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AIM OF THE STUDY: Case report on risk management for the epidemiology of an infectious disease threat scenario at the municipal level using the example of the Asian tiger mosquito (ATM) with communication of figures based on experience to stakeholders in the public health service METHODS: Formal and substantive presentation of a list of defined control measures together with site-specific modification and evaluation of efficacy RESULTS: Based on a timely education campaign, establishment of a population of ATM first observed in the fall of 2016 could be prevented at the local level. With favourable low temperatures during the 2016/2017 winter months, primarily physical control methods were effective. In the spring of 2017, ATM was no longer detected by a total of 4 monitoring units, each with a suction trap and 3 passive traps. In the following period, up to and including the spring of 2019, no invasive species of mosquito were identified in the cemetery originally involved or in the adjacent residential areas or recreational grounds Overall, cooperation among external experts and stakeholders from the public health service at the level of individualised medicine were able to prevent an insect-borne infection of the local population; a gradual approach following defined criteria for insect control proved to be effective and efficient. CONCLUSION: The occurrence of the ATM is primarily a local event that requires a differentiated weighing-up between a specific and abstract hazard potential by the regional health authorities. In addition to an objective and prompt education campaign for the population involved as a trust-building action, primary physical control measures in terms of barrier measures are effective; if necessary, chemical and biological controls can be used as complementary measures.
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Aedes , Gestão de Riscos , Animais , Humanos , Alemanha , Espécies IntroduzidasRESUMO
Some agroforestry residues such as orange and olive tree pruning have been extensively evaluated for their valorization due to its high carbohydrates content. However, lignin-enriched residues generated during carbohydrates valorization are normally incinerated to produce energy. In order to find alternative high added-value applications for these lignins, a depth characterization of them is required. In this study, lignins isolated from the black liquors produced during soda/anthraquinone (soda/AQ) pulping of orange and olive tree pruning residues were analyzed by analytical standard methods and Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (solid state 13C NMR and 2D NMR) and size exclusion chromatography (SEC). Thermal analysis (thermogravimetric analysis (TGA), differential scanning calorimetry (DSC)) and antioxidant capacity (Trolox equivalent antioxidant capacity) were also evaluated. Both lignins showed a high OH phenolic content as consequence of a wide breakdown of ß-aryl ether linkages. This extensive degradation yielded lignins with low molecular weights and polydispersity values. Moreover, both lignins exhibited an enrichment of syringyl units together with different native as well as soda/AQ lignin derived units. Based on these chemical properties, orange and olive lignins showed relatively high thermal stability and good antioxidant activities. These results make them potential additives to enhance the thermo-oxidation stability of synthetic polymers.
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Antioxidantes/análise , Citrus sinensis/química , Lignina/química , Lignina/farmacologia , Olea/química , Fenóis/análise , Varredura Diferencial de Calorimetria , Cromatografia em Gel , Espectroscopia de Ressonância Magnética , Espectroscopia de Infravermelho com Transformada de Fourier , TermogravimetriaRESUMO
We have studied how cellulose nanocrystals (CNC) self-assemble into liquid crystalline phases in shrinking, isolated droplets. By adjusting the water dissolution rate of an aqueous CNC droplet immersed in a binary toluene-ethanol mixture we can control the final morphology of the consolidated microbead. At low ethanol concentration in the surrounding fluid dense microbeads of spherical morphology are produced while collapsed core-shell particles are obtained at high ethanol concentration. Polarized light microscopy was used to follow the spatial evolution and coalescence of birefringent spheroids during droplet shrinkage. Electron microscopy reveals the resultant nematic microstructure. This method of confined CNC assembly provides thus the possibility to prepare ordered microbeads, which can be useful as templates or for their optical properties.
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Celulose/química , Nanopartículas/química , Cristais Líquidos/química , Microesferas , Propriedades de Superfície , Água/químicaRESUMO
In an era marked by increasing environmental challenges affecting human well-being, traditional acoustic materials struggle to effectively handle the diverse and multi-frequency nature of harmful environmental noises. This has spurred a demand for innovative acoustic metamaterial solutions by utilizing sustainable design strategies. This research introduces tunable Schwarz metamaterial capable of transforming into a soft meta-foam to solve the complex problems of varying environmental noises. This study primarily focuses on adjusting single to multiple sound-blocking bandgaps mechanism using a multi-layered approach, incorporating the Schwarz P-type triply periodic minimal surface (TPMS) and its elective soft foam counterpart, known as tunable Schwarz meta-foams (TSMF-x). The tunable design parameters of the unit cell, multi-layered TPMS, and soft programmable TSMF-lichen version are comprehensively explored including a fire-safety test. The results demonstrate these enhanced flame retardant meta-foam families have the potential to be used for mid-to-high-frequency environmental noises in industrial equipment and smart homes for sustainable architecture and environmental health applications.
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MXenes are highly versatile and conductive 2D materials that can significantly enhance the triboelectric properties of polymer nanocomposites. Despite the growing interest in the tunable chemistry of MXenes for energy applications, the effect of their chemical composition on triboelectric power generation has yet to be thoroughly studied. Here, we investigate the impact of the chemical composition of MXenes, specifically the Ti3CNTx carbonitride vs the most studied carbide, Ti3C2Tx, on their interactions with sodium alginate biopolymer and, ultimately, the performance of a triboelectric nanogenerator (TENG) device. Our results show that adding 2 wt % of Ti3CNTx to alginate produces a synergistic effect that generates a higher triboelectric output than the Ti3C2Tx system. Spectroscopic analyses suggest that a higher oxygen and fluorine content on the surface of Ti3CNTx enhances hydrogen bonding with the alginate matrix, thereby increasing the surface charge density of the alginate oxygen atoms. This was further supported by Kelvin probe force microscopy, which revealed a more negative surface potential on Ti3CNTx-alginate, facilitating high charge transfer between the TENG electrodes. The optimized Ti3CNTx-alginate nanogenerator delivered an output of 670 V, 15 µA, and 0.28 W/m2. Additionally, we demonstrate that plasma oxidation of the MXene surface further enhances triboelectric performance. Due to the diverse surface terminations of MXene, we show that Ti3CNTx-alginate can function as either tribopositive or tribonegative material, depending on the counter-contacting material. Our findings provide a deeper understanding of how MXene composition affects their interaction with biopolymers and resulting tunable triboelectrification behavior. This opens up new avenues for developing flexible and efficient MXene-based TENG devices.
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Natural polymers such as cellulose have interesting tribo- and piezoelectric properties for paper-based energy harvesters, but their low performance in providing sufficient output power is still an impediment to a wider deployment for IoT and other low-power applications. In this study, different types of celluloses were combined with nanosized carbon fillers to investigate their effect on the enhancement of the electrical properties in the final nanogenerator devices. Cellulose pulp (CP), microcrystalline cellulose (MCC) and cellulose nanofibers (CNFs) were blended with carbon black (CB), carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs). The microstructure of the nanocomposite films was characterized by scanning electron and probe microscopies, and the electrical properties were measured macroscopically and at the local scale by piezoresponse force microscopy. The highest generated output voltage in triboelectric mode was obtained from MCC films with CNTs and CB, while the highest piezoelectric voltage was produced in CNF-CNT films. The obtained electrical responses were discussed in relation to the material properties. Analysis of the microscopic response shows that pulp has a higher local piezoelectric d33 coefficient (145 pC/N) than CNF (14 pC/N), while the macroscopic response is greatly influenced by the excitation mode and the effective orientation of the crystals relative to the mechanical stress. The increased electricity produced from cellulose nanocomposites may lead to more efficient and biodegradable nanogenerators.
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Representative, actively collected surveillance data on asymptomatic SARS-CoV-2 infections in primary schoolchildren remain scarce. We evaluated the feasibility of a saliva mass screening concept and assessed infectious activity in primary schools. During a 10-week period from 3 March to 21 May 2021, schoolchildren and staff from 17 primary schools in Munich participated in the sentinel surveillance, cohort study. Participants were tested using the Salivette® system, testing was supervised by trained school staff, and samples were processed via reverse transcription quantitative polymerase chain reaction (RT-qPCR). We included 4433 participants: 3752 children (median age, 8 [range, 6-13] years; 1926 girls [51%]) and 681 staff members (median age, 41 [range, 14-71] years; 592 women [87%]). In total, 23,905 samples were processed (4640 from staff), with participants representing 8.3% of all primary schoolchildren in Munich. Only eight cases were detected: Five out of 3752 participating children (0.13%) and three out of 681 staff members (0.44%). There were no secondary cases. In conclusion, supervised Salivette® self-sampling was feasible, reliable, and safe and thus constituted an ideal method for SARS-CoV-2 mass screenings in primary schoolchildren. Our findings suggest that infectious activity among asymptomatic primary schoolchildren and staff was low. Primary schools appear to continue to play a minor role in the spread of SARS-CoV-2 despite high community incidence rates.
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Rechargeable batteries are a major element in the transition to renewable energie systems, but the current lithium-ion battery technology may face limitations in the future concerning the availability of raw materials and socio-economic insecurities. Sodium-sulfur (Na-S) batteries are a promising alternative energy storage device for small- to large-scale applications driven by more favorable environmental and economic perspectives. However, scientific and technological problems are still hindering a commercial breakthrough of these batteries. This review discusses strategies to remedy some of the current drawbacks such as the polysulfide shuttle effect, catastrophic volume expansion, Na dendrite growth, and slow reaction kinetics by nanostructuring both the sulfur cathode and the Na anode. Moreover, a survey of recent patents on room temperature (RT) Na-S batteries revealed that nanostructured sulfur and sodium electrodes are still in the minority, which suggests that much investigation and innovation is needed until RT Na-S batteries can be commercialized.
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TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl)-oxidized cellulose nanofibers (CNF) were assembled to fibrous clay sepiolite (SEP) by means of a high shear homogenizer and an ultrasound treatment followed by lyophilization using three different methods: normal freezing, directional freezing, and a sequential combination of both methods. Methyltrimethoxysilane (MTMS) was grafted to the foam surface by the vapor deposition method to introduce hydrophobicity to the resulting materials. Both the SEP addition (for the normal and directional freezing methods) and the refreezing preparation procedure enhanced the compressive strength of the foams, showing compressive moduli in the range from 28 to 103 kPa for foams loaded with 20% w/w sepiolite. Mercury intrusion porosimetry shows that the average pore diameters were in the range of 30-45 µm depending on the freezing method. This large porosity leads to materials with very low apparent density, around 6 mg/cm3, and very high porosity >99.5%. In addition, water contact angle measurement and Fourier-transform infrared spectroscopy (FTIR) were applied to confirm the foam hydrophobicity, which is suitable for use as an oil sorbent. The sorption ability of these composite foams has been tested using olive and motor oils as models of organophilic liquid adsorbates, observing a maximum sorption capacity of 138 and 90 g/g, respectively.
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Silicatos de Magnésio , Nanofibras , Interações Hidrofóbicas e Hidrofílicas , ÓleosRESUMO
In order to identify new sustainable sources for producing cellulose nanofibers (CNFs), fast-growing poplar (Populus alba L.) wood was evaluated herein. For that purpose, bleached poplar kraft pulp was produced and submitted to TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) mediated oxidation (TEMPO-ox) chemical pretreatment followed by microfluidization. The resulting CNFs were thoroughly characterized, including a rheological study at different pH values. Poplar CNFs showed properties comparable to eucalypt CNFs (reference material for CNFs production), showing high carboxylate content (1048 ± 128 µmol g-1), fibrillation yield (87.3% ± 8.1%), optical transmittance (83% at 700 nm) and thermal stability (up to more than 200 °C). Regarding the rheological study, whereas pH from 4 to 10 did not produce significant changes in rheological behavior, a reduction of pH down to 1 led to an order-of-magnitude increase on the viscoelastic functions. Therefore, poplar CNF shows potential in the pH-sensitive hydrogels application field. Finally, the possible ecotoxicity of poplar CNF was assessed. The decrease in cell viability was very low so that only concentrations causing a 10% cytotoxicity could be calculated for the assay detecting alterations in cell metabolism (10 µg mL-1) and plasma membrane integrity (60 µg mL-1).
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Kraft pulping, organosolv process and acid hydrolysis were applied on an elm clone. The solubilized lignins were recovered and analyzed. Kraft pulping and acid hydrolysis led to lignins with higher phenolic OH content as result of extensive cleavage of ß-O-4' linkages, as revealed by 13C solid state and 13C-1H heteronuclear single quantum coherence nuclear magnetic resonance. This depolymerization also yielded lower molecular weight lignins inferred by size exclusion chromatography. Contrarily, organosolv process gave rise to a lignin with a more preserved structure, maintaining a large number of ß-O-4' linkages. Consequently, organosolv lignin presented lower phenolic OH content and higher molecular weight. Moreover, the high content of the labile native ß-O-4' linkages in organosolv lignin resulted in a lower thermostability as compared to the kraft and acid lignins. On the other hand, the solubilized lignins from kraft and acid processes displayed an enrichment of S-units, whereas lignin from organosolv process was slightly enriched in G-units, containing all of them different native as well as pre-treatment derived units. These results could help to increase the inventory of lignin sources available for future lignin-based products, for which knowledge of the lignin properties versus application requirements is crucial.
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Lignina/química , Ulmus/química , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Células Clonais , Conformação Molecular , Peso Molecular , Solubilidade , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura , TermogravimetriaRESUMO
A new type of hybrid biomaterials based on the clay minerals montmorillonite and sepiolite as well as phosphatidylcholine, acting as environment-friendly biomodifier, was prepared. The biohybrids were characterized by sampling of adsorption isotherms in different organic solvents. The results suggest bilayer formation both on the external sepiolite surface as well as in the intracrystalline space of the montmorillonite. The obtained supported lipid membranes were further investigated by X-ray diffraction, multinuclear solid state NMR, Fourier transformed IR spectroscopy and thermal analysis. From these results an adsorption model based on electrostatic interaction between the polar phospholipid headgroups and the silicate surface could be postulated. The versatility of bio-organoclays as immobilization host for biological species was demonstrated in a mycotoxin retention study.
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Materiais Biocompatíveis/química , Bentonita/química , Silicatos de Magnésio/química , Espectroscopia de Ressonância Magnética , Modelos Teóricos , Fosfatidilcolinas/química , Espectroscopia de Infravermelho com Transformada de Fourier , Difração de Raios XRESUMO
Biohybrid materials were prepared by co-assembling the three following components: nanotubular halloysite, microfibrous sepiolite, and cellulose nanofibers dispersed in water, in order to exploit the most salient features of each individual component and to render homogeneous, flexible, yet strong films. Indeed, the incorporation of halloysite improves the mechanical performance of the resulting hybrid nanopapers and the assembly of the three components modifies the surface features concerning wetting properties compared to pristine materials, so that the main characteristics of the resulting materials become tunable with regard to certain properties. Owing to their hierarchical porosity together with their diverse surface characteristics, these hybrids can be used in diverse biomedical/pharmaceutical applications. Herein, for instance, loading with two model drugs, salicylic acid and ibuprofen, allows controlled and sustained release as deduced from antimicrobial assays, opening a versatile path for developing other related organic-inorganic materials of potential interest in diverse application fields.
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Antibacterianos/farmacologia , Celulose/química , Ibuprofeno/química , Ibuprofeno/farmacologia , Nanofibras/química , Ácido Salicílico/farmacologia , Antibacterianos/química , Relação Dose-Resposta a Droga , Bactérias Gram-Negativas/efeitos dos fármacos , Bactérias Gram-Positivas/efeitos dos fármacos , Testes de Sensibilidade Microbiana , Tamanho da Partícula , Ácido Salicílico/química , Relação Estrutura-Atividade , Propriedades de SuperfícieRESUMO
Researchers, engineers, and medical doctors are made aware of the severity of the COVID-19 infection and act quickly against the coronavirus SARS-CoV-2 using a large variety of tools. In this review, a panoply of nanoscience and nanotechnology approaches show how these disciplines can help the medical, technical, and scientific communities to fight the pandemic, highlighting the development of nanomaterials for detection, sanitation, therapies, and vaccines. SARS-CoV-2, which can be regarded as a functional core-shell nanoparticle (NP), can interact with diverse materials in its vicinity and remains attached for variable times while preserving its bioactivity. These studies are critical for the appropriate use of controlled disinfection systems. Other nanotechnological approaches are also decisive for the development of improved novel testing and diagnosis kits of coronavirus that are urgently required. Therapeutics are based on nanotechnology strategies as well and focus on antiviral drug design and on new nanoarchitectured vaccines. A brief overview on patented work is presented that emphasizes nanotechnology applied to coronaviruses. Finally, some comments are made on patents of the initial technological responses to COVID-19 that have already been put in practice.
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Betacoronavirus , Infecções por Coronavirus , Nanotecnologia/métodos , Pandemias , Pneumonia Viral , Antivirais/administração & dosagem , Betacoronavirus/química , Betacoronavirus/ultraestrutura , COVID-19 , Teste para COVID-19 , Vacinas contra COVID-19 , Técnicas de Laboratório Clínico/métodos , Infecções por Coronavirus/diagnóstico , Infecções por Coronavirus/prevenção & controle , Infecções por Coronavirus/terapia , Desinfecção/métodos , Humanos , Nanopartículas/química , Nanopartículas/ultraestrutura , Nanoestruturas/química , Nanotecnologia/legislação & jurisprudência , Pandemias/prevenção & controle , Patentes como Assunto , Pneumonia Viral/diagnóstico , Pneumonia Viral/prevenção & controle , Pneumonia Viral/terapia , SARS-CoV-2 , Propriedades de Superfície , Vacinas Virais/administração & dosagemRESUMO
BACKGROUND: COVID-19 pandemic is a global problem that requires the point of view of basic sciences and medicine as well as social, economics and politics disciplines. Viral particles of coronaviruses including SARS-CoV-2 as well as other enveloped viruses like influenza virus could be considered as an approximation to functional core-shell nanoparticles and therefore, their study enters the realm of nanotechnology. In this context, nanotechnology can contribute to alleviate some of the current challenges posed by COVID-19 pandemic. METHODS: The present analysis contributed to diverse sources of general information, databases on scientific literature and patents to produce a review affording information on relevant areas where as nanotechnology has offered response to coronavirus challenges in the past and may be relevant now, and has offered an update of the current information on SARS-CoV-2 and COVID-19 issues. RESULTS: This review contribution includes specific information including: 1) An introduction to current research on nanotechnology and related recent patents for COVID-19 responses; 2) Analysis of nonimmunogenic and immunogenic prophylaxis of COVID-19 using Nanotechnology; 3) Tools devoted to detection & diagnosis of coronaviruses and COVID-19: the role of Nanotechnology; and 4) A compilation on the research and patents on nanotechnology dealing with therapeutics & treatments of COVID-19. CONCLUSION: Among the increasing literature on COVID-19, there are few works analyzing the relevance of Nanotechnology, and giving an analysis on patents dealing with coronaviruses that may provide useful information on the area. This review offers a general view of the current research investigation and recent patents dealing with aspects of immunogenic and non-immunogenic prophylaxis, detection and diagnosis as well as therapeutics and treatments.
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Antivirais/uso terapêutico , Tratamento Farmacológico da COVID-19 , COVID-19 , Nanotecnologia , Pandemias , SARS-CoV-2 , COVID-19/epidemiologia , Patentes como AssuntoRESUMO
BACKGROUND: In December, 2019, the newly identified severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) emerged in Wuhan, China, causing COVID-19, a respiratory disease presenting with fever, cough, and often pneumonia. WHO has set the strategic objective to interrupt spread of SARS-CoV-2 worldwide. An outbreak in Bavaria, Germany, starting at the end of January, 2020, provided the opportunity to study transmission events, incubation period, and secondary attack rates. METHODS: A case was defined as a person with SARS-CoV-2 infection confirmed by RT-PCR. Case interviews were done to describe timing of onset and nature of symptoms and to identify and classify contacts as high risk (had cumulative face-to-face contact with a confirmed case for ≥15 min, direct contact with secretions or body fluids of a patient with confirmed COVID-19, or, in the case of health-care workers, had worked within 2 m of a patient with confirmed COVID-19 without personal protective equipment) or low risk (all other contacts). High-risk contacts were ordered to stay at home in quarantine for 14 days and were actively followed up and monitored for symptoms, and low-risk contacts were tested upon self-reporting of symptoms. We defined fever and cough as specific symptoms, and defined a prodromal phase as the presence of non-specific symptoms for at least 1 day before the onset of specific symptoms. Whole genome sequencing was used to confirm epidemiological links and clarify transmission events where contact histories were ambiguous; integration with epidemiological data enabled precise reconstruction of exposure events and incubation periods. Secondary attack rates were calculated as the number of cases divided by the number of contacts, using Fisher's exact test for the 95% CIs. FINDINGS: Patient 0 was a Chinese resident who visited Germany for professional reasons. 16 subsequent cases, often with mild and non-specific symptoms, emerged in four transmission generations. Signature mutations in the viral genome occurred upon foundation of generation 2, as well as in one case pertaining to generation 4. The median incubation period was 4·0 days (IQR 2·3-4·3) and the median serial interval was 4·0 days (3·0-5·0). Transmission events were likely to have occurred presymptomatically for one case (possibly five more), at the day of symptom onset for four cases (possibly five more), and the remainder after the day of symptom onset or unknown. One or two cases resulted from contact with a case during the prodromal phase. Secondary attack rates were 75·0% (95% CI 19·0-99·0; three of four people) among members of a household cluster in common isolation, 10·0% (1·2-32·0; two of 20) among household contacts only together until isolation of the patient, and 5·1% (2·6-8·9; 11 of 217) among non-household, high-risk contacts. INTERPRETATION: Although patients in our study presented with predominately mild, non-specific symptoms, infectiousness before or on the day of symptom onset was substantial. Additionally, the incubation period was often very short and false-negative tests occurred. These results suggest that although the outbreak was controlled, successful long-term and global containment of COVID-19 could be difficult to achieve. FUNDING: All authors are employed and all expenses covered by governmental, federal state, or other publicly funded institutions.
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Betacoronavirus/isolamento & purificação , Doenças Transmissíveis Importadas/transmissão , Infecções por Coronavirus/transmissão , Surtos de Doenças , Transmissão de Doença Infecciosa , Pneumonia Viral/transmissão , Doença Relacionada a Viagens , Adolescente , Adulto , Betacoronavirus/classificação , Betacoronavirus/genética , COVID-19 , Criança , Pré-Escolar , China , Doenças Transmissíveis Importadas/epidemiologia , Doenças Transmissíveis Importadas/patologia , Doenças Transmissíveis Importadas/virologia , Infecções por Coronavirus/epidemiologia , Alemanha/epidemiologia , Humanos , Entrevistas como Assunto , Pessoa de Meia-Idade , Mutação , Pandemias , Pneumonia Viral/epidemiologia , RNA Viral/genética , Reação em Cadeia da Polimerase Via Transcriptase Reversa , Medição de Risco , SARS-CoV-2 , Viagem , Adulto JovemRESUMO
Based on the unique ability of defibrillated sepiolite (SEP) to form stable and homogeneous colloidal dispersions of diverse types of nanoparticles in aqueous media under ultrasonication, multicomponent conductive nanoarchitectured materials integrating halloysite nanotubes (HNTs), graphene nanoplatelets (GNPs) and chitosan (CHI) have been developed. The resulting nanohybrid suspensions could be easily formed into films or foams, where each individual component plays a critical role in the biocomposite: HNTs act as nanocontainers for bioactive species, GNPs provide electrical conductivity (enhanced by doping with MWCNTs) and, the CHI polymer matrix introduces mechanical and membrane properties that are of key significance for the development of electrochemical devices. The resulting characteristics allow for a possible application of these active elements as integrated multicomponent materials for advanced electrochemical devices such as biosensors and enzymatic biofuel cells. This strategy can be regarded as an "a la carte" menu, where the selection of the nanocomponents exhibiting different properties will determine a functional set of predetermined utility with SEP maintaining stable colloidal dispersions of different nanoparticles and polymers in water.
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Lignin streams produced in biorefineries are commonly used to obtain energy. In order to increase the competitiveness of this industry, new lignin valorization routes are necessary, for which a depth characterization of this biological macromolecule is essential. In this context, this study analyzed lignin streams of Robinia pseudoacacia L. generated during organosolv and acid hydrolysis pre-treatments and during the subsequent enzymatic hydrolysis. These lignins included dissolved lignins from pre-treatment liquors and saccharification lignins from pre-treated materials. Chemical composition and structural features were analyzed by analytical standard methods and Fourier Transform Infrared spectroscopy (FTIR), size exclusion chromatography (SEC), 13C solid state nuclear magnetic resonance (13C NMR) and 1H-13C two-dimensional nuclear magnetic resonance (2D NMR); while thermal characterization included thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). In general, all studied lignins contained a predominance of ß-O-4' aryl ether linkages, followed by resinol (ß-ß') and phenylcoumaran (ß-5'), with a predominance of syringyl over guaiacyl and hydroxyphenyl units. Nevertheless, the dissolved lignins revealed a removal of linkages, especially ß-O-4', leading to an enrichment of phenolic groups. Moreover, high thermal stability and good thermoplasticity were characteristics of these lignins. Contrary, the saccharification lignins exhibited a more intact structure, but with an important remaining carbohydrates content.
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Lignina/química , Robinia/química , Ácidos , Cromatografia em Gel , Hidrólise , Espectroscopia de Ressonância Magnética , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
The complexity and heterogeneity of lignin requires a detailed understanding in order to decide about more efficient lignin valorization approaches. This study deals with the characterization of lignins from Populus alba L. generated as by-products in different transformation processes: kraft pulping, organosolv and dilute acid hydrolysis. In addition to the composition, the chemical and structural features of the different lignins were investigated by Fourier Transform infrared spectroscopy (FTIR), solid-state 13C nuclear magnetic resonance (13C NMR), two-dimensional nuclear magnetic spectrometry (2D NMR), size exclusion chromatography (SEC), and thermal analysis. Organosolv lignin showed noticeably different characteristics compared to kraft and acid hydrolysis lignins; higher molar mass, higher amount of side-chain linkages (mainly aryl-ß ether and resinol) together with lower phenolic content. On the contrary, kraft and acid hydrolysis lignins presented an extensive elimination of lateral chains and therefore a higher phenolic content, which suggests a much stronger lignin depolymerization (lower molar mass) during these processes. Moreover, thermal analysis results revealed that the thermal stability of kraft and acid hydrolysis lignins was higher than that of organosolv lignin, especially in the case of acid hydrolysis lignin. According to all these characteristics, several valorization pathways for studied lignin are discussed.
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Biotecnologia/métodos , Lignina/análise , Populus/química , Ácidos Sulfúricos/química , Madeira/química , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Cromatografia em Gel , Análise Diferencial Térmica , Hidrólise , Lignina/química , Peso Molecular , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura , TermogravimetriaRESUMO
Pure cellulosic foams suffer from low thermal stability and high flammability, limiting their fields of application. Here, light-weight and flame-resistant nanostructured foams are produced by combining cellulose nanofibrils prepared from phosphorylated pulp fibers (P-CNF) with microfibrous sepiolite clay using the freeze-casting technique. The resultant nanocomposite foams show excellent flame-retardant properties such as self-extinguishing behavior and extremely low heat release rates in addition to high flame penetration resistance attributed mainly to the intrinsic charring ability of the phosphorylated fibrils and the capability of sepiolite to form heat-protective intumescent-like barrier on the surface of the material. Investigation of the chemical structure of the charred residue by FTIR and solid state NMR spectroscopy reveals the extensive graphitization of the carbohydrate as a result of dephosphorylation of the modified cellulose and further dehydration due to acidic catalytic effects. Originating from the nanoscale dimensions of sepiolite particles, their high specific surface area and stiffness as well as its close interaction with the phosphorylated fibrils, the incorporation of clay nanorods also significantly improves the mechanical strength and stiffness of the nanocomposite foams. The novel foams prepared in this study are expected to have great potential for application in sustainable building construction.