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1.
Nature ; 570(7759): 52-57, 2019 06.
Artigo em Inglês | MEDLINE | ID: mdl-31168102

RESUMO

Plate tectonics is among the most important geological processes on Earth, but its emergence and evolution remain unclear. Here we extrapolate models of present-day plate tectonics to the past and propose that since about three billion years ago the rise of continents and the accumulation of sediments at continental edges and in trenches has provided lubrication for the stabilization of subduction and has been crucial in the development of plate tectonics on Earth. We conclude that the two largest surface erosion and subduction lubrication events occurred after the Palaeoproterozoic Huronian global glaciations (2.45 to 2.2 billion years ago), leading to the formation of the Columbia supercontinent, and after the Neoproterozoic 'snowball' Earth glaciations (0.75 to 0.63 billion years ago). The snowball Earth event followed the 'boring billion'-a period of reduced plate tectonic activity about 1.75 to 0.75 billion years ago that was probably caused by a shortfall of sediments in trenches-and it kick-started the modern episode of active plate tectonics.

2.
Emerg Med J ; 40(1): 61-66, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36344240

RESUMO

BACKGROUND: The Pulmonary Embolism Severity Index (PESI) and the simplified PESI (sPESI) are validated scores for mortality prediction in patients with pulmonary embolism (PE). National Early Warning Score (NEWS) is a general prognostic risk score for multiple clinical settings. We investigated whether the NEWS had a comparable performance with the PESI and sPESI, for predicting intensive care unit (ICU) admission and death in patients with acute PE. METHODS: In haemodynamically stable patients with confirmed PE from the YEARS Study (2013-2015), we evaluated the performance of the NEWS, PESI and sPESI for predicting 7-day ICU admission and 30-day mortality. Receiver operating characteristic curves were plotted and the area under the curve (AUC) was calculated. RESULTS: Of 352 patients, 12 (3.4%) were admitted to the ICU and 5 (1.4%) died. The AUC of the NEWS for ICU admission was 0.80 (95% CI 0.66 to 0.94) and 0.92 (95% CI 0.82 to 1.00) for 30-day mortality. At a threshold of 3 points, NEWS yielded a sensitivity and specificity of 92% and 53% for ICU admission and 100% and 52% for 30-day mortality. The AUC of the PESI was 0.64 (95% CI 0.48 to 0.79) for ICU admission and 0.94 (95% CI 0.87 to 1.00) for mortality. At a threshold of 66 points, PESI yielded a sensitivity of 75% and a specificity of 38% for ICU admission. For mortality, these were 100% and 37%, respectively. The performance of the sPESI was similar to that of PESI. CONCLUSION: In comparison with PESI and sPESI, NEWS adequately predicted 7-day ICU admission as well as 30-day mortality, supporting its potential relevance for clinical practice.


Assuntos
Escore de Alerta Precoce , Embolia Pulmonar , Humanos , Medição de Risco , Índice de Gravidade de Doença , Valor Preditivo dos Testes , Prognóstico , Embolia Pulmonar/diagnóstico , Doença Aguda , Estudos Retrospectivos
3.
Small ; 18(9): e2105896, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-34913586

RESUMO

The poor chemical miscibility between metal and organic materials usually leads to both structural and energetic mismatches at gold/organic interfaces, and thereby, high contact resistance of organic electronic devices. This study shows that the contact resistance of organic field-effect transistors is significantly reduced by one order of magnitude, by reforming the contact interface between gold electrodes and conjugated polymers upon a polymer insulator-assisted thermal annealing. Upon an optimized solution process, the conjugated polymer is homogenously distributed within the amorphous polymer insulator matrix with relatively low glass transition temperature, and thus, even a moderate annealing temperature can induce sufficient motion of conjugated polymer chains to simultaneously adjust the polymer orientation and improve the packing of gold atoms. Consequently, gold/conjugated polymer contact is reorganized after annealing, which improves both charge transport from bulk gold to interface and charge injection from gold into conjugated polymers. This method, with appropriate insulator matrix, is effective for improving the injection of both holes and electrons, and widely applicable for many unipolar and ambipolar conjugated polymers to optimize the device performance and simultaneously increase the optical transparency (over 80%). A frequency doubler and a phase modulator are demonstrated, respectively, using the ambipolar transistors with optimized charge injection properties.

4.
Langmuir ; 38(39): 11983-11993, 2022 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-36150131

RESUMO

Ultrasmall nanoparticles (NPs) with a high active surface area are essential for optoelectronic and photovoltaic applications. However, the structural stability and sustainability of these ultrasmall NPs at higher temperatures remain a critical problem. Here, we have synthesized the nanocomposites (NCs) of Ag NPs inside the silica matrix using the atom beam co-sputtering technique. The post-deposition growth of the embedded Ag NPs is systematically investigated at a wide range of annealing temperatures (ATs). A novel, fast, and effective procedure, correlating the experimental (UV-vis absorption results) and theoretical (quantum mechanical modeling, QMM) results, is used to estimate the size of NPs. The QMM-based simulation, employed for this work, is found to be more accurate in reproducing the absorption spectra over the classical/modified Drude model, which fails to predict the expected shift in the LSPR for ultrasmall NPs. Unlike the classical Drude model, the QMM incorporates the intraband transition of the conduction band electrons to calculate the effective dielectric function of metallic NCs, which is the major contribution of LSPR shifts for ultrasmall NPs. In this framework, a direct comparison is made between experimentally and theoretically observed LSPR peak positions, and it is observed that the size of NPs grows from 3 to 18 nm as AT increases from room temperature to 900 °C. Further, in situ grazing-incidence small- & wide-angle X-ray scattering and transmission electron microscopy measurements are employed to comprehend the growth of Ag NPs and validate the UV + QMM results. We demonstrate that, unlike chemically grown NPs, the embedded Ag NPs ensure greater stability in size and remain in an ultrasmall regime up to 800 °C, and beyond this temperature, the size of NPs increases exponentially due to dominant Ostwald ripening. Finally, a three-stage mechanism is discussed to understand the process of nucleation and growth of the silica-embedded Ag NPs.

5.
Eur Heart J ; 42(33): 3146-3157, 2021 08 31.
Artigo em Inglês | MEDLINE | ID: mdl-34363386

RESUMO

AIMS: The aim of this study is to compare the Hestia rule vs. the simplified Pulmonary Embolism Severity Index (sPESI) for triaging patients with acute pulmonary embolism (PE) for home treatment. METHODS AND RESULTS: Normotensive patients with PE of 26 hospitals from France, Belgium, the Netherlands, and Switzerland were randomized to either triaging with Hestia or sPESI. They were designated for home treatment if the triaging tool was negative and if the physician-in-charge, taking into account the patient's opinion, did not consider that hospitalization was required. The main outcomes were the 30-day composite of recurrent venous thrombo-embolism, major bleeding or all-cause death (non-inferiority analysis with 2.5% absolute risk difference as margin), and the rate of patients discharged home within 24 h after randomization (NCT02811237). From January 2017 through July 2019, 1975 patients were included. In the per-protocol population, the primary outcome occurred in 3.82% (34/891) in the Hestia arm and 3.57% (32/896) in the sPESI arm (P = 0.004 for non-inferiority). In the intention-to-treat population, 38.4% of the Hestia patients (378/984) were treated at home vs. 36.6% (361/986) of the sPESI patients (P = 0.41 for superiority), with a 30-day composite outcome rate of 1.33% (5/375) and 1.11% (4/359), respectively. No recurrent or fatal PE occurred in either home treatment arm. CONCLUSIONS: For triaging PE patients, the strategy based on the Hestia rule and the strategy based on sPESI had similar safety and effectiveness. With either tool complemented by the overruling of the physician-in-charge, more than a third of patients were treated at home with a low incidence of complications.


Assuntos
Embolia Pulmonar , Doença Aguda , Humanos , Alta do Paciente , Prognóstico , Embolia Pulmonar/tratamento farmacológico , Medição de Risco , Índice de Gravidade de Doença
6.
J Antimicrob Chemother ; 76(4): 1010-1018, 2021 03 12.
Artigo em Inglês | MEDLINE | ID: mdl-33367751

RESUMO

BACKGROUND: The development and clinical implementation of the cap-dependent endonuclease (CEN) inhibitor baloxavir marboxil was a breakthrough in influenza therapy, but it was associated with the emergence of drug-resistant variants. OBJECTIVES: To design and synthesize structural analogues of CEN inhibitors and evaluate their safety, pharmacokinetics and antiviral potency in vitro and in vivo. METHODS: The drug candidate AV5124 and its active metabolite AV5116 were synthesized based on pharmacophore modelling. Stability in plasma and microsomes, plasma protein binding, cytotoxicity and antiviral activities were assessed in vitro. Pharmacokinetics after IV or oral administration were analysed in CD-1 mice. Acute toxicity and protective efficacy against lethal A(H1N1)pdm09 influenza virus challenge were examined in BALB/c mice. RESULTS: Pharmacophore model-assisted, 3D molecular docking predicted key supramolecular interactions of the metal-binding group and bulky hydrophobic group of AV5116 with the CEN binding site (Protein Data Bank code: 6FS6) that are essential for high antiviral activity. AV5116 inhibited influenza virus polymerase complexes in cell-free assays and replication of oseltamivir-susceptible and -resistant influenza A and B viruses at nanomolar concentrations. Notably, AV5116 was equipotent or more potent than baloxavir acid (BXA) against WT (I38-WT) viruses and viruses with reduced BXA susceptibility carrying an I38T polymerase acidic (PA) substitution. AV5116 exhibited low cytotoxicity in Madin-Darby canine kidney cells and lacked mitochondrial toxicity, resulting in favourable selective indices. Treatment with 20 or 50 mg/kg AV5124 prevented death in 60% and 100% of animals, respectively. CONCLUSIONS: Overall, AV5124 and A5116 are promising inhibitors of the influenza virus CEN and warrant further development as potent anti-influenza agents.


Assuntos
Vírus da Influenza A Subtipo H1N1 , Influenza Humana , Animais , Antivirais/farmacologia , Antivirais/uso terapêutico , Dibenzotiepinas , Cães , Endonucleases , Humanos , Influenza Humana/tratamento farmacológico , Camundongos , Camundongos Endogâmicos BALB C , Simulação de Acoplamento Molecular , Morfolinas , Piridonas , Triazinas
7.
Biomacromolecules ; 22(10): 4274-4283, 2021 10 11.
Artigo em Inglês | MEDLINE | ID: mdl-34541856

RESUMO

The nano- to microscale structures at the interface between materials can define the macroscopic material properties. These structures are extremely difficult to investigate for complex material systems, such as cellulose-rich materials. The development of new model cellulose materials and measuring techniques has opened new possibilities to resolve this problem. We present a straightforward approach combining micro-focusing grazing-incidence small-angle X-ray scattering and atomic force microscopy (AFM) to investigate the structural rearrangements of cellulose/cellulose interfaces in situ during drying. Based on the results, we propose that molecular interdiffusion and structural rearrangement play a major role in the development of the properties of the cellulose/cellulose interphase; this model is representative of the development of the properties of joint/contact points between macroscopic cellulose fibers.


Assuntos
Celulose , Incidência , Interfase , Difração de Raios X , Raios X
8.
J Chem Phys ; 155(12): 124902, 2021 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-34598569

RESUMO

We examine network formation and percolation of carbon black by means of Monte Carlo simulations and experiments. In the simulation, we model carbon black by rigid aggregates of impenetrable spheres, which we obtain by diffusion-limited aggregation. To determine the input parameters for the simulation, we experimentally characterize the micro-structure and size distribution of carbon black aggregates. We then simulate suspensions of aggregates and determine the percolation threshold as a function of the aggregate size distribution. We observe a quasi-universal relation between the percolation threshold and a weighted average radius of gyration of the aggregate ensemble. Higher order moments of the size distribution do not have an effect on the percolation threshold. We conclude further that the concentration of large carbon black aggregates has a stronger influence on the percolation threshold than the concentration of small aggregates. In the experiment, we disperse the carbon black in a polymer matrix and measure the conductivity of the composite. We successfully test the hypotheses drawn from simulation by comparing composites prepared with the same type of carbon black before and after ball milling, i.e., on changing only the distribution of aggregate sizes in the composites.

9.
Soft Matter ; 16(23): 5439-5449, 2020 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-32469347

RESUMO

Hydrodynamic alignment of proteinaceous or polymeric nanofibrillar building blocks can be utilized for subsequent assembly into intricate three-dimensional macrostructures. The non-equilibrium structure of flowing nanofibrils relies on a complex balance between the imposed flow-field, colloidal interactions and Brownian motion. The understanding of the impact of non-equilibrium dynamics is not only weak, but is also required for structural control. Investigation of underlying dynamics imposed by the flow requires in situ dynamic characterization and is limited by the time-resolution of existing characterization methods, specifically on the nanoscale. Here, we present and demonstrate a flow-stop technique, using polarized optical microscopy (POM) to quantify the anisotropic orientation and diffusivity of nanofibrils in shear and extensional flows. Microscopy results are combined with small-angle X-ray scattering (SAXS) measurements to estimate the orientation of nanofibrils in motion and simultaneous structural changes in a loose network. Diffusivity of polydisperse systems is observed to act on multiple timescales, which is interpreted as an effect of apparent fibril lengths that also include nanoscale entanglements. The origin of the fastest diffusivity is correlated to the strength of velocity gradients, independent of type of deformation (shear or extension). Fibrils in extensional flow results in highly anisotropic systems enhancing interfibrillar contacts, which is evident through a slowing down of diffusive timescales. Our results strongly emphasize the need for careful design of fluidic microsystems for assembling fibrillar building blocks into high-performance macrostructures relying on improved understanding of nanoscale physics.

10.
Proc Natl Acad Sci U S A ; 114(6): 1232-1237, 2017 02 07.
Artigo em Inglês | MEDLINE | ID: mdl-28123065

RESUMO

Some of the most remarkable materials in nature are made from proteins. The properties of these materials are closely connected to the hierarchical assembly of the protein building blocks. In this perspective, amyloid-like protein nanofibrils (PNFs) have emerged as a promising foundation for the synthesis of novel bio-based materials for a variety of applications. Whereas recent advances have revealed the molecular structure of PNFs, the mechanisms associated with fibril-fibril interactions and their assembly into macroscale structures remain largely unexplored. Here, we show that whey PNFs can be assembled into microfibers using a flow-focusing approach and without the addition of plasticizers or cross-linkers. Microfocus small-angle X-ray scattering allows us to monitor the fibril orientation in the microchannel and compare the assembly processes of PNFs of distinct morphologies. We find that the strongest fiber is obtained with a sufficient balance between ordered nanostructure and fibril entanglement. The results provide insights in the behavior of protein nanostructures under laminar flow conditions and their assembly mechanism into hierarchical macroscopic structures.


Assuntos
Lactoglobulinas/química , Nanoestruturas/química , Microscopia de Força Atômica , Reologia , Espalhamento a Baixo Ângulo
11.
J Am Chem Soc ; 141(50): 19700-19707, 2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31747277

RESUMO

Perovskite solar cells (PSCs) has skyrocketed in the past decade to an unprecedented level due to their outstanding photoelectric properties and facile processability. However, the utilization of expensive hole transport materials (HTMs) and the inevitable instability instigated by the deliquescent dopants represent major concerns hindering further commercialization. Here, a series of low-cost, conjugated polymers are designed and applied as dopant-free HTMs in PSCs, featuring tuned energy levels, good temperature and humidity resistivity, and excellent photoelectric properties. Further studies highlight the critical and multifaceted roles of the polymers with respect to facilitating charge separation, passivating the surface trap sites of perovskite materials, and guaranteeing long-term stability of the devices. A stabilized power conversion efficiency (PCE) of 20.3% and remarkably enhanced device longevity are achieved using the dopant-free polymer P3 with a low concentration of 5 mg/mL, qualifying the device as one of the best PSC systems constructed on the basis of dopant-free HTMs so far. In addition, the flexible PSCs based on P3 also exhibit a PCE of 16.2%. This work demonstrates a promising route toward commercially viable, stable, and efficient PSCs.

12.
Angew Chem Int Ed Engl ; 58(51): 18562-18569, 2019 12 16.
Artigo em Inglês | MEDLINE | ID: mdl-31600016

RESUMO

Designing engineering materials with high stiffness and high toughness is challenging as stiff materials tend to be brittle. Many biological materials realize this objective through multiscale (i.e., atomic- to macroscale) mechanisms that are extremely difficult to replicate in synthetic materials. Inspired from the architecture of such biological structures, we here present flow-assisted organization and assembly of renewable native cellulose nanofibrils (CNFs), which yields highly anisotropic biofibers characterized by a unique combination of high strength (1010 MPa), high toughness (62 MJ m-3 ) and high stiffness (57 GPa). We observed that properties of the fibers are primarily governed by specific ion characteristics such as hydration enthalpy and polarizability. A fundamental facet of this study is thus to elucidate the role of specific anion binding following the Hofmeister series on the mechanical properties of wet fibrillar networks, and link this to the differences in properties of dry nanostructured fibers. This knowledge is useful for rational design of nanomaterials and is critical for validation of specific ion effect theories. The bioinspired assembly demonstrated here is relevant example for designing high-performance materials with absolute structural control.


Assuntos
Íons/química , Nanofibras/química , Humanos
13.
J Neurophysiol ; 119(3): 796-807, 2018 03 01.
Artigo em Inglês | MEDLINE | ID: mdl-29142094

RESUMO

Teaching nonhuman primates the complex cognitive behavioral tasks that are central to cognitive neuroscience research is an essential and challenging endeavor. It is crucial for the scientific success that the animals learn to interpret the often complex task rules and reliably and enduringly act accordingly. To achieve consistent behavior and comparable learning histories across animals, it is desirable to standardize training protocols. Automatizing the training can significantly reduce the time invested by the person training the animal. In addition, self-paced training schedules with individualized learning speeds based on automatic updating of task conditions could enhance the animals' motivation and welfare. We developed a training paradigm for across-task unsupervised training (AUT) of successively more complex cognitive tasks to be administered through a stand-alone housing-based system optimized for rhesus monkeys in neuroscience research settings (Calapai A, Berger M, Niessing M, Heisig K, Brockhausen R, Treue S, Gail A. Behav Res Methods 5: 1-11, 2016). The AUT revealed interindividual differences in long-term learning progress between animals, helping to characterize learning personalities, and commonalities, helping to identify easier and more difficult learning steps in the training protocol. Our results demonstrate that 1) rhesus monkeys stay engaged with the AUT over months despite access to water and food outside the experimental sessions but with lower numbers of interaction compared with conventional fluid-controlled training; 2) with unsupervised training across sessions and task levels, rhesus monkeys can learn tasks of sufficient complexity for state-of-the-art cognitive neuroscience in their housing environment; and 3) AUT learning progress is primarily determined by the number of interactions with the system rather than the mere exposure time. NEW & NOTEWORTHY We demonstrate that highly structured training of behavioral tasks, as used in neuroscience research, can be achieved in an unsupervised fashion over many sessions and task difficulties in a monkey housing environment. Employing a predefined training strategy allows for an observer-independent comparison of learning between animals and of training approaches. We believe that self-paced standardized training can be utilized for pretraining and animal selection and can contribute to animal welfare in a neuroscience research environment.


Assuntos
Pesquisa Comportamental/instrumentação , Pesquisa Comportamental/métodos , Condicionamento Operante , Aprendizagem , Bem-Estar do Animal , Animais , Comportamento Animal , Macaca mulatta , Masculino , Projetos de Pesquisa
14.
Allergy ; 73(3): 615-626, 2018 03.
Artigo em Inglês | MEDLINE | ID: mdl-28975640

RESUMO

BACKGROUND: Epidemiologic evidence indicates a relevant association between atopic dermatitis (AD) and attention-deficit/hyperactivity disorder (ADHD). Underlying mechanisms and ways to best identify subgroups of AD patients at risk for ADHD are poorly understood. AIMS OF THE STUDY: To compare sociodemographic, clinical and psychosocial characteristics of children with AD, ADHD, comorbid AD/ADHD and age-matched healthy controls and to investigate aspects of AD related to ADHD symptoms. METHODS: Applying a factorial design, we investigated 4 groups of children aged 6-12 years: AD-only (ie, without ADHD), ADHD-only (ie, without AD), AD + ADHD and healthy controls (HC; ie, no AD/no ADHD). Using validated instruments, ADHD symptoms and other behavioural problems, quality of life, parenting stress and sleeping problems were compared between groups. In children with AD-only, clinical signs (objective SCORAD), symptoms (POEM, VAS pruritus, VAS sleeping problems) and previous treatment of AD were assessed to investigate disease patterns related to ADHD symptoms. RESULTS: Compared to HC (n = 47), children with AD-only (n = 42), ADHD-only (n = 34) and comorbid AD + ADHD (n = 31) had significantly increased behavioural problems and decreased quality of life. Children with AD-only had significantly higher levels of ADHD symptoms than HC. In children with AD-only, previous use of antihistamines was significantly associated with increased ADHD symptoms (OR 1.88; 95% CI 1.04-3.39). Current clinical signs and AD symptoms were unrelated to the level of ADHD symptoms. CONCLUSIONS: Even if the clinical diagnosis of ADHD is excluded, children with AD show increased levels of ADHD symptoms. Further investigations need to determine whether early antihistamine exposure is a major risk factor for ADHD or a surrogate for previous AD severity and/or associated sleeping problems.


Assuntos
Transtorno do Deficit de Atenção com Hiperatividade/etiologia , Dermatite Atópica/complicações , Antagonistas dos Receptores Histamínicos/uso terapêutico , Comportamento Problema , Transtorno do Deficit de Atenção com Hiperatividade/epidemiologia , Criança , Dermatite Atópica/tratamento farmacológico , Feminino , Humanos , Masculino
15.
Curr Opin Pulm Med ; 24(5): 425-431, 2018 09.
Artigo em Inglês | MEDLINE | ID: mdl-30020141

RESUMO

PURPOSE OF REVIEW: Historically, because of the necessity of parenteral anticoagulation, patients with acute pulmonary embolism are hospitalized until stable oral anticoagulation is achieved. Despite improvements in prognostic risk stratification and the introduction of the direct oral anticoagulants, home treatment is still not widely applied. Main advantages of home treatment involve improvement of quality of life and significant healthcare cost reduction. In this review, we summarized recent published data on home treatment of patients with acute pulmonary embolism. RECENT FINDINGS: Although a significant decrease in mean duration of hospital admission for pulmonary embolism has been demonstrated over the last decade in Europe, most pulmonary embolism patients are currently hospitalized while they might be treated in an outpatient setting. In recent years, five major studies have been performed, in which the decision to initiate home treatment was based on the Hestia criteria in most patients. Over 98% of patients treated at home had an uncomplicated course. SUMMARY: Home treatment of acute pulmonary embolism is suggested to be feasible and safe in 30-55% of all patients. Results of ongoing trials will provide more insight in the optimal strategy to select patients with pulmonary embolism who are eligible for home treatment and likely will result in more widespread application of this practice.


Assuntos
Assistência Ambulatorial , Anticoagulantes/administração & dosagem , Seleção de Pacientes , Embolia Pulmonar/tratamento farmacológico , Doença Aguda , Serviços de Assistência Domiciliar , Humanos , Terapia Trombolítica
16.
Soft Matter ; 14(31): 6582-6594, 2018 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-30052259

RESUMO

The effect of chain architecture on the swelling and thermal response of thin films obtained from an amphiphilic three-arm star-shaped thermo-responsive block copolymer poly(methoxy diethylene glycol acrylate)-block-polystyrene ((PMDEGA-b-PS)3) is investigated by in situ neutron reflectivity (NR) measurements. The PMDEGA and PS blocks are micro-phase separated with randomly distributed PS nanodomains. The (PMDEGA-b-PS)3 films show a transition temperature (TT) at 33 °C in white light interferometry. The swelling capability of the (PMDEGA-b-PS)3 films in a D2O vapor atmosphere is better than that of films from linear PS-b-PMDEGA-b-PS triblock copolymers, which can be attributed to the hydrophilic end groups and limited size of the PS blocks in (PMDEGA-b-PS)3. However, the swelling kinetics of the as-prepared (PMDEGA-b-PS)3 films and the response of the swollen film to a temperature change above the TT are significantly slower than that in the PS-b-PMDEGA-b-PS films, which may be related to the conformation restriction by the star-shape. Unlike in the PS-b-PMDEGA-b-PS films, the amount of residual D2O in the collapsed (PMDEGA-b-PS)3 films depends on the final temperature. It decreases from (9.7 ± 0.3)% to (7.0 ± 0.3)% or (6.0 ± 0.3)% when the final temperatures are set to 35 °C, 45 °C and 50 °C, respectively. This temperature-dependent reduction of embedded D2O originates from the hindrance of chain conformation from the star-shaped chain architecture.

17.
Nature ; 477(7364): 312-6, 2011 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-21921914

RESUMO

Large igneous provinces (LIPs) are known for their rapid production of enormous volumes of magma (up to several million cubic kilometres in less than a million years), for marked thinning of the lithosphere, often ending with a continental break-up, and for their links to global environmental catastrophes. Despite the importance of LIPs, controversy surrounds even the basic idea that they form through melting in the heads of thermal mantle plumes. The Permo-Triassic Siberian Traps--the type example and the largest continental LIP--is located on thick cratonic lithosphere and was synchronous with the largest known mass-extinction event. However, there is no evidence of pre-magmatic uplift or of a large lithospheric stretching, as predicted above a plume head. Moreover, estimates of magmatic CO(2) degassing from the Siberian Traps are considered insufficient to trigger climatic crises, leading to the hypothesis that the release of thermogenic gases from the sediment pile caused the mass extinction. Here we present petrological evidence for a large amount (15 wt%) of dense recycled oceanic crust in the head of the plume and develop a thermomechanical model that predicts no pre-magmatic uplift and requires no lithospheric extension. The model implies extensive plume melting and heterogeneous erosion of the thick cratonic lithosphere over the course of a few hundred thousand years. The model suggests that massive degassing of CO(2) and HCl, mostly from the recycled crust in the plume head, could alone trigger a mass extinction and predicts it happening before the main volcanic phase, in agreement with stratigraphic and geochronological data for the Siberian Traps and other LIPs.

18.
Langmuir ; 32(17): 4251-8, 2016 05 03.
Artigo em Inglês | MEDLINE | ID: mdl-27070283

RESUMO

Fabrication of nanoparticle arrays on a substrate is one of the most concerned aspects for manipulating assembly of nanoparticles and preparing functional nanocomposites. Here, we studied in situ the assembly kinetics of polystyrene nanocolloids by using grazing incidence small-angle X-ray scattering. The structure formation of the nanoparticle film is monitored during air-brush spraying, which provides a rapid and scalable preparation. By optimizing the substrate temperature, the dispersion of the nanocolloids can be tailored to prepare monolayer film. The success of the monolayer preparations is attributed to the fast solvent evaporation which inhibits the aggregation of the nanocolloids. The present study may open a new avenue for the manufacture-friendly preparation of well-dispersed nanoparticle thin films.

20.
Proc Natl Acad Sci U S A ; 110(17): 6706-11, 2013 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-23569240

RESUMO

The flow orientation of anisotropic particles through narrow channels is of importance in many fields, ranging from the spinning and molding of fibers to the flow of cells and proteins through thin capillaries. It is commonly assumed that anisotropic particles align parallel to the flow direction. When flowing through narrowed channel sections, one expects the increased flow rate to improve the parallel alignment. Here, we show by microfocus synchrotron X-ray scattering and polarized optical microscopy that anisotropic colloidal particles align perpendicular to the flow direction after passing a narrow channel section. We find this to be a general behavior of anisotropic colloids, which is also observed for disk-like particles. This perpendicular particle alignment is stable, extending downstream throughout the remaining part of the channel. We show by microparticle image velocimetry that the particle reorientation in the expansion zone after a narrow channel section occurs in a region with considerable extensional flow. This extensional flow is promoted by shear thinning, a typical property of complex fluids. Our discovery has important consequences when considering the flow orientation of polymers, micelles, fibers, proteins, or cells through narrow channels, pipes, or capillary sections. An immediate consequence for the production of fibers is the necessity for realignment by extension in the flow direction. For fibrous proteins, reorientation and stable plug flow are likely mechanisms for protein coagulation.


Assuntos
Coloides/química , Micelas , Microfluídica/métodos , Anisotropia , Microscopia de Polarização , Tamanho da Partícula , Reologia , Espalhamento a Baixo Ângulo
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