2011, 142 graduates were surveyed; the questionnaire included 59 questions on their sociodemographic environment, living conditions and social integration, motivation to study, learning capacity and health quality during their career. Compared to other students, these distinguished students more often lived in the city, far from their families; had been educated at private or universitary high schools, their economic needs were financed by their parents, who were on the whole professionals. Most of them were single and childless. The possibility of future employment oportunities (work) did not influence their choice of a medical career, academic success was important to them and they believed that success depended largely on personal effort; they knew how to handle anxiety, were sociable but independent and preferred solid experience to abstract conceptuality in order to obtain information. Our conclusion, within the current system of candidate selection, these results serve to calculate the covert self-selection mechanisms during the career, or in a more restrictive regime, to select those likely to reach academic success due to their privileged ambience. The analysis of demographic factors indicates some degree of inequality for socially disadvantaged students. Perhaps, a selection system based only on intellectual abilities would help identify and support the best candidates regardless of their social context.
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Logro , Educação Médica/estatística & dados numéricos , Estudantes de Medicina/psicologia , Adulto , Ansiedade/prevenção & controle , Argentina , Aspirações Psicológicas , Feminino , Nível de Saúde , Humanos , Vida Independente/estatística & dados numéricos , Aprendizagem , Masculino , Motivação , Condições Sociais/estatística & dados numéricos , Habilidades Sociais , Inquéritos e Questionários , UniversidadesRESUMO
INTRODUCTION: Since the number of applicants to residencies in general surgery in Argentina seems to be decreasing, we designed this work with the objective of studying the factors considered undesirable by students when choosing surgery as a specialty. MATERIAL AND METHODS: Between March and April 2012, one-hundred students were surveyed with a structured questionnaire with true/false binary answers in an observational case-control design. The survey contained 26 statements that made reference to characteristics of surgery as a specialty, or about the personality and lifestyle of surgeons, as they could be perceived by students. As a control group the same survey was applied to 20 surgeons who were in contact with the students and that could represent a role model for them during their rotation in surgery. RESULTS: Comparison between students and surgeons showed no difference in most answers, except in «surgery has poor reimbursement¼ (OR: 8,9; P=.0001), «there is not enough job demand¼ (OR: 8,1; P=.015), «surgery restrains intellectual development¼ (OR: 17,5; P=.014), «surgeons have too many non-scheduled activities¼ (OR: 9,36; P=.024), «they have a limited patient-physician relationship¼ (OR: 3,61; P=.009), «they have little time for family¼ (OR: 4,27; P=.036) and «they are exposed to infectious diseases¼ (OR: 5,90; P=.007). CONCLUSIONS: Women would be as interested as men in working as surgeons; a remarkable fact when considering that the surgical specialties have been predominantly filled by men. The fact that surgeons mostly coincide with the views of students means that role models should be reviewed to promote vocations.
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Atitude , Escolha da Profissão , Cirurgia Geral , Estudantes de Medicina , Cirurgiões , Adulto , Estudos de Casos e Controles , Feminino , Humanos , Masculino , Inquéritos e QuestionáriosRESUMO
The objective was to explore the usefulness of the logistic EuroSCORE to stratify the long-term survival curves in a sample of patients undergoing cardiac surgery. The 8-year survival of 390 patients undergoing cardiac surgery between 2003 and 2004 was analyzed, according to the basal value of the EuroSCORE, patients were classified into three risk groups: < 5%, 5-14.9% and > 15%. Eight-years Kaplan-Meier's survival after coronary artery bypass grafting divided by the basal EuroSCORE was 83.5% for a basal risk < 5%, 65.2% for a basal risk 5 to 14.9% and 40.0% for a basal risk >15% (p = 0.000); whereas for valve or combined surgery it was 86.1%, 60.0% and 18.2% respectively (p = 0.0000). For all patients, ROC area was 0.759 (p = 0.000), for a EuroSCORE < 5% it was 0.689 (p = 0.002), between 5 and 14.9% it was 0.544 (p = 0.499) and for >15% it was 0.725 (p = 0.067). In conclusion, the logistic EuroSCORE allowed properly stratify the long-term survival curves in a sample of patients undergoing cardiac surgery, both the coronary and valve or combined surgery. Long-term results stratified by risk are a reasonable way to present late postoperative survival.
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Procedimentos Cirúrgicos Cardíacos/mortalidade , Idoso , Feminino , Mortalidade Hospitalar , Humanos , Estimativa de Kaplan-Meier , Masculino , Pessoa de Meia-Idade , Período Perioperatório , Prognóstico , Curva ROC , Medição de Risco/métodos , Fatores de Risco , Fatores de Tempo , Resultado do TratamentoRESUMO
Purpose: This study investigated the effects of combined mouth rinse and topical application of L-menthol on perceptual responses and running performance under thermoneutral conditions (22 ± 2°C and 30-60% relative humidity). Methods: Twelve recreational male runners (age: 31.7 ± 3.8 years; age range: 27-39 years) completed a familiarization, a control test (CON) and two maximal 10-km time trials (counterbalanced randomized crossover design) performed in different days with a non-thermal cooling intervention (combined application of a L-menthol mouth rinse and topical L-menthol gel - MEN) or placebo (PLA). Performance and perceptual measures (thermal sensation, thermal comfort, ratings of perceived exertion and affective response) were recorded for every km completed in the 10-km test. Results: Performance time was lower in MEN (P = 0.03) and PLA (P = 0.003) compared to CON, but no differences were found between MEN vs PLA (P = 1.00). All perceptual responses increased over time in all conditions (P < 0.0001), but only the thermal sensation was lower (P = 0.01) in the MEN compared to CON. Conclusion: L-menthol strategies promote fresh sensations and may improve running performance in 10-km time trial in recreational runners, but the performance improvement could mainly be due to a placebo effect.
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Desempenho Atlético , Corrida , Adulto , Humanos , Masculino , Desempenho Atlético/fisiologia , Mentol/farmacologia , Antissépticos Bucais/farmacologia , Poliésteres/farmacologia , Corrida/fisiologia , Sensação Térmica , Estudos Cross-OverRESUMO
Telomeres and telomerase are closely linked to uncontrolled cellular proliferation, immortalization and carcinogenesis. Telomerase has been largely studied in the context of cancer, including leukemias. Deregulation of human telomerase gene hTERT is a well-established step in leukemia development. B-acute lymphoblastic leukemia (B-ALL) recovery rates exceed 90% in children; however, the relapse rate is around 20% among treated patients, and 10% of these are still incurable. This review highlights the biological and clinical relevance of telomerase for B-ALL and the implications of its canonical and non-canonical action on signaling pathways in the context of disease and treatment. The physiological role of telomerase in lymphocytes makes the study of its biomarker potential a great challenge. Nevertheless, many works have demonstrated that high telomerase activity or hTERT expression, as well as short telomeres, correlate with poor prognosis in B-ALL. Telomerase and related proteins have been proven to be promising pharmacological targets. Likewise, combined therapy with telomerase inhibitors may turn out to be an alternative strategy for B-ALL.
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Leucemia-Linfoma Linfoblástico de Células Precursoras B , Leucemia-Linfoma Linfoblástico de Células Precursoras , Telomerase , Criança , Humanos , Telomerase/genética , Telomerase/metabolismo , Leucemia-Linfoma Linfoblástico de Células Precursoras/genética , Leucemia-Linfoma Linfoblástico de Células Precursoras B/genética , Encurtamento do Telômero , Telômero/genética , Telômero/metabolismoRESUMO
INTRODUCTION: This study aimed to determine whether cytokine receptor-like factor 2 (CRLF2) antigen expression evaluated using multiparametric flow cytometry (MFC) could predict the genotype of CRLF2 and Janus kinase 2 (JAK2) status for application in the diagnosis of pediatric B-cell precursor acute lymphoblastic leukemia (BCP-ALL). METHODS: A total of 321 BCP-ALL bone marrow samples were collected, 291 at diagnosis and 13 at first relapse, while 17 samples were excluded due to low cellular viability. The CRLF2 antigen expression was evaluated using flow cytometry (percentage of positivity and median fluorescence intensity [MFI]). The CRLF2 transcript levels were assessed via quantitative reverse transcription polymerase chain reaction using SYBR Green. The CRLF2 rearrangements (CRLF2-r) were identified using the CRLF2 break-apart probe via fluorescence in situ hybridization. Sanger sequencing was performed to identify the JAK2 exon 16 mutations. RESULTS: We observed that 60 of the 291 cases (20.6%) presented CRLF2 antigen positivity, whereas the CRLF2 transcript overexpression was found in 19 of 113 cases (16.8%). The JAK2 mutation was found in four out of 116 cases (3.4%), all of which had CRLF2 ≥10% of positive cells and intermediate or high MFI (p < 0.0001). In addition, in the 13 cases with the CRLF2-r, a positive correlation was found with the CRLF2 antigen intermediate (61.5%) MFI (p = 0.017). Finally, the CRLF2-positive antigen was identified in the BCP-ALL subclones. CONCLUSION: The identification of the CRLF2 antigen using the MFC, based on the percentage of positivity and MFI values, is a useful tool for predicting JAK2 mutations and CRLF2-r.
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In this work, poly(hexamethylene-ran-octamethylene carbonate) copolycarbonates were synthesized by melt polycondensation in a wide range of compositions. The copolymers displayed some of the characteristic isodimorphic thermal behavior, such as crystallization for all the compositions and a pseudoeutectic behavior of the melting temperature (Tm) versus composition. The pseudoeutectic point was located at 33 mol % poly(octamethylene carbonate) (POC) content (i.e., corresponding to the PH67O33C copolymer). Surprisingly, the crystallinities (Xc) for a wide range of copolymer compositions were higher than those of the parent components, a phenomenon that has not been observed before in isodimorphic random copolymers. The structural characterization, performed by wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering experiments, revealed unexpected results depending on composition. On the one hand, the poly(hexamethylene carbonate) (PHC)- and POC-rich copolymers crystallize in PHC- and POC-type crystals, as expected. Moreover, upon cooling and heating, in situ WAXS experiments evidenced that these materials undergo reversible solid-solid transitions [δ-α (PHC) and δ-α-ß (POC)] present in the parent components but at lower temperatures. On the other hand, a novel behavior was found for copolymers with 33-73 mol % POC (including the pseudoeutectic point), which are those with higher crystallinities than the parent components. For these copolymers, a new crystalline phase that is different from that of both homopolymers was observed. The in situ WAXS results for these copolymers confirmed that this novel phase is stable upon cooling and heating and does not show any crystallographic feature of the parent components or their solid-solid transitions. FTIR experiments confirmed this behavior, revealing that the new phase adopts a polyethylene-like chain conformation that differs from the trans-dominant ones exhibited by the parent components. This finding challenges the established concepts of isodimorphism and questions whether a combination of crystallization modes (isodimorphism and isomorphism) is possible in the same family of random copolymers just by changing the composition.
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Stingless bees are responsible for pollinating up to 90% of Brazilian flora, so their study is of commercial and ecological importance. Stingless bees mix plant resins with wax and soil, forming geopropolis. Studies of the variability in composition and activity due to species, place and season of collection are lacking. Yield, total phenolic and flavonoid content, and antioxidant activity (via DPPH) of the extracts of fifteen M. quadrifasciata (Mandaçaia) geopropolis samples collected over a year in the State of São Paulo, Brazil, as well as two samples from different regions of the state of Minas Gerais in Brazil were compared. Composition was determined by ultra-high-resolution liquid chromatography and mass spectrometry, identifying 16 compounds. The month and region of collection affected the available plant resins and influenced their yield, composition and antioxidant capacity. Depending on the place of collection, M. quadrifasciata geopropolis is a promising natural source of antioxidant phenolic compounds.
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Antioxidantes , Própole , Animais , Antioxidantes/química , Abelhas , Brasil , Flavonoides/análise , Fenóis/análise , Própole/químicaRESUMO
The impact of plastics on the environment can be mitigated by employing biobased and/or biodegradable materials (i.e., bioplastics) instead of the traditional "commodities". In this context, poly (butylene succinate) (PBS) emerges as one of the most promising alternatives due to its good mechanical, thermal, and barrier properties, making it suitable for use in a wide range of applications. Still, the PBS has some drawbacks, such as its high crystallinity, which must be overcome to position it as a real and viable alternative to "commodities". This contribution covers the actual state-of-the-art of the PBS through different sections. The first section reviews the different synthesis routes, providing a complete picture regarding the obtained molecular weights and the greener alternatives. Afterward, we examine how different strategies such as random copolymerization and the incorporation of fillers can effectively modulate PBS properties to satisfy the needs for different applications. The impact of these strategies is evaluated in the crystallization behavior, crystallinity, mechanical and barrier properties, and biodegradation. The biodegradation is carefully analyzed, highlighting the wide variety of methodologies existing in the literature to measure PBS degradation through different routes (hydrolytic, enzymatic, and soil).
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Polylactide is one of the most versatile biopolymers, but its slow crystallization limits its temperature usage range. Hence finding ways to enhance it is crucial to widen its applications. Linear and cyclic poly (L-lactide) (l-PLLA and c-PLLA) of similarly low molecular weights (MW) were synthesized by ring-opening polymerization of L-lactide, and ring-expansion methodology, respectively. Two types of blends were prepared by solution mixing: (a) l-PLLA/c-PLLA, at extreme compositions (rich in linear or in cyclic chains), and (b) blends of each of these low MW materials with a commercial high MW linear PLA. The crystallization of the different blends was evaluated by polarized light optical microscopy and differential scanning calorimetry. It was found, for the first time, that in the l-PLLA rich blends, small amounts of c-PLLA (i.e., 5 and 10 wt%) increase the nucleation density, nucleation rate (1/τ0), spherulitic growth rate (G), and overall crystallization rate (1/τ50%), when compared to neat l-PLLA, due to a synergistic effect (i.e., nucleation plus plasticization). In contrast, the opposite effect was found in the c-PLLA rich blends. The addition of small amounts of l-PLLA to a matrix of c-PLLA chains causes a decrease in the nucleation density, 1/τ0, G, and 1/τ50% values, due to threading effects between cyclic and linear chains. Small amounts of l-PLLA and c-PLLA enhance the crystallization ability of a commercial high MW linear PLA without affecting its melting temperature. The l-PLLA only acts as a plasticizer for the PLA matrix, whereas c-PLLA has a synergistic effect in accelerating the crystallization of PLA that goes beyond simple plasticization. The addition of small amounts of c-PLLA affects not only PLA crystal growth but also its nucleation due to the unique cyclic chains topology.
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Plastificantes/química , Poliésteres/química , Cristalização , Cinética , Modelos Moleculares , Conformação Molecular , Peso Molecular , TemperaturaRESUMO
Free-standing nanopapers based on graphene and its related materials have been widely studied and proposed for flexible heat spreader applications. Given that these materials are typically brittle, this work reports the exploitation of polycaprolactone (PCL) as a polymer binder to enhance resistance and flexibility of nanopapers based on graphite nanoplates (GNP), while maintaining a high thermal conductivity. Properties of nanopapers appear to correlate with the excellent PCL adhesion and strong nucleation of the surface of GNP flakes. Furthermore, different crystalline populations were observed for PCL within the nanopaper and were investigated in detail via differential scanning calorimetry advanced techniques and X-ray diffraction. These demonstrated the coexistence of conventional unoriented PCL crystals, oriented PCL crystals obtained as a consequence of the strong nucleation effect, and highly stable PCL fractions explained by the formation of crystalline pre-freezing layers, the latter having melting temperatures well above the equilibrium melting temperature for pristine PCL. This peculiar crystallization behavior of PCL, reported in this paper for the first time for a tridimensional structure, has a direct impact on material properties. Indeed, the presence of high thermal stability crystals, strongly bound to GNP flakes, coexisting with the highly flexible amorphous fraction, delivers an ideal solution for the strengthening and toughening of GNP nanopapers. Thermomechanical properties of PCL/GNP nanopapers, investigated both on a heating ramp and by creep tests at high temperatures, demonstrated superior stiffness well above the conventional melting temperature of PCL. At the same time, a thermal conductivity > 150 W/m·K was obtained for PCL/GNP nanopapers, representing a viable alternative to traditional metals in terms of heat dissipation, while affording flexibility and light weight, unmatched by conventional thermally conductive metals or ceramics. Besides the obtained performance, the formation of polymer crystals that are stable above the equilibrium melting temperature constitutes a novel approach in the self-assembly of highly ordered nanostructures based on graphene and related materials.
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We previously showed that nanoparticles (NPs) could be ordered into structures by using the growth rate of polymer crystals as the control variable. In particular, for slow enough spherulitic growth fronts, the NPs grafted with amorphous polymer chains are selectively moved into the interlamellar, interfibrillar, and interspherulitic zones of a lamellar morphology, specifically going from interlamellar to interspherulitic with progressively decreasing crystal growth rates. Here, we examine the effect of NP polymer grafting density on crystallization kinetics. We find that while crystal nucleation is practically unaffected by the presence of the NPs, spherulitic growth, final crystallinity, and melting point values decrease uniformly as the volume fraction of the crystallizable polymer, poly(ethylene oxide) or PEO, ÏPEO, decreases. A surprising aspect here is that these results are apparently unaffected by variations in the relative amounts of the amorphous polymer graft and silica NPs at constant Ï, implying that chemical details of the amorphous defect apparently only play a secondary role. We therefore propose that the grafted NPs in this size range only provide geometrical confinement effects which serve to set the crystal growth rates and melting point depressions without causing any changes to crystallization mechanisms.
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[This corrects the article DOI: 10.1371/journal.pone.0194050.].
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Multiechelon supply chains are complex logistics systems that require flexibility and coordination at a tactical level to cope with environmental uncertainties in an efficient and effective manner. To cope with these challenges, mathematical programming models are developed to evaluate supply chain flexibility. However, under uncertainty, supply chain models become complex and the scope of flexibility analysis is generally reduced. This paper presents a unified approach that can evaluate the flexibility of a four-echelon supply chain via a robust stochastic programming model. The model simultaneously considers the plans of multiple business divisions such as marketing, logistics, manufacturing, and procurement, whose goals are often conflicting. A numerical example with deterministic parameters is presented to introduce the analysis, and then, the model stochastic parameters are considered to evaluate flexibility. The results of the analysis on supply, manufacturing, and distribution flexibility are presented. Tradeoff analysis of demand variability and service levels is also carried out. The proposed approach facilitates the adoption of different management styles, thus improving supply chain resilience. The model can be extended to contexts pertaining to supply chain disruptions; for example, the model can be used to explore operation strategies when subtle events disrupt supply, manufacturing, or distribution.
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Comércio/métodos , Equipamentos e Provisões , Marketing/métodos , Modelos Teóricos , IncertezaRESUMO
In this study, nanocomposites were prepared by melt blending poly(butylene succinate) (PBS) with a polycarbonate (PC)/multi-wall carbon nanotubes (MWCNTs) masterbatch, in a twin-screw extruder. The nanocomposites contained 0.5, 1.0, 2.0, and 4.0 wt% MWCNTs. Differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) results indicate that the blends are partially miscible, hence they form two phases (i.e., PC-rich and PBS-rich phases). The PC-rich phase contained a small amount of PBS chains that acted as a plasticizer and enabled crystallization of the PC component. In the PBS-rich phase, the amount of the PC chains present gave rise to increases in the glass transition temperature of the PBS phase. The presence of two phases was supported by scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis, where most MWCNTs aggregated in the PC-rich phase (especially at the high MWCNTs content of 4 wt%) and a small amount of MWCNTs were able to diffuse to the PBS-rich phase. Standard DSC scans showed that the MWCNTs nucleation effects saturated at 0.5 wt% MWCNT content on the PBS-rich phase, above this content a negative nucleation effect was observed. Isothermal crystallization results indicated that with 0.5 wt% MWCNTs the crystallization rate was accelerated, but further increases in MWCNTs loading (and also in PC content) resulted in progressive decreases in crystallization rate. The results are explained by increased MWCNTs aggregation and reduced diffusion rates of PBS chains, as the masterbatch content in the blends increased.