In nanometer-sized apertures with charged surfaces, the extension of the electrical double layer results in the electrostatic exclusion of co-ions and enrichment in counterions, which affects the ...permselectivity of such structures. A modeling of this phenomenon is proposed and is compared with quantitative measurements of the ionic permeability change of a Pyrex nanoslit at low ionic strength. The comparison of experimental results with theoretical predictions justifies that electrostatic forces are the governing forces in nanofluidics.
In this study, thermal analysis, infrared spectroscopy (near and mid) in conjunction with low field NMR, have been used to characterize the crosslinking reaction involving phenol formaldehyde resin ...and a crosslinking agent, hexamethylenetetramine (HMTA) used as adhesive in organic-inorganic composites. The strong hydrogen bonds in the resin and the completely crystalline HMTA (Tm = 280°C) severely hamper the crosslinking process. Yet the addition of a small amount of plasticizer can induce an efficient (> 50% increase) crosslinking reaction as compared to the system without plasticizer. The infrared spectroscopy clarifies the dissolution process of the crystalline crosslinker and the specific interactions needed to achieve miscibility of the reactants. The thermal analysis enabled us to follow the reaction as a function of temperature. The low field NMR with the T1 inverse recovery technique allowed us to monitor the crosslinking process directly. For the first time, it is now possible to identify the functionality of the plasticizer and correlate the degree of crosslinking achieved in order to assess the macroscopic cohesive strength needed for high performance adhesives.
A uniform dispersion of reactants is necessary to achieve a complete reaction involving multiple components. Utilizing a combination of infrared spectroscopy, thermal analysis and low field NMR, we ...have elucidated the role of three types of reactive plasticizers on the crosslinking reaction between hexamethylenetetramine and phenol formaldehyde resin. These two seemingly dissimilar reactants are responsible for the exceptionally high mechanical strength in a number of organic-inorganic composites. The efficiencies of the curing reaction and the achieved crosslinked structures are strongly dependent on the type of plasticizer employed. Infrared active vibrations are used to characterize the changing molecular structures of the individual reactants as a function of temperature. The T1 spin-lattice relaxation time measured using low field NMR is especially useful for the characterization of segmental dynamics of the chains in the formation of the extremely rigid crosslinked product. This study shows that the amount of crosslinking and the crosslinked structure can be very different for the three types of reactive plasticizers and also different in comparison to non-reactive plasticizers. We are also able to correlate the reactivity and functionality of the plasticizer to the crosslink density in the reacted product.
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Filtration of molecules by nanometer-sized structures is ubiquitous in our everyday life, but our understanding of such molecular filtration processes is far less than desired. Until recently, one of ...the main reasons was the lack of experimental methods that can help provide detailed, microscopic pictures of molecule-nanostructure interactions. Several innovations in experimental methods, such as nuclear track-etched membranes developed in the 70s, and more recent development of nanofluidic molecular filters, played pivotal roles in advancing our understanding. With the ability to make truly molecular-scale filters and pores with well-defined sizes, shapes, and surface properties, now we are well positioned to engineer better functionality in molecular sieving, separation and other membrane applications. Reviewing past theoretical developments (often scattered across different fields) and connecting them to the most recent advances in the field would be essential to get a full, unified view on this important engineering question.
Microfabricated regular sieving structures hold great promise as an alternative to gels to improve the speed and resolution of biomolecule separation. In contrast to disordered porous gel networks, ...these regular structures also provide well defined environments ideal for the study of molecular dynamics in confining spaces. However, the use of regular sieving structures has, to date, been limited to the separation of long DNA molecules, however separation of smaller, physiologically relevant macromolecules, such as proteins, still remains a challenge. Here we report a microfabricated anisotropic sieving structure consisting of a two-dimensional periodic nanofluidic filter array. The designed structural anisotropy causes different-sized or -charged biomolecules to follow distinct trajectories, leading to efficient separation. Continuous-flow size-based separation of DNA and proteins, as well as electrostatic separation of proteins, was achieved, demonstrating the potential use of this device as a generic molecular sieving structure for an integrated biomolecule sample preparation and analysis system.
We present a technique which enables the separation of small RNAs-such as microRNAs (miRNAs), short interfering RNAs (siRNAs), and Piwi-interacting RNAs (piRNAs)-from >or=66 nucleotide RNAs and other ...biomolecules contained in a cell lysate. In particular, the method achieves separation of small RNAs from precursor miRNAs (pre-miRNAs) in less than 3 min. We use on-chip isotachophoresis (ITP) for the simultaneous extraction, isolation, preconcentration and quantitation of small RNAs (approximately 22 nucleotides) and employ the high-efficiency sieving matrix Pluronic F-127; a thermo-responsive triblock copolymer which allows convenient microchannel loading at low temperature. We present the isolation of small RNAs from the lysate of 293A human kidney cells, and quantitate the number of short RNA molecules per cell to be 2.9x10(7). We estimate this quantity is an aggregate of roughly 500 types of short RNA molecules per 293A cell. Currently, the minimal cell number for small RNA extraction and detection with our method is approximately 900 (from a 5 microL sample volume), and we believe that small RNA analysis from tens of cells is realizable. Techniques for rapid and sensitive extraction and isolation of small RNAs from cell lysate are much-needed to further uncover their full range and functionality, including RNA interference studies.
Cerebellar ataxic gait is influenced greatly by balance disorders, most likely caused by lesions of the medial zone of the cerebellum. The contributions of the intermediate and lateral zone to the ...control of limb dynamics for gait and the adaptation of locomotor patterns are less well understood. In this study, we analysed locomotion and goal-directed leg movements in 12 patients with chronic focal lesions after resection of benign cerebellar tumours. The extent of the cortical lesion and possible involvement of the cerebellar nuclei was determined by 3D-MR imaging. The subjects (age range 13–39 years, mean 20.3; seven female; ICARS score: mean 5.7, SD 6.3) performed three tasks: goal-directed leg placement, walking and walking with additional weights on the shanks. Based on the performance on the first two tasks, patients were categorized as impaired or unimpaired for leg placement and for dynamic balance control in gait. The subgroup with impaired leg placement but not the subgroup with impaired balance showed abnormalities in the adaptation of locomotion to additional loads. A detailed analysis revealed specific abnormalities in the temporal aspects of intra-limb coordination for leg placement and adaptive locomotion. These findings indicate that common neural substrates could be responsible for intra-limb coordination in both tasks. Lesion-based MRI subtraction analysis revealed that the interposed and the adjacent dentate nuclei were more frequently affected in patients with impaired compared to unimpaired leg placement, whereas the fastigial nuclei (and to a lesser degree the interposed nuclei) were more frequently affected in patients with impaired compared with unimpaired dynamic balance control. The intermediate zone appears thus to be of particular importance for multi-joint limb control in both goal-directed leg movements and in locomotion. For locomotion, our results indicate an influence of the intermediate zone on dynamic balance control as well as on the adaptation to changes in limb dynamics.
Gold nanoparticles stabilized by thiol-terminated poly(ethylene glycol) monomethyl ethers with molecular weights ranging from 350 to 2000 have been prepared at thiol-to-gold molar ratios ranging from ...3:1 to 1:8. Particle size distributions have been constructed for these particles from transmission electron microscopy images of hundreds of particles for each variation in synthetic conditions. The mean diameters of these particles range from 1.5 to 3.2 nm, with a slight increase in particle size with decreasing thiol content; these particles are smaller than those prepared using alkanethiols at similar thiol-to-gold ratios. Particles prepared under thiol-poor conditions exhibit much greater polydispersity than those prepared under thiol-rich conditions and include numerically rare large-particle outliers that contain much of the gold in the sample. The mean diameters of the gold nanoparticles decrease slightly with increasing polymer weight, especially under thiol-rich conditions. A simple model is developed to predict the trends in nanoparticle diameter that would result were the polymer's steric bulk protecting the nanoparticles from additional growth the principal factor controlling nanoparticle size in this system. This model predicts a much stronger dependence on thiol concentration than has been experimentally observed and a dependence on polymer molecular weight opposite to that experimentally observed. This suggests that the polymers' steric bulk is not the principal reason that these polymers yield smaller nanoparticles than alkanethiols at similar thiol-to-gold ratios. It is instead proposed that polar polymers may yield small nanoparticles by accelerating particle nucleation via coordination between functional groups in the polymer and atomic gold.
The aim of the present study was to examine somatotopy in the cerebellar cortex and a possible differential role of the cerebellar cortex and nuclei in functional outcome. Clinical findings and 3D ...MRI-based cerebellar lesions site were compared in a group of 90 patients with focal cerebellar lesion using International Cooperative Ataxia Rating Scale (ICARS) and voxel-based lesion–symptom mapping (VLSM). Separate analysis was performed in patients with acute and chronic ischemic lesions (
n = 43) and patients with acute and chronic surgical lesions (
n = 47). Thirty-eight patients were included after resection of a cerebellar tumor in childhood or adolescence.
The most significant lesion symptom correlations were observed in the subgroup with acute ischemic lesions. Limb ataxia was significantly correlated with lesions of the interposed (NI) and part of the dentate nuclei (ND), ataxia of posture and gait with lesions of the fastigial nuclei (NF) including NI. Correlations with cortical lesions were less significant and present in the superior cerebellum only. Upper limb ataxia was correlated with lesions of vermal, paravermal and hemispheral lobules IV–V and VI, lower limb ataxia with lesions of vermal, paravermal and hemispheral lobules III and VI, dysarthria with lesions of paravermal and hemispheral lobules V and VI and ataxia of posture and gait with lesions of vermal and paravermal lobules II, III and IV. In the subgroups with chronic focal lesions, similar correlations were observed with lesions of the cerebellar nuclei, but significantly less correlations with lesions of the cerebellar cortex.
Functional localization based on VLSM backs findings in previous animal and functional brain images studies in healthy human subjects. The lesion site appears to be critical for motor recovery. Lesions affecting the cerebellar nuclei are not fully compensated at any age and independent of the pathology in humans.
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