Cooperative Carbon Dioxide Adsorption in Alcoholamine- and Alkoxyalkylamine-Functionalized Metal-Organic Frameworks.

A series of structurally diverse alcoholamine- and alkoxyalkylamine-functionalized variants of the metal-organic framework Mg2 (dobpdc) are shown to adsorb CO2 selectively via cooperative chain-forming mechanisms. Solid-state NMR spectra and optimized structures obtained from van der Waals-corrected density functional theory calculations indicate that the adsorption profiles can be attributed to the formation of carbamic acid or ammonium carbamate chains that are stabilized by hydrogen bonding interactions within the framework pores. These findings significantly expand the scope of chemical functionalities that can be utilized to design cooperative CO2 adsorbents, providing further means of optimizing these powerful materials for energy-efficient CO2 separations

Effects of layer shift and yarn path variability on mechanical properties of a twill weave composite

Experimental and numerical analysis of a woven composite were performed in order to assess the effect of yarn path and layer shift variability on properties of the composite. Analysis of the geometry of a 12K carbon fibre 2×2 twill weave at the meso- and macro-scales showed the prevalence of the yarn path variations at the macro-scale over the meso-scale variations. Numerical analysis of yarn path variability showed that it is responsible for a Young’s modulus reduction of 0.5% and CoV of 1% which makes this type of variability in the selected reinforcement almost insignificant for an elastic analysis. Finite element analysis of damage propagation in laminates with layer shift showed good agreement with the experiments. Both numerical analysis and experiments showed that layer shift has a strong effect on the shape of the stress-strain curve. In particular, laminates with no layer shift tend to exhibit a kink in the stress-strain curve which was attributed solely to the layer configuration

Frictional behaviour of non-crimp fabrics (NCFs) in contact with a forming tool

Microscopic observation and analysis are used to examine the role that contact conditions play in determining the frictional behaviour of non-crimp fabrics (NCFs). The true fibre contact length is measured over a range of normal pressures. For the NCF considered, the contact length is 67% lower than for a corresponding unidirectional tow-on-tool contact at a pressure of 240 kPa. The difference in contact behaviour is associated with the fabric architecture, specifically stitching and gaps between tows. These microscopic observations are used to predict friction using a constant interface shear strength model. These predictions are found to compare well with macroscopic friction measurements taken using a sliding sled arrangement, once the roughness of the sled tool is taken into account

THERMORESPONSIVE, REDOX-POLYMERIZED CELLULOSIC HYDROGELS UNDERGO IN SITU GELATION AND RESTORE INTERVERTEBRAL DISC BIOMECHANICS POST DISCECTOMY

Back and neck pain are commonly associated with intervertebral disc (IVD) degeneration. Structural augmentation of diseased nucleus pulposus (NP) tissue with biomaterials could restore degeneration-related IVD height loss and degraded biomechanical behaviors; however, effective NP replacement biomaterials are not commercially available. This study developed a novel, crosslinked, dual-polymer network (DPN) hydrogel comprised of methacrylated carboxymethylcellulose (CMC) and methylcellulose (MC), and used in vitro, in situ and in vivo testing to assess its efficacy as an injectable, in situ gelling, biocompatible material that matches native NP properties and restores IVD biomechanical behaviors. Thermogelling MC was required to enable consistent and timely gelation of CMC in situ within whole IVDs. The CMC-MC hydrogel was tuned to match compressive and swelling NP tissue properties. When injected into whole IVDs after discectomy injury, CMC-MC restored IVD height and compressive biomechanical behaviors, including range of motion and neutral zone stiffness, to intact levels. Subcutaneous implantation of the hydrogels in rats further demonstrated good biocompatibility of CMC-MC with a relatively thin fibrous capsule, similar to comparable biomaterials. In conclusion, CMC-MC is an injectable, tunable and biocompatible hydrogel with strong potential to be used as an NP replacement biomaterial since it can gel in situ, match NP properties, and restore IVD height and biomechanical function. Future investigations will evaluate herniation risk under severe loading conditions and assess long-term in vivo performance

Influence of Pore Size on Carbon Dioxide Diffusion in Two Isoreticular Metal-Organic Frameworks

The rapid diffusion of molecules in porous materials is critical for numerous applications including separations, energy storage, sensing, and catalysis. A common strategy for tuning guest diffusion rates is to vary the material pore size, although detailed studies that isolate the effect of changing this particular variable are lacking. Here, we begin to address this challenge by measuring the diffusion of carbon dioxide in two isoreticular metal-organic frameworks featuring channels with different diameters, Zn2(dobdc) (dobdc4- = 2,5-dioxidobenzene-1,4-dicarboxylate) and Zn2(dobpdc) (dobpdc4- = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate), using pulsed field gradient NMR spectroscopy. An increase in the pore diameter from 15 Å in Zn2(dobdc) to 22 Å in Zn2(dobpdc) is accompanied by an increase in the self-diffusion of CO2 by a factor of 4 to 6, depending on the gas pressure. Analysis of the diffusion anisotropy in Zn2(dobdc) reveals that the self-diffusion coefficient for motion of CO2 along the framework channels is at least 10000 times greater than for motion between the framework channels. Our findings should aid the design of improved porous materials for a range of applications where diffusion plays a critical role in determining performance

Uncertainty in geometry of fibre preforms manufactured with Automated Dry Fibre Placement (ADFP) and its effects on permeability

Resin transfer moulding is one of several processes available for manufacturing fibre-reinforced composites from dry fibre reinforcement. Recently, dry reinforcements made with Automated Dry Fibre Placement have been introduced into the aerospace industry. Typically, the permeability of the reinforcement is assumed to be constant throughout the dry preform geometry whereas in reality it possesses inevitable uncertainty due to variability in geometry. This uncertainty propagates to the uncertainty of the mould filling and the fill time, one of the important variables in resin injection. It makes characterisation of the permeability and its variability an important task for design of the resin transfer moulding process. In this study, variability of the geometry of a reinforcement manufactured using Automated Dry Fibre Placement is studied. Permeability of the manufactured preforms is measured experimentally and compared to stochastic simulations based on an analytical model and a stochastic geometry model. The simulations showed that difference between the actual geometry and the designed geometry can result in 50% reduction of the permeability. The stochastic geometry model predicts results within 20% of the experimental values

Mitochondrial targeting adaptation of the hominoid-specific glutamate dehydrogenase driven by positive Darwinian selection

Many new gene copies emerged by gene duplication in hominoids, but little is known with respect to their functional evolution. Glutamate dehydrogenase (GLUD) is an enzyme central to the glutamate and energy metabolism of the cell. In addition to the single, GLUD-encoding gene present in all mammals (GLUD1), humans and apes acquired a second GLUD gene (GLUD2) through retroduplication of GLUD1, which codes for an enzyme with unique, potentially brain-adapted properties. Here we show that whereas the GLUD1 parental protein localizes to mitochondria and the cytoplasm, GLUD2 is specifically targeted to mitochondria. Using evolutionary analysis and resurrected ancestral protein variants, we demonstrate that the enhanced mitochondrial targeting specificity of GLUD2 is due to a single positively selected glutamic acid-to-lysine substitution, which was fixed in the N-terminal mitochondrial targeting sequence (MTS) of GLUD2 soon after the duplication event in the hominoid ancestor ~18–25 million years ago. This MTS substitution arose in parallel with two crucial adaptive amino acid changes in the enzyme and likely contributed to the functional adaptation of GLUD2 to the glutamate metabolism of the hominoid brain and other tissues. We suggest that rapid, selectively driven subcellular adaptation, as exemplified by GLUD2, represents a common route underlying the emergence of new gene functions

A compact statistical model of the song syntax in Bengalese finch

Songs of many songbird species consist of variable sequences of a finite number of syllables. A common approach for characterizing the syntax of these complex syllable sequences is to use transition probabilities between the syllables. This is equivalent to the Markov model, in which each syllable is associated with one state, and the transition probabilities between the states do not depend on the state transition history. Here we analyze the song syntax in a Bengalese finch. We show that the Markov model fails to capture the statistical properties of the syllable sequences. Instead, a state transition model that accurately describes the statistics of the syllable sequences includes adaptation of the self-transition probabilities when states are repeatedly revisited, and allows associations of more than one state to the same syllable. Such a model does not increase the model complexity significantly. Mathematically, the model is a partially observable Markov model with adaptation (POMMA). The success of the POMMA supports the branching chain network hypothesis of how syntax is controlled within the premotor song nucleus HVC, and suggests that adaptation and many-to-one mapping from neural substrates to syllables are important features of the neural control of complex song syntax