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1.
Magn Reson Med ; 89(5): 1777-1790, 2023 05.
Artigo em Inglês | MEDLINE | ID: mdl-36744619

RESUMO

PURPOSE: To develop a robust retrospective motion-correction technique based on repeating k-space guidance lines for improving motion correction in Cartesian 2D and 3D brain MRI. METHODS: The motion guidance lines are inserted into the standard sequence orderings for 2D turbo spin echo and 3D MPRAGE to inform a data consistency-based motion estimation and reconstruction, which can be guided by a low-resolution scout. The extremely limited number of required guidance lines are repeated during each echo train and discarded in the final image reconstruction. Thus, integration within a standard k-space acquisition ordering ensures the expected image quality/contrast and motion sensitivity of that sequence. RESULTS: Through simulation and in vivo 2D multislice and 3D motion experiments, we demonstrate that respectively 2 or 4 optimized motion guidance lines per shot enables accurate motion estimation and correction. Clinically acceptable reconstruction times are achieved through fully separable on-the-fly motion optimizations (˜1 s/shot) using standard scanner GPU hardware. CONCLUSION: The addition of guidance lines to scout accelerated motion estimation facilitates robust retrospective motion correction that can be effectively introduced without perturbing standard clinical protocols and workflows.


Assuntos
Encéfalo , Imageamento por Ressonância Magnética , Estudos Retrospectivos , Encéfalo/diagnóstico por imagem , Imageamento por Ressonância Magnética/métodos , Movimento (Física) , Simulação por Computador , Imageamento Tridimensional/métodos , Processamento de Imagem Assistida por Computador/métodos
2.
Phys Chem Chem Phys ; 25(16): 11205-11215, 2023 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-37039571

RESUMO

Poly(3-alkyl(thienylene-vinylene)) (P3TV) and its longer oligomers have negligibly low photoluminescence quantum yields, however, the reason for their low yields is currently debated. Here, we prepare a series of regioregular (3-dodecyl)thienylene-vinylene oligomers with n = 2-8 repeat units by iterative Horner-Wadsworth-Emmons reactions, and report their steady-state, transient absorption, and emission spectroscopy. The results presented here demonstrate that 3-alkyl(thienylene-vinylene) oligomers form part of the polyene family. The shortest (n = 2) oligomer emits from the bright 1Bu state, while fluorescence in oligomers with n = 3, 4 is from the formally dark 2Ag state, allowed via Herzberg-Teller vibronic coupling to the nearby bright 1Bu state as described for diphenyl-polyenes. Longer oligomers and the polymer are essentially non-emissive as the 2Ag state can no longer intensity-borrow from the 1Bu state. We demonstrate that the spectral shapes, photoluminescence quantum yield, and transient spectral behaviour can all be explained using a polyene model with weak electronic correlations.

3.
Magn Reson Med ; 87(1): 163-178, 2022 01.
Artigo em Inglês | MEDLINE | ID: mdl-34390505

RESUMO

PURPOSE: To demonstrate a navigator/tracking-free retrospective motion estimation technique that facilitates clinically acceptable reconstruction time. METHODS: Scout accelerated motion estimation and reduction (SAMER) uses a single 3-5 s, low-resolution scout scan and a novel sequence reordering to independently determine motion states by minimizing the data-consistency error in a SENSE plus motion forward model. This eliminates time-consuming alternating optimization as no updates to the imaging volume are required during the motion estimation. The SAMER approach was assessed quantitatively through extensive simulation and was evaluated in vivo across multiple motion scenarios and clinical imaging contrasts. Finally, SAMER was synergistically combined with advanced encoding (Wave-CAIPI) to facilitate rapid motion-free imaging. RESULTS: The highly accelerated scout provided sufficient information to achieve accurate motion trajectory estimation (accuracy ~0.2 mm or degrees). The novel sequence reordering improved the stability of the motion parameter estimation and image reconstruction while preserving the clinical imaging contrast. Clinically acceptable computation times for the motion estimation (~4 s/shot) are demonstrated through a fully separable (non-alternating) motion search across the shots. Substantial artifact reduction was demonstrated in vivo as well as corresponding improvement in the quantitative error metric. Finally, the extension of SAMER to Wave-encoding enabled rapid high-quality imaging at up to R = 9-fold acceleration. CONCLUSION: SAMER significantly improved the computational scalability for retrospective motion estimation and correction.


Assuntos
Artefatos , Processamento de Imagem Assistida por Computador , Algoritmos , Simulação por Computador , Imageamento por Ressonância Magnética , Movimento (Física) , Estudos Retrospectivos
4.
Phys Chem Chem Phys ; 24(34): 20138-20151, 2022 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-35993400

RESUMO

Diketopyrrolopyrroles are a popular class of electron-withdrawing unit in optoelectronic materials. When combined with electron donating side-chain functional groups such as thiophenes, they form a very broad class of donor-acceptor molecules: thiophene-diketopyrrolopyrroles (TDPPs). Despite their widescale use in biosensors and photovoltaic materials, studies have yet to establish the important link between the electronic structure of the specific TDPP and the critical optical properties. To bridge this gap, ultrafast transient absorption with 22 fs time resolution has been used to explore the photophysics of three prototypical TDPP molecules: a monomer, dimer and polymer in solution. Interpretation of experimental data was assisted by a recent high-level theoretical study, and additional density functional theory calculations. These studies show that the photophysics of these molecular prototypes under visible photoexcitation are determined by just two excited electronic states, having very different electronic characters (one is optically bright, the other dark), their relative energetic ordering and the timescales for internal conversion from one to the other and/or to the ground state. The underlying difference in electronic structure alters the branching between these excited states and their associated dynamics. In turn, these factors dictate the fluorescence quantum yields, which are shown to vary by ∼1-2 orders of magnitude across the TDPP prototypes investigated here. The fast non-radiative transfer of molecules from the bright to dark states is mediated by conical intersections. Remarkably, wavepacket signals in the measured transient absorption data carry signatures of the nuclear motions that enable mixing of the electronic-nuclear wavefunction and facilitate non-adiabatic coupling between the bright and dark states.

5.
J Am Chem Soc ; 142(32): 13898-13907, 2020 08 12.
Artigo em Inglês | MEDLINE | ID: mdl-32672948

RESUMO

Advances in protein design and engineering have yielded peptide assemblies with enhanced and non-native functionalities. Here, various molecular organic semiconductors (OSCs), with known excitonic up- and down-conversion properties, are attached to a de novo-designed protein, conferring entirely novel functions on the peptide scaffolds. The protein-OSC complexes form similarly sized, stable, water-soluble nanoparticles that are robust to cryogenic freezing and processing into the solid-state. The peptide matrix enables the formation of protein-OSC-trehalose glasses that fix the proteins in their folded states under oxygen-limited conditions. The encapsulation dramatically enhances the stability of protein-OSC complexes to photodamage, increasing the lifetime of the chromophores from several hours to more than 10 weeks under constant illumination. Comparison of the photophysical properties of astaxanthin aggregates in mixed-solvent systems and proteins shows that the peptide environment does not alter the underlying electronic processes of the incorporated materials, exemplified here by singlet exciton fission followed by separation into weakly bound, localized triplets. This adaptable protein-based approach lays the foundation for spectroscopic assessment of a broad range of molecular OSCs in aqueous solutions and the solid-state, circumventing the laborious procedure of identifying the experimental conditions necessary for aggregate generation or film formation. The non-native protein functions also raise the prospect of future biocompatible devices where peptide assemblies could complex with native and non-native systems to generate novel functional materials.


Assuntos
Peptídeos/química , Proteínas/química , Temperatura , Estrutura Molecular , Estabilidade Proteica , Semicondutores , Análise Espectral , Xantofilas/química
6.
Magn Reson Med ; 84(3): 1456-1469, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-32129529

RESUMO

PURPOSE: To improve the image quality of highly accelerated multi-channel MRI data by learning a joint variational network that reconstructs multiple clinical contrasts jointly. METHODS: Data from our multi-contrast acquisition were embedded into the variational network architecture where shared anatomical information is exchanged by mixing the input contrasts. Complementary k-space sampling across imaging contrasts and Bunch-Phase/Wave-Encoding were used for data acquisition to improve the reconstruction at high accelerations. At 3T, our joint variational network approach across T1w, T2w and T2-FLAIR-weighted brain scans was tested for retrospective under-sampling at R = 6 (2D) and R = 4 × 4 (3D) acceleration. Prospective acceleration was also performed for 3D data where the combined acquisition time for whole brain coverage at 1 mm isotropic resolution across three contrasts was less than 3 min. RESULTS: Across all test datasets, our joint multi-contrast network better preserved fine anatomical details with reduced image-blurring when compared to the corresponding single-contrast reconstructions. Improvement in image quality was also obtained through complementary k-space sampling and Bunch-Phase/Wave-Encoding where the synergistic combination yielded the overall best performance as evidenced by exemplary slices and quantitative error metrics. CONCLUSION: By leveraging shared anatomical structures across the jointly reconstructed scans, our joint multi-contrast approach learnt more efficient regularizers, which helped to retain natural image appearance and avoid over-smoothing. When synergistically combined with advanced encoding techniques, the performance was further improved, enabling up to R = 16-fold acceleration with good image quality. This should help pave the way to very rapid high-resolution brain exams.


Assuntos
Processamento de Imagem Assistida por Computador , Imageamento Tridimensional , Imageamento por Ressonância Magnética , Estudos Prospectivos , Estudos Retrospectivos
7.
NMR Biomed ; 33(12): e4271, 2020 12.
Artigo em Inglês | MEDLINE | ID: mdl-32078756

RESUMO

High-quality Quantitative Susceptibility Mapping (QSM) with Nonlinear Dipole Inversion (NDI) is developed with pre-determined regularization while matching the image quality of state-of-the-art reconstruction techniques and avoiding over-smoothing that these techniques often suffer from. NDI is flexible enough to allow for reconstruction from an arbitrary number of head orientations and outperforms COSMOS even when using as few as 1-direction data. This is made possible by a nonlinear forward-model that uses the magnitude as an effective prior, for which we derived a simple gradient descent update rule. We synergistically combine this physics-model with a Variational Network (VN) to leverage the power of deep learning in the VaNDI algorithm. This technique adopts the simple gradient descent rule from NDI and learns the network parameters during training, hence requires no additional parameter tuning. Further, we evaluate NDI at 7 T using highly accelerated Wave-CAIPI acquisitions at 0.5 mm isotropic resolution and demonstrate high-quality QSM from as few as 2-direction data.


Assuntos
Algoritmos , Imageamento por Ressonância Magnética , Dinâmica não Linear , Artefatos , Humanos , Processamento de Imagem Assistida por Computador
8.
Magn Reson Med ; 81(3): 1620-1633, 2019 03.
Artigo em Inglês | MEDLINE | ID: mdl-30252157

RESUMO

PURPOSE: Wave-CAIPI is a novel acquisition approach that enables highly accelerated 3D imaging. This paper investigates the combination of Wave-CAIPI with LORAKS-based reconstruction (Wave-LORAKS) to enable even further acceleration. METHODS: LORAKS is a constrained image reconstruction framework that can impose spatial support, smooth phase, sparsity, and/or parallel imaging constraints. LORAKS requires minimal prior information, and instead uses the low-rank subspace structure of the raw data to automatically learn which constraints to impose and how to impose them. Previous LORAKS implementations addressed 2D image reconstruction problems. In this work, several recent advances in structured low-rank matrix recovery were combined to enable large-scale 3D Wave-LORAKS reconstruction with improved quality and computational efficiency. Wave-LORAKS was investigated by retrospective subsampling of two fully sampled Wave-encoded 3D MPRAGE datasets, and comparisons were made against existing Wave reconstruction approaches. RESULTS: Results show that Wave-LORAKS can yield higher reconstruction quality with 16×-accelerated data than is obtained by traditional Wave-CAIPI with 9×-accerated data. CONCLUSIONS: There are strong synergies between Wave encoding and LORAKS, which enables Wave-LORAKS to achieve higher acceleration and more flexible sampling compared to Wave-CAIPI.


Assuntos
Encéfalo/diagnóstico por imagem , Processamento de Imagem Assistida por Computador/métodos , Imageamento Tridimensional/métodos , Imageamento por Ressonância Magnética , Algoritmos , Calibragem , Simulação por Computador , Análise de Fourier , Humanos , Interpretação de Imagem Assistida por Computador/métodos , Análise dos Mínimos Quadrados , Modelos Lineares , Razão Sinal-Ruído
9.
J Magn Reson Imaging ; 50(3): 961-974, 2019 09.
Artigo em Inglês | MEDLINE | ID: mdl-30734388

RESUMO

BACKGROUND: Rapid volumetric imaging protocols could better utilize limited scanner resources. PURPOSE: To develop and validate an optimized 6-minute high-resolution volumetric brain MRI examination using Wave-CAIPI encoding. STUDY TYPE: Prospective. POPULATION/SUBJECTS: Ten healthy subjects and 20 patients with a variety of intracranial pathologies. FIELD STRENGTH/SEQUENCE: At 3 T, MPRAGE, T2 -weighted SPACE, SPACE FLAIR, and SWI were acquired at 9-fold acceleration using Wave-CAIPI and for comparison at 2-4-fold acceleration using conventional GRAPPA. ASSESSMENT: Extensive simulations were performed to optimize the Wave-CAIPI protocol and minimize both g-factor noise amplification and potential T1 /T2 blurring artifacts. Moreover, refinements in the autocalibrated reconstruction of Wave-CAIPI were developed to ensure high-quality reconstructions in the presence of gradient imperfections. In a randomized and blinded fashion, three neuroradiologists assessed the diagnostic quality of the optimized 6-minute Wave-CAIPI exam and compared it to the roughly 3× slower GRAPPA accelerated protocol using both an individual and head-to-head analysis. STATISTICAL TEST: A noninferiority test was used to test whether the diagnostic quality of Wave-CAIPI was noninferior to the GRAPPA acquisition, with a 15% noninferiority margin. RESULTS: Among all sequences, Wave-CAIPI achieved negligible g-factor noise amplification (gavg ≤ 1.04) and burring artifacts from T1 /T2 relaxation. Improvements of our autocalibration approach for gradient imperfections enabled increased robustness to gradient mixing imperfections in tilted-field of view (FOV) prescriptions as well as variations in gradient and analog-to-digital converter (ADC) sampling rates. In the clinical evaluation, Wave-CAIPI achieved similar mean scores when compared with GRAPPA (MPRAGE: ØW = 4.03, ØG = 3.97; T2 w SPACE: ØW = 4.00, ØG = 4.00; SPACE FLAIR: ØW = 3.97, ØG = 3.97; SWI: ØW = 3.93, ØG = 3.83) and was statistically noninferior (N = 30, P < 0.05 for all sequences). DATA CONCLUSION: The proposed volumetric brain exam retained comparable image quality when compared with the much longer conventional protocol. LEVEL OF EVIDENCE: 2 Technical Efficacy: Stage 1 J. Magn. Reson. Imaging 2019;50:961-974.


Assuntos
Encefalopatias/diagnóstico por imagem , Encefalopatias/patologia , Encéfalo/diagnóstico por imagem , Encéfalo/patologia , Interpretação de Imagem Assistida por Computador/métodos , Imageamento por Ressonância Magnética/métodos , Adulto , Idoso , Idoso de 80 Anos ou mais , Artefatos , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Tamanho do Órgão , Estudos Prospectivos , Reprodutibilidade dos Testes , Método Simples-Cego , Adulto Jovem
10.
Magn Reson Med ; 79(1): 401-406, 2018 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-28220617

RESUMO

PURPOSE: To introduce a highly accelerated T1-weighted magnetization-prepared rapid gradient echo (MP-RAGE) acquisition that uses wave-controlled aliasing in parallel imaging (wave-CAIPI) encoding to retain high image quality. METHODS: Significant acceleration of the MP-RAGE sequence is demonstrated using the wave-CAIPI technique. Here, sinusoidal waveforms are used to spread aliasing in all three directions to improve the g-factor. Combined with a rapid (2 s) coil sensitivity acquisition and data-driven trajectory calibration, we propose an online integrated acquisition-reconstruction pipeline for highly efficient MP-RAGE imaging. RESULTS: The 9-fold accelerated MP-RAGE acquisition can be performed in 71 s, with a maximum and average g-factor of gmax = 1.27 and gavg = 1.06 at 3T. Compared with the state-of-the-art method controlled aliasing in parallel imaging results in higher acceleration (2D-CAIPIRINHA), this is a factor of 4.6/1.4 improvement in gmax /gavg . In addition, we demonstrate a 57 s acquisition at 7T with 12-fold acceleration. This acquisition has a g-factor performance of gmax = 1.15 and gavg = 1.04. CONCLUSION: Wave encoding overcomes the g-factor noise amplification penalty and allows for an order of magnitude acceleration of MP-RAGE acquisitions. Magn Reson Med 79:401-406, 2018. © 2017 International Society for Magnetic Resonance in Medicine.


Assuntos
Encéfalo/diagnóstico por imagem , Imageamento por Ressonância Magnética , Algoritmos , Calibragem , Feminino , Substância Cinzenta/diagnóstico por imagem , Voluntários Saudáveis , Humanos , Aumento da Imagem , Processamento de Imagem Assistida por Computador , Imageamento Tridimensional , Magnetismo , Masculino , Software
11.
Med Phys ; 50(4): 2148-2161, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36433748

RESUMO

BACKGROUND: Intra-scan rigid-body motion is a costly and ubiquitous problem in clinical magnetic resonance imaging (MRI) of the head. PURPOSE: State-of-the-art methods for retrospective motion correction in MRI are often computationally expensive or in the case of image-to-image deep learning (DL) based methods can be prone to undesired alterations of the image (hallucinations'). In this work we introduce a novel rigid-body motion correction method which combines the advantages of classical model-driven and data-consistency (DC) preserving approaches with a novel DL algorithm, to provide fast and robust retrospective motion correction. METHODS: The proposed Motion Parameter Estimating Densenet (MoPED) retrospectively estimates subject head motion during MRI acquisitions using a DL network with DenseBlocks and multitask learning. It quantifies the 2D rigid in-plane motion parameters slice-wise for each echo train (ET) of a Cartesian T2-weighted 2D Turbo-Spin-Echo sequence. The network receives a center patch of the motion corrupted k-space as well as an additional motion-free low-resolution reference scan to provide the ground truth orientation. The supervised training utilizes motion simulations based on 28 acquisitions with subject-wise training, validation, and test data splits of 70%, 23%, and 7%. During inference, MoPED is embedded in an iterative DC-driven motion correction algorithm which alternatingly updates estimates of the motion parameters and motion-corrected low-resolution k-space data. The estimated motion parameters are then used to reconstruct the final motion corrected image. The mean absolute/squared error and the Pearson correlation coefficient were used to analyze the motion parameter estimation quality on in-silico data in a quantitative evaluation. Structural similarity (SSIM), DC error and root mean squared error (RMSE) were used as metrics of image quality improvement. Furthermore, the generalization capability of the network was analyzed on two in-vivo motion volumes with 28 slices each and on one simulated T1-weighted volume. RESULTS: The motion estimation achieves a Pearson correlation of 0.968 to the simulated ground-truth of the 2433 test data slices used. In-silico results indicate that MoPED decreases the time for the optimization by a factor of around 27 compared to a conventional method and is able to reduce the RMSE of the reconstructions and average DC error by more than a factor of two compared to uncorrected images. In-vivo experiments show a decrease in computation time by a factor of around 20, a RMSE decrease from 0.055 to 0.033 and an SSIM increase from 0.795 to 0.862. Furthermore, contrast independence is demonstrated as MoPED is also able to correct T1-weighted images in simulations without retraining. Due to the model-based correction, no hallucinations were observed. CONCLUSIONS: Incorporating DL in a model-based motion correction algorithm shows great benefit on the optimization and computation time. The k-space-based estimation also allows a data consistent correction and therefore avoids the risk of hallucinations of image-to-image approaches.


Assuntos
Aprendizado Profundo , Estudos Retrospectivos , Processamento de Imagem Assistida por Computador/métodos , Imageamento por Ressonância Magnética/métodos , Movimento (Física) , Artefatos
12.
J Phys Chem B ; 127(38): 8199-8207, 2023 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-37708380

RESUMO

Despite many decades of study, the excited state photophysics of polyenes remains controversial. In diphenylpolyenes with conjugated backbones that contain between 2 and 4 double carbon-carbon bonds, the first two excited electronic states are nearly degenerate but of entirely different character, and their energy splitting is strongly dependent on solvent polarizability. To examine the interplay between these different states, steady-state and time-resolved fluorescence spectroscopies were used to undertake a comprehensive investigation of diphenylocatetraene's (DPO) excited state dynamics in 10 solvents of different polarizabilities and polarities, ranging from weakly interacting alkanes to polar hydrogen-bonding alcohols. These data revealed that photopreparation of the optically bright 1Bu state resulted in fast (<170 ps) internal conversion to the lower-lying optically dark 2Ag state. The 2Ag state is responsible for almost all the observed DPO fluorescence and gains oscillator strength via vibronic intensity stealing with the near-degenerate 1Bu state. The fluorescence lifetime associated with the 2Ag state decayed monoexponentially (4.2-7.2 ns) in contrast to prior biexponential decay kinetics reported for similar polyenes, diphenylbutadiene and diphenylhexatriene. An analysis combining the measured fluorescence lifetimes and fluorescence quantum yields (the latter varying between 7 and 21%) allowed for a 190 cm-1 Herzberg-Teller vibronic coupling constant between the 1Bu and 2Ag states to be determined. The analysis also revealed that the ordering of electronic states remains constant in all the solvents studied, with the 2Ag state minimum always lower in energy than that of the 1Bu state, thus making it a relatively simple polyene compared to structurally similar diphenylhexatriene.

13.
Materials (Basel) ; 15(18)2022 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-36143769

RESUMO

Heterogeneous membranes made of a polymer matrix and containing nano-metric fillers in their structure may present improved physicochemical and process properties compared to homogeneous membranes made only of polymer materials. Membranes made of a PEBAX®2533 block copolymer were tested with fillers such as ZIF-8, SiO2 and POSS-Ph being dosed to them. The material analysis and process tests indicate that these nanomaterials can be used as fillers for heterogeneous membranes. Chemometric analyses determined the influence of individual fillers on selected physicochemical properties of the materials which were used to produce the membranes. For specific concentrations of these fillers, improvement in the permeability and selectivity of the membranes, or at least in one of these parameters, was achieved. The greatest increase in permeability against the homogeneous membrane was obtained for membranes containing 10 wt% ZIF-8 (for CO2, an increase of 2.07 times; for CH4, 2.36 times; for N2, 3.08 times). In turn, the greatest increase in selectivity was obtained for the CO2/CH4 mixture for the membrane containing 5 wt% SiO2 (1.15 times), and for the CO2/N2 mixture for the membrane containing 2 wt% POSS-Ph (1.21 times).

14.
Membranes (Basel) ; 12(10)2022 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-36295775

RESUMO

Heterogeneous membranes, otherwise known as Mixed Matrix Membranes (MMMs), which are used in gas separation processes, are the subject of growing interest. This is due to their potential to improve the process properties of membranes compared to those of homogeneous membranes, i.e., those made of polymer only. Using such membranes in a process involves subjecting them to varying temperatures and pressures. This paper investigates the effects of temperature and feed pressure on the process properties of homogeneous and heterogeneous membranes. Membranes made of Pebax®2533 copolymer and containing additional fillers such as SiO2, ZIF-8, and POSS-Ph were investigated. Tests were performed over a temperature range of 25-55 °C and a pressure range of 2-8 bar for N2, CH4, and CO2 gases. It was found that temperature positively influences the increase in permeability, while pressure influences permeability depending on the gas used, which is related to the effect of pressure on the solubility of the gas in the membrane.

15.
Membranes (Basel) ; 13(1)2022 Dec 29.
Artigo em Inglês | MEDLINE | ID: mdl-36676851

RESUMO

In the aquatic environment, substances of pharmacological origin are common contaminants. The difficulty of removing them from water is a problem for the implementation of a circular economy policy. When recycling water, an effort should be made to remove, or at least, minimize the presence of these substances in the water. Porous membranes with a new functionality consisting in their adsorption capacity towards pharmaceutical substances have been developed. A Polyvinylidene Fluoride (PVDF) membrane with Calcium Carbonate (CaCO3) nanoparticles as an adsorbent was prepared. By implementing an integrated filtration-adsorption process using sulphadiazine, as a representative of pharmacological substances, 57 mg/m2 of adsorption capacity has been obtained, which is an improvement in adsorption properties of more than 50 times that of a commercial membrane. At the same time the membrane permeability is 0.29 m3/(h·m2·bar), which means that the membrane's permeability was improved by 75%.

16.
Membranes (Basel) ; 11(7)2021 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-34203550

RESUMO

The aim of this work is to develop a new type of carbon-ceramic membranes for the removal of pharmaceutical substances from water. The membranes were prepared by the chemical modification method using an organosilicon precursor-octadecyltrichlorosilane (ODTS). Graphene oxide, multi-walled carbon nanotubes with carboxylic groups, and single-walled carbon nanotubes were used in the modification process. The filtration properties and adsorption properties of the developed membranes were tested. In order to characterize the membrane, the water permeability, the change of the permeate flux in time, and the adsorbed mass of the substance were determined. Additionally, the surface properties of the membranes were characterized by contact angle measurements and porosimetry. The antibiotic tetracycline was used in the adsorption tests. Based on the results, the improved adsorption properties of the modified membrane in relation to the unmodified membrane were noticed. Novel ceramic membranes modified with MWCNT are characterized by 45.4% removal of tetracycline and permeate flux of 520 L·h·m-2·bar-1. We demonstrated the ability of modified membranes to adsorb pharmaceuticals from water streams that are in contact with the membrane. Novel membranes retain their filtration properties. Therefore, such membranes can be used in an integrated filtration-adsorption process.

17.
J Phys Chem Lett ; 12(23): 5448-5455, 2021 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-34081477

RESUMO

Reaction centers (RCs) are the pivotal component of natural photosystems, converting solar energy into the potential difference between separated electrons and holes that is used to power much of biology. RCs from anoxygenic purple photosynthetic bacteria such as Rhodobacter sphaeroides only weakly absorb much of the visible region of the solar spectrum, which limits their overall light-harvesting capacity. For in vitro applications such as biohybrid photodevices, this deficiency can be addressed by effectively coupling RCs with synthetic light-harvesting materials. Here, we studied the time scale and efficiency of Förster resonance energy transfer (FRET) in a nanoconjugate assembled from a synthetic quantum dot (QD) antenna and a tailored RC engineered to be fluorescent. Time-correlated single-photon counting spectroscopy of biohybrid conjugates enabled the direct determination of FRET from QDs to attached RCs on a time scale of 26.6 ± 0.1 ns and with a high efficiency of 0.75 ± 0.01.


Assuntos
Transferência de Energia , Transferência Ressonante de Energia de Fluorescência/métodos , Nanoconjugados/química , Complexo de Proteínas do Centro de Reação Fotossintética/química , Proteobactérias/química , Pontos Quânticos/química , Nanoconjugados/análise , Fotossíntese , Complexo de Proteínas do Centro de Reação Fotossintética/análise , Pontos Quânticos/análise , Rhodobacter sphaeroides/química , Energia Solar
18.
J Neuroimaging ; 31(5): 893-901, 2021 09.
Artigo em Inglês | MEDLINE | ID: mdl-34081374

RESUMO

BACKGROUND AND PURPOSE: High-resolution three-dimensional (3D) post-contrast imaging of the brain is essential for comprehensive evaluation of inflammatory, neoplastic, and neurovascular diseases of the brain. 3D T1-weighted spin-echo-based sequences offer increased sensitivity for the detection of enhancing lesions but are relatively prolonged examinations. We evaluated whether a highly accelerated Wave-controlled aliasing in parallel imaging (Wave-CAIPI) post-contrast 3D T1-sampling perfection with application-optimized contrasts using different flip angle evolutions (T1-SPACE) sequence (Wave-T1-SPACE) was noninferior to the standard high-resolution 3D T1-SPACE sequence for visualizing enhancing lesions with comparable diagnostic quality. METHODS: One hundred and three consecutive patients were prospectively evaluated with a standard post-contrast 3D T1-SPACE sequence (acquisition time [TA] = 4 min 19 s) and an optimized Wave-CAIPI 3D T1-SPACE sequence (TA = 1 min 40 s) that was nearly three times faster than the standard sequence. Two blinded neuroradiologists performed a head-to-head comparison to evaluate the visualization of enhancing pathology, perception of artifacts, and overall diagnostic quality. A 15% margin was used to test whether post-contrast Wave-T1-SPACE was noninferior to standard T1-SPACE. RESULTS: Wave-T1-SPACE was noninferior to standard T1-SPACE for delineating parenchymal and meningeal enhancing pathology (p < 0.01). Wave-T1-SPACE showed marginally higher background noise compared to the standard sequence and was noninferior in the overall diagnostic quality (p = 0.03). CONCLUSIONS: Our findings show that Wave-T1-SPACE was noninferior to standard T1-SPACE for visualization of enhancing pathology and overall diagnostic quality with a three-fold reduction in acquisition time compared to the standard sequence. Wave-T1-SPACE may be used to accelerate 3D post-contrast T1-weighted spin-echo imaging without loss of clinically important information.


Assuntos
Gadolínio , Imageamento Tridimensional , Artefatos , Encéfalo/diagnóstico por imagem , Humanos , Imageamento por Ressonância Magnética
19.
Front Neurol ; 11: 587327, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-33193054

RESUMO

Background and Purpose: Brain magnetic resonance imaging (MRI) examinations using high-resolution 3D post-contrast sequences offer increased sensitivity for the detection of metastases in the central nervous system but are usually long exams. We evaluated whether the diagnostic performance of a highly accelerated Wave-controlled aliasing in parallel imaging (Wave-CAIPI) post-contrast 3D T1 SPACE sequence was non-inferior to the standard high-resolution 3D T1 SPACE sequence for the evaluation of brain metastases. Materials and Methods: Thirty-three patients undergoing evaluation for brain metastases were prospectively evaluated with a standard post-contrast 3D T1 SPACE sequence and an optimized Wave-CAIPI 3D T1 SPACE sequence, which was three times faster than the standard sequence. Two blinded neuroradiologists performed a head-to-head comparison to evaluate the visualization of pathology, perception of artifacts, and the overall diagnostic quality. Wave-CAIPI post-contrast T1 SPACE was tested for non-inferiority relative to standard T1 SPACE using a 15% non-inferiority margin. Results: Wave-CAIPI post-contrast T1 SPACE was non-inferior to the standard T1 SPACE for visualization of enhancing lesions (P < 0.01) and offered equivalent diagnostic quality performance and only marginally higher background noise compared to the standard sequence. Conclusions: Our findings suggest that Wave-CAIPI post-contrast T1 SPACE provides equivalent visualization of pathology and overall diagnostic quality with three times reduced scan time compared to the standard 3D T1 SPACE.

20.
Chem Sci ; 11(2): 343-354, 2020 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-32190258

RESUMO

Exciton-polaritons are quasiparticles with mixed photon and exciton character that demonstrate rich quantum phenomena, novel optoelectronic devices and the potential to modify chemical properties of materials. Organic materials are of current interest as active materials for their ability to sustain exciton-polaritons even at room temperature. However, within organic optoelectronic devices, it is often the 'dark' spin-1 triplet excitons that dominate operation. These triplets have been largely ignored in treatments of polaritons, which instead only consider the role of states that directly and strongly interact with light. Here we demonstrate that these 'dark' states can also play a major role in polariton dynamics, observing polariton population transferred directly from the triplet manifold via triplet-triplet annihilation. The process leads to polariton emission that is longer-lived (>µs) even than exciton emission in bare films. This enhancement is directly linked to spin-2 triplet-pair states, which are formed in films and microcavities by singlet fission or triplet-triplet annihilation. Such high-spin multiexciton states are generally non-emissive and cannot directly couple to light, yet the formation of polaritons creates for them entirely new radiative decay pathways. This is possible due to weak mixing between singlet and triplet-pair manifolds, which - in the strong coupling regime - enables direct interaction between the bright polariton states and those that are formally non-emissive. Our observations offer the enticing possibility of using polaritons to harvest or manipulate population from states that are formally dark.

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