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1.
Med Image Anal ; 90: 102913, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37660483

RESUMO

Neuroimaging markers based on Magnetic Resonance Imaging (MRI) combined with various other measures (such as genetic covariates, biomarkers, vascular risk factors, neuropsychological tests etc.) might provide useful predictions of clinical outcomes during the progression towards Alzheimer's disease (AD). The use of multiple features in predictive frameworks for clinical outcomes has become increasingly prevalent in AD research. However, many studies do not focus on systematically and accurately evaluating combinations of multiple input features. Hence, the aim of the present work is to explore and assess optimal combinations of various features for MR-based prediction of (1) cognitive status and (2) biomarker positivity with a multi-kernel learning Gaussian process framework. The explored features and parameters included (A) combinations of brain tissues, modulation, smoothing, and image resolution; (B) incorporating demographics & clinical covariates; (C) the impact of the size of the training data set; (D) the influence of dimensionality reduction and the choice of kernel types. The approach was tested in a large German cohort including 959 subjects from the multicentric longitudinal study of cognitive impairment and dementia (DELCODE). Our evaluation suggests the best prediction of memory performance was obtained for a combination of neuroimaging markers, demographics, genetic information (ApoE4) and CSF biomarkers explaining 57% of outcome variance in out-of-sample predictions. The highest performance for Aß42/40 status classification was achieved for a combination of demographics, ApoE4, and a memory score while usage of structural MRI further improved the classification of individual patient's pTau status.

2.
AJNR Am J Neuroradiol ; 41(10): 1841-1848, 2020 10.
Artigo em Inglês | MEDLINE | ID: mdl-32883668

RESUMO

BACKGROUND AND PURPOSE: Transcranial MR imaging-guided focused ultrasound is a promising novel technique to treat multiple disorders and diseases. Planning for transcranial MR imaging-guided focused ultrasound requires both a CT scan for skull density estimation and treatment-planning simulation and an MR imaging for target identification. It is desirable to simplify the clinical workflow of transcranial MR imaging-guided focused ultrasound treatment planning. The purpose of this study was to examine the feasibility of deep learning techniques to convert MR imaging ultrashort TE images directly to synthetic CT of the skull images for use in transcranial MR imaging-guided focused ultrasound treatment planning. MATERIALS AND METHODS: The U-Net neural network was trained and tested on data obtained from 41 subjects (mean age, 66.4 ± 11.0 years; 15 women). The derived neural network model was evaluated using a k-fold cross-validation method. Derived acoustic properties were verified by comparing the whole skull-density ratio from deep learning synthesized CT of the skull with the reference CT of the skull. In addition, acoustic and temperature simulations were performed using the deep learning CT to predict the target temperature rise during transcranial MR imaging-guided focused ultrasound. RESULTS: The derived deep learning model generates synthetic CT of the skull images that are highly comparable with the true CT of the skull images. Their intensities in Hounsfield units have a spatial correlation coefficient of 0.80 ± 0.08, a mean absolute error of 104.57 ± 21.33 HU, and a subject-wise correlation coefficient of 0.91. Furthermore, deep learning CT of the skull is reliable in the skull-density ratio estimation (r = 0.96). A simulation study showed that both the peak target temperatures and temperature distribution from deep learning CT are comparable with those of the reference CT. CONCLUSIONS: The deep learning method can be used to simplify workflow associated with transcranial MR imaging-guided focused ultrasound.


Assuntos
Aprendizado Profundo , Imageamento por Ressonância Magnética/métodos , Neuroimagem/métodos , Crânio/diagnóstico por imagem , Ultrassonografia Doppler Transcraniana/métodos , Idoso , Simulação por Computador , Feminino , Humanos , Pessoa de Meia-Idade , Tomografia Computadorizada por Raios X/métodos
3.
Osteoarthritis Cartilage ; 27(9): 1382-1391, 2019 09.
Artigo em Inglês | MEDLINE | ID: mdl-31121293

RESUMO

OBJECTIVE: Given the structural changes associated with the progression of Osteoarthritis (OA), we hypothesized that patterns of through-thickness, large-strain shear evolve with early-stage OA. We therefore aimed to determine whether and how patterns of shear strains change during early-stage OA to 1) gain insight into the progression of OA by quantifying changes in local deformations; 2) gauge the potential of patterns in shear strain to serve as image-based biomarkers of early-stage OA; and 3) provide high-resolution, through-thickness data for proposing, fitting, and validating constitutive models for cartilage. DESIGN: We completed displacement-driven, large-strain shear tests (5, 10, 15%) on 44 specimens of variably advanced osteoarthritic human articular cartilage as determined by both Osteoarthritis Research Society International (OARSI) grade and PLM-CO score. We recorded the through-thickness deformations with a stereo-camera system and processed these data using digital image correlation (DIC) to determine full-thickness patterns of strains and relative zonal recruitments, i.e., the average shear strain in a through-thickness zone weighted by its relative thickness and normalized by the applied strain. RESULTS: We observed three general shapes for the curves of averaged through-thickness, Green-Lagrange shear strains during progression of OA. We also observed that during the progression of OA only the deep zone is recruited differently under shear in a statistically significant way. CONCLUSIONS: We propose that changes in through-thickness patterns of shear strain could provide sensitive biomarkers for early clinical detection of OA. The relative zonal recruitment of the deep zone decreases with progressing OA (OARSI grade) and microstructural remodeling (PLM-CO score), which do not consistently affect recruitment of the superficial and middle zones.


Assuntos
Osteoartrite/patologia , Idoso , Cartilagem Articular/patologia , Progressão da Doença , Feminino , Humanos , Masculino , Osteoartrite/etiologia , Osteoartrite do Joelho/etiologia , Osteoartrite do Joelho/patologia , Resistência ao Cisalhamento , Estresse Mecânico
4.
Osteoarthritis Cartilage ; 27(5): 810-822, 2019 05.
Artigo em Inglês | MEDLINE | ID: mdl-30660720

RESUMO

OBJECTIVE: The composition and structure of articular cartilage evolves during the development and progression of osteoarthritis (OA) resulting in changing mechanical responses. We aimed to assess the evolution of the intrinsic, large-strain mechanics of human articular cartilage-governed by collagen and proteoglycan and their interactions-during the progression of OA. DESIGN: We completed quasi-static, large-strain shear tests on 64 specimens from ten donors undergoing total knee arthroplasty (TKA), and quantified the corresponding state of OA (OARSI grade), structural integrity (PLM score), and composition (glycosaminoglycan and collagen content). RESULTS: We observed nonlinear stress-strain relationships with distinct hystereses for all magnitudes of applied strain where stiffnesses, nonlinearities, and hystereses all reduced as OA advanced. We found a reduction in energy dissipation density up to 80% in severely degenerated (OARSI grade 4, OA-4) vs normal (OA-1) cartilage, and more importantly, we found that even cartilage with a normal appearance in structure and composition (OA-1) dissipated 50% less energy than healthy (control) load-bearing cartilage (HL0). Changes in stresses and stiffnesses were in general less pronounced and did not allow us to distinguish between healthy load-bearing controls and very early-stage OA (OA-1), or to distinguish consistently among different levels of degeneration, i.e., OARSI grades. CONCLUSIONS: Our results suggest that reductions in energy dissipation density can be detected by bulk-tissue testing, and that these reductions precede visible signs of degeneration. We highlight the potential of energy dissipation, as opposed to stress- or stiffness-based measures, as a marker to diagnose early-stage OA.


Assuntos
Cartilagem Articular/fisiopatologia , Articulação do Joelho/fisiopatologia , Osteoartrite do Joelho/fisiopatologia , Idoso , Envelhecimento/metabolismo , Envelhecimento/fisiologia , Anisotropia , Artroplastia do Joelho , Fenômenos Biomecânicos/fisiologia , Cartilagem Articular/química , Cartilagem Articular/patologia , Colágeno/análise , Progressão da Doença , Feminino , Glicosaminoglicanos/análise , Humanos , Articulação do Joelho/química , Articulação do Joelho/patologia , Masculino , Pessoa de Meia-Idade , Osteoartrite do Joelho/metabolismo , Osteoartrite do Joelho/patologia , Osteoartrite do Joelho/cirurgia , Índice de Gravidade de Doença , Estresse Mecânico
5.
Nat Chem ; 9(9): 862-867, 2017 09.
Artigo em Inglês | MEDLINE | ID: mdl-28837180

RESUMO

A strategy to develop improved catalysts is to create systems that merge the advantages of heterogeneous and molecular catalysis. One such system involves supported liquid-phase catalysts, which feature a molecularly defined, catalytically active liquid film/droplet layer adsorbed on a porous solid support. In the past decade, this concept has also been extended to supported ionic liquid-phase catalysts. Here we develop this idea further and describe supported catalytically active liquid metal solutions (SCALMS). We report a liquid mixture of gallium and palladium deposited on porous glass that forms an active catalyst for alkane dehydrogenation that is resistant to coke formation and is thus highly stable. X-ray diffraction and X-ray photoelectron spectroscopy, supported by theoretical calculations, confirm the liquid state of the catalytic phase under the reaction conditions. Unlike traditional heterogeneous catalysts, the supported liquid metal reported here is highly dynamic and catalysis does not proceed at the surface of the metal nanoparticles, but presumably at homogeneously distributed metal atoms at the surface of a liquid metallic phase.

6.
J Chem Phys ; 146(17): 170901, 2017 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-28477594

RESUMO

This perspective analyzes the potential of X-ray photoelectron spectroscopy under ultrahigh vacuum (UHV) conditions to follow chemical reactions in ionic liquids in situ. Traditionally, only reactions occurring on solid surfaces were investigated by X-ray photoelectron spectroscopy (XPS) in situ. This was due to the high vapor pressures of common liquids or solvents, which are not compatible with the required UHV conditions. It was only recently realized that the situation is very different when studying reactions in Ionic Liquids (ILs), which have an inherently low vapor pressure, and first studies have been performed within the last years. Compared to classical spectroscopy techniques used to monitor chemical reactions, the advantage of XPS is that through the analysis of their core levels all relevant elements can be quantified and their chemical state can be analyzed under well-defined (ultraclean) conditions. In this perspective, we cover six very different reactions which occur in the IL, with the IL, or at an IL/support interface, demonstrating the outstanding potential of in situ XPS to gain insights into liquid phase reactions in the near-surface region.

7.
Osteoarthritis Cartilage ; 25(4): 544-553, 2017 04.
Artigo em Inglês | MEDLINE | ID: mdl-27903450

RESUMO

OBJECTIVE: We aimed to determine the minimum mechanical impact to cause microstructural damage in the network of collagen (microcracking) within human cartilage and hypothesized that energies below 0.1 J or 1 mJ/mm3 would suffice. DESIGN: We completed 108 low-energy impact tests (0.05, 0.07, or 0.09 J; 0.75 or 1.0 m/s2) using healthy cartilage specimens from six male donors (30.2 ± 8.8 yrs old). Before and after impact we acquired, imaging the second harmonic generation (SHG), ten images from each specimen (50 µm depth, 5 µm step size), resulting in 2160 images. We quantified both the presence and morphology of microcracks. We then correlated test parameters (predictors) impact energy/energy dissipation density, nominal stress/stress rate, and strain/strain rate to microcracking and tested for significance. Where predictors significantly correlated with microstructural outcomes we fitted binary logistic regression plots with 95% confidence intervals (CIs). RESULTS: No specimens presented visible damage following impact. We found that impact energy/energy dissipation density and nominal stress/stress rate were significant (P < 0.05) predictors of microcracking while both strain and strain rate were not. In our test configuration, an impact energy density of 2.93 mJ/mm3, an energy dissipation density of 1.68 mJ/mm3, a nominal stress of 4.18 MPa, and a nominal stress rate of 689 MPa/s all corresponded to a 50% probability of microcracking in the network of collagen. CONCLUSIONS: An impact energy density of 1.0 mJ/mm3 corresponded to a ∼20% probability of microcracking. Such changes may initiate a degenerative cascade leading to post-traumatic osteoarthritis.


Assuntos
Cartilagem Articular/lesões , Colágeno/metabolismo , Estresse Mecânico , Adulto , Fenômenos Biomecânicos , Cartilagem Articular/metabolismo , Cartilagem Articular/patologia , Humanos , Modelos Logísticos , Masculino , Microscopia de Geração do Segundo Harmônico , Adulto Jovem
8.
Phys Chem Chem Phys ; 18(36): 25143-25150, 2016 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-27711556

RESUMO

Combining in vacuo deposition of ultrathin ionic liquid (UTIL) films with angle-resolved X-ray photoelectron spectroscopy (ARXPS), we demonstrate that by deposition of submonolayer amounts of Pd onto Au(111) the initial growth mode of the ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([C2C1Im][OTf]) can be switched from three-dimensional (3D) to two-dimensional (2D) growth, that is, from non-wetting to wetting. On clean Au(111), pronounced 3D growth occurs on top of an initially formed 2D wetting layer with cations and anions next to each other in a checkerboard arrangement. After pre- or postdeposition of only 0.7 ML Pd, two-dimensional layer-by-layer growth is found, which is attributed to strong attractive interactions between [C2C1Im][OTf] and surface Pd. For Pd post deposition onto the IL, the ARXPS data revealed particularly strong interactions between the dialkylimidazolium cation and Pd atoms, which considerably reduce the regular surface alloying of Pd with the Au substrate stabilizing Pd at the metal surface. In the context of heterogeneous catalysis using the SCILL (solid catalyst coated with ionic liquid layer) concept, these results directly provide a possible explanation on the molecular level for the beneficial influence of the IL layer in case of heterogeneous metal alloy catalysts.

9.
Nuklearmedizin ; 55(2): 63-70, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-27067794

RESUMO

This review addresses small animal optical imaging (OI) applications in diverse fields of basic research. In the past, OI has proven to be cost- and time-effective, allows real-time imaging as well as high-throughput analysis and does not imply the usage of ionizing radiation (with the exception of Cerenkov imaging applications). Therefore, this technique is widely spread - not only geographically, but also among very different fields of basic research - and is represented by a large body of publications. Originally used in oncology research, OI is nowadays emerging in further areas like inflammation and infectious disease as well as neurology. Besides fluorescent probe-based contrast, the feasibility of Cerenkov luminescence imaging (CLI) has been recently shown in small animals and thus represents a new route for future applications. Thus, this review will focus on examples for OI applications in inflammation, infectious disease, cell tracking as well as neurology, and provides an overview over CLI.


Assuntos
Corantes Fluorescentes/química , Medições Luminescentes/veterinária , Microscopia de Fluorescência/veterinária , Imagem Molecular/veterinária , Imagem Corporal Total/veterinária , Experimentação Animal , Animais , Camundongos , Ratos
10.
Ultrason Imaging ; 38(1): 96-112, 2016 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-26149314

RESUMO

High intensity focused ultrasound (HIFU) thermal therapies are limited by deficiencies in existing image-guidance techniques. Previous studies using single-wavelength photoacoustic (PA) imaging have demonstrated that HIFU lesions generate contrast with respect to native tissues but have not sufficiently assessed lesion extent. The purpose of this study is to demonstrate feasibility of characterization of in vitro HIFU ablation lesion dimensions using 3D multi-wavelength PA imaging. Fresh porcine cardiac and liver tissue samples were embedded in agar phantoms and ablated using a 2.5 MHz small-animal HIFU system. Both 2D and 3D multi-wavelength photoacoustic-ultrasonic (PAUS) scans were performed in the near-infrared (NIR) range to characterize the change in the absorption spectrum of tissues following ablation and were compared to stained gross pathology to assess treatment margins and lesion extent. Comprehensive 2D multi-wavelength PA imaging yielded a spectrum in ablated tissue that did not display the characteristic local maximum in the optical absorption spectrum of deoxy-hemoglobin (Hb) near 760 nm. Two-dimensional tissue characterization map (TCM) images reconstructed from 3D TCM volumes reliably characterized lesion area and showed >70% area agreement with stained gross pathology. In addition, tissue samples were heated via water bath and concurrently interrogated with 2D PAUS imaging. PA signal exhibited an initial amplitude increase across all wavelengths, corresponding to an initial temperature increase, before then exhibiting a spectral change. This study suggests that multi-wavelength PA imaging has potential to obtain accurate characterization of HIFU lesion extent and may be better suited to guide HIFU ablation therapies during clinical treatments than single-wavelength methods.


Assuntos
Ablação por Ultrassom Focalizado de Alta Intensidade/métodos , Técnicas Fotoacústicas/métodos , Animais , Coração , Imageamento Tridimensional/métodos , Fígado , Imagens de Fantasmas , Suínos
11.
Psychol Med ; 45(1): 73-85, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25066623

RESUMO

BACKGROUND: Clinical and ethical implications of personality and mood changes in Parkinson's disease (PD) patients treated with subthalamic deep brain stimulation (STN-DBS) are under debate. Although subjectively perceived personality changes are often mentioned by patients and caregivers, few empirical studies concerning these changes exist. Therefore, we analysed subjectively perceived personality and mood changes in STN-DBS PD patients. METHOD: In this prospective study of the ELSA-DBS group, 27 PD patients were assessed preoperatively and 1 year after STN-DBS surgery. Two categories, personality and mood changes, were analysed with semi-structured interviews. Patients were grouped into personality change yes/no, as well as positive/negative mood change groups. Caregivers were additionally interviewed about patients' personality changes. Characteristics of each group were assessed with standard neurological and psychiatric measurements. Predictors for changes were analysed. RESULTS: Personality changes were perceived by six of 27 (22%) patients and by 10 of 23 caregivers (44%). The preoperative hypomania trait was a significant predictor for personality change perceived by patients. Of 21 patients, 12 (57%) perceived mood as positively changed. Higher apathy and anxiety ratings were found in the negative change group. CONCLUSIONS: Our results show that a high proportion of PD patients and caregivers perceived personality changes under STN-DBS, emphasizing the relevance of this topic. Mood changed in positive and negative directions. Standard measurement scales failed to adequately reflect personality or mood changes subjectively perceived by patients. A more individualized preoperative screening and preparation for patients and caregivers, as well as postoperative support, could therefore be useful.


Assuntos
Estimulação Encefálica Profunda/efeitos adversos , Transtornos do Humor/epidemiologia , Transtornos da Personalidade/epidemiologia , Adulto , Idoso , Análise de Variância , Cuidadores , Feminino , Alemanha/epidemiologia , Humanos , Entrevistas como Assunto , Masculino , Pessoa de Meia-Idade , Transtornos do Humor/etiologia , Doença de Parkinson/cirurgia , Transtornos da Personalidade/etiologia , Estudos Prospectivos , Escalas de Graduação Psiquiátrica , Qualidade de Vida , Subtálamo
12.
Int J Comput Assist Radiol Surg ; 9(4): 659-67, 2014 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-24091853

RESUMO

PURPOSE: An open-source software system for planning magnetic resonance (MR)-guided laser-induced thermal therapy (MRgLITT) in brain is presented. The system was designed to provide a streamlined and operator-friendly graphical user interface (GUI) for simulating and visualizing potential outcomes of various treatment scenarios to aid in decisions on treatment approach or feasibility. METHODS: A portable software module was developed on the 3D Slicer platform, an open-source medical imaging and visualization framework. The module introduces an interactive GUI for investigating different laser positions and power settings as well as the influence of patient-specific tissue properties for quickly creating and evaluating custom treatment options. It also provides a common treatment planning interface for use by both open-source and commercial finite element solvers. In this study, an open-source finite element solver for Pennes' bioheat equation is interfaced to the module to provide rapid 3D estimates of the steady-state temperature distribution and potential tissue damage in the presence of patient-specific tissue boundary conditions identified on segmented MR images. RESULTS: The total time to initialize and simulate an MRgLITT procedure using the GUI was [Formula: see text]5 min. Each independent simulation took [Formula: see text]30 s, including the time to visualize the results fused with the planning MRI. For demonstration purposes, a simulated steady-state isotherm contour [Formula: see text] was correlated with MR temperature imaging (N = 5). The mean Hausdorff distance between simulated and actual contours was 2.0 mm [Formula: see text], whereas the mean Dice similarity coefficient was 0.93 [Formula: see text]. CONCLUSIONS: We have designed, implemented, and conducted initial feasibility evaluations of a software tool for intuitive and rapid planning of MRgLITT in brain. The retrospective in vivo dataset presented herein illustrates the feasibility and potential of incorporating fast, image-based bioheat predictions into an interactive virtual planning environment for such procedures.


Assuntos
Encéfalo/cirurgia , Terapia a Laser/métodos , Imageamento por Ressonância Magnética/métodos , Humanos , Estudos Retrospectivos , Software
13.
G Ital Med Lav Ergon ; 34(3): 229-35, 2012.
Artigo em Italiano | MEDLINE | ID: mdl-23213794

RESUMO

The importance of the refractories sintering and manufacture can be better understood considering that the worldwide refractories consumption is about 2,3 kg per year/human being. The RHI Group, world leader in the refractories production, is present in Italy with the production of refractories for the steel and glass sectors in two important industrial sites, in Marone (Brescia) and in San Vito al Tagliamento (Pordenone) respectively. Describes origin, structure and characteristics of the different refractory materials, with particular focus on the different production technologies used in the manufacture of basic refractories (dolomite refractories) and mixed based on alumina, zirconia and silica. We describe the main hygienistics aspects relevant for the protection to the exposure of the workers involved in described production processes. In the production of dolomite refractories, we present the actions that have been implemented in order to reduce the exposure to the Polycyclic Aromatic Hydrocarbons (PAHs). In this process, we report the results of a decade of exposure's monitoring to polycyclic aromatic hydrocarbons in a group of refractory workers.


Assuntos
Metalurgia , Exposição Ocupacional/prevenção & controle , Saúde Ocupacional , Humanos
14.
Phys Chem Chem Phys ; 14(15): 5153-63, 2012 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-22382789

RESUMO

Ultrathin films of the ionic liquid 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([C(1)C(1)Im][Tf(2)N]) were deposited on differently terminated Ni(111) single crystal surfaces. The initial wetting behaviour, the growth characteristics, the molecular arrangement at the interface, and thermal reactivity were investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS). On clean Ni(111), the initial growth occurs in a layer-by-layer mode. At submonolayer coverages up to at least 0.40 ML, a preferential arrangement of the IL ions in a bilayer structure, with the imidazolium cations in contact with the Ni surface atoms and the anions on top of the cation, is deduced. For higher coverages, a transition to a checkerboard-type arrangement occurs, which is most likely due to repulsive dipole-dipole interactions in the first layer. An overall preference for a checkerboard-type adsorption behaviour, i.e., anions and cations adsorbing next to each other, is found on the oxygen-precovered O(√3×√3)R30° Ni(111) surface. The thermal stability of adsorbed IL layers on Ni(111) and on a fully oxidised Ni(111) surface was studied by heating the layers to elevated temperatures. For clean Ni(111) reversible adsorption takes place. For the oxidised surface, however, only cation-related moieties desorb, starting at ~450 K, while anion-related signals remain on the surface up to much higher temperatures.

15.
Adv Mater ; 23(22-23): 2571-87, 2011 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-21520462

RESUMO

Materials making use of thin ionic liquid (IL) films as support-modifying functional layer open up a variety of new possibilities in heterogeneous catalysis, which range from the tailoring of gas-surface interactions to the immobilization of molecularly defined reactive sites. The present report reviews recent progress towards an understanding of "supported ionic liquid phase (SILP)" and "solid catalysts with ionic liquid layer (SCILL)" materials at the microscopic level, using a surface science and model catalysis type of approach. Thin film IL systems can be prepared not only ex-situ, but also in-situ under ultrahigh vacuum (UHV) conditions using atomically well-defined surfaces as substrates, for example by physical vapor deposition (PVD). Due to their low vapor pressure, these systems can be studied in UHV using the full spectrum of surface science techniques. We discuss general strategies and considerations of this approach and exemplify the information available from complementary methods, specifically photoelectron spectroscopy and surface vibrational spectroscopy.


Assuntos
Líquidos Iônicos/química , Modelos Químicos , Catálise , Complexos de Coordenação/química , Nanopartículas/química , Propriedades de Superfície , Vácuo
16.
Langmuir ; 27(7): 3662-71, 2011 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-21361299

RESUMO

Ultrathin films of two imidazolium-based ionic liquids (IL), [C(1)C(1)Im][Tf(2)N] (= 1,3-dimethylimidazolium bis(trifluoromethyl)imide) and [C(8)C(1)Im][Tf(2)N] (= 1-methyl-3-octylimidazolium bis(trifluoromethyl)imide) were prepared on a Au(111) single-crystal surface by physical vapor deposition in ultrahigh vacuum. The adsorption behavior, orientation, and growth were monitored via angle-resolved X-ray photoelectron spectroscopy (ARXPS). Coverage-dependent chemical shifts of the IL-derived core levels indicate that for both ILs the first layer is formed from anions and cations directly in contact with the Au surface in a checkerboard arrangement and that for [C(8)C(1)Im][Tf(2)N] a reorientation of the alkyl chain with increasing coverage is found. For both ILs, geometry models of the first adsorption layer are proposed. For higher coverages, both ILs grow in a layer-by-layer fashion up to thicknesses of at least 9 nm (>10 ML). Moreover, beam damage effects are discussed, which are mainly related to the decomposition of [Tf(2)N](-) anions directly adsorbed at the gold surface.

17.
J Phys Chem B ; 114(51): 17025-36, 2010 Dec 30.
Artigo em Inglês | MEDLINE | ID: mdl-21141903

RESUMO

We measured the density and surface tension of 9 bis[(trifluoromethyl)sulfonyl]imide ([Tf(2)N](-))-based and 12 1-methyl-3-octylimidazolium ([C(8)C(1)Im](+))-based ionic liquids (ILs) with the vibrating tube and the pendant drop method, respectively. This comprehensive set of ILs was chosen to probe the influence of the cations and anions on density and surface tension. When the alkyl chain length in the [C(n)C(1)Im][Tf(2)N] series (n = 1, 2, 4, 6, 8, 10, 12) is increased, a decrease in density is observed. The surface tension initially also decreases but reaches a plateau for alkyl chain lengths greater than n = 8. Functionalizing the alkyl chains with ethylene glycol groups results in a higher density as well as a higher surface tension. For the dependence of density and surface tension on the chemical nature of the anion, relations are only found for subgroups of the studied ILs. Density and surface tension values are discussed with respect to intermolecular interactions and surface composition as determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). The absence of nonvolatile surface-active contaminants was proven by ARXPS.

18.
Fortschr Neurol Psychiatr ; 78(9): 513-8, 2010 Sep.
Artigo em Alemão | MEDLINE | ID: mdl-20827651

RESUMO

Cognitive decline is a common disorder in idiopathic Parkinson's syndrome, the risk for the development of a dementia is four- to six-fold higher for Parkinsonian patients. The cognitive profile in Parkinson's disease dementia (PDD) differs from that of Alzheimer-type dementias. The affected cognitive functions include attention, executive functions, visual-spatial functions and recall. The main differential diagnosis for PDD is the Lewy body dementia (LBD), which can be differentiated through the temporal development of motor and cognitive symptoms. Cognitive symptoms in Parkinsonian syndromes have a relevant negative impact on quality of life, on the burden for the care-givers, on the prognosis of the disease and on the possible referral to a nursing home. Dementias in Parkinsonian syndromes (PDD and LBD) need a confirmatory diagnosis at an early stage in order to initiate further therapeutic steps with, e. g., acetylcholine esterase inhibitors or, perspectively, neuropsychological training methods.


Assuntos
Demência/diagnóstico , Demência/etiologia , Doença de Parkinson/complicações , Doença de Parkinson/terapia , Idoso , Atenção/fisiologia , Cuidadores , Cognição/fisiologia , Demência/terapia , Diagnóstico Diferencial , Função Executiva , Humanos , Doença por Corpos de Lewy/diagnóstico , Doença por Corpos de Lewy/psicologia , Rememoração Mental/fisiologia , Percepção Espacial/fisiologia , Percepção Visual/fisiologia
19.
Ultramicroscopy ; 110(11): 1358-61, 2010 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-20692099

RESUMO

The lateral resolution of a surface sensitive low-energy electron microscope (LEEM) has been improved below 4 nm for the first time. This breakthrough has only been possible by simultaneously correcting the unavoidable spherical and chromatic aberrations of the lens system. We present an experimental criterion to quantify the aberration correction and to optimize the electron optical system. The obtained lateral resolution of 2.6 nm in LEEM enables the first surface sensitive, electron microscopic observation of the herringbone reconstruction on the Au(111) surface.

20.
Phys Chem Chem Phys ; 12(8): 1905-15, 2010 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-20145858

RESUMO

A systematic study of ionic liquid surfaces by angle resolved X-ray photoelectron spectroscopy (ARXPS) is presented. By reviewing recent and presenting new results for imidazolium-based ionic liquids (ILs), we discuss the impact of chemical differences on surface composition and on surface enrichment effects. (1) For the hydrophilic ethylene glycol (EG) functionalised ILs [Me(EG)MIm][Tf(2)N], [Et(EG)(2)MIm][Tf(2)N] and [Me(EG)(3)MIm][Tf(2)N], which vary in the number of ethylene glycol units (from 1 to 3), we find that the surface composition of the near-surface region is in excellent agreement with the bulk composition, which is attributed to attractive interactions between the oxygen atoms on the cation to the hydrogen atoms on the imidazolium ring. (2) For [C(n)C(1)Im][Tf(2)N] (where n = 1-16), i.e. ILs with an alkyl chain of increasing length, an enrichment of the aliphatic carbons is observed for longer chains (n > 2), at the expense of the polar cation head groups and the anions in the first molecular layer, both of which are located approximately at the same distance from the outer surface. (3) To study the influence of the anion on the surface enrichment, we investigated ten ILs [C(8)C(1)Im][X] with the same cation, but very different anions [X](-). In all cases, surface enrichment of the cation alkyl chains is found, with the degree of enrichment decreasing with increasing size of the anion, i.e., it is most pronounced for the smallest anions and least pronounced for the largest anions. (4) For the IL mixture [C(2)C(1)Im][Tf(2)N] and [C(12)C(1)Im][Tf(2)N] we find a homogeneous distribution in the outermost surface region with no specific enrichment of the [C(12)C(1)Im](+) cation.


Assuntos
Líquidos Iônicos/química , Ânions/química , Imidazóis/química , Espectroscopia Fotoeletrônica , Polietilenoglicóis/química , Propriedades de Superfície , Termodinâmica
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