Patella height measurements in patients with patellofemoral instability: the power to predict patella height indices.

INTRODUCTION: Numerous indices for patella height measurement are described in the literature; however, there is not a universally accepted 'gold standard'. Choice of indices varies depending on personal preference and previous experience, making it difficult to compare results between studies. The aims of this study were to assess the correlation between different patella height indices and generate statistically derived formulae that can be used to predict the value of one patella height ratio when another is known. MATERIALS AND METHODS: Patients with patellofemoral instability were radiologically evaluated using both X-ray and Magnetic Resonance Imaging (MRI) of the knee. Two observers measured six validated patella height indices at two separate time intervals. All measurements were aggregated together and a mean average for each patella height ratio was calculated. These results were then statistically analysed using Pearson product-moment correlation and linear regression tests. RESULTS: Forty-four patients were included in the study. A statistically significant correlation was found between the majority of patella height ratios. On X-ray, the strongest correlation (r = 0.92, p < 0.001) and regression (R2 = 0.85, p < 0.001) coefficients were between the Blackburne-Peel and Caton-Dechamps ratios, with the formula; CD = 0.20 + (0.95xBP). On MRI, the strongest correlation (r = - 0.84, p < 0.001) and regression (R2 = 0.71, p < 0.001) coefficients were between the Patellophyseal index and Patellotrochlear index, with the formula; PP = 1.02-(1.10xPT). CONCLUSION: The formulae produced in this study can predict the value of one patella height ratio when the results of another are known. This could facilitate systematic reviews and meta-analyses by allowing the pooling together of data from many studies.

Affine Deformation and Self-Assembly Alignment in Hydrogel Nanocomposites.

Tailoring the order in hierarchical structures is a key goal of bioinspired nanocomposite design. Recently, nacre-like materials have been developed by solvent evaporation methods that are scalable and attain advanced functionalities. However, understanding the alignment mechanisms of 2D fillers, nanosheets, or platelets remains challenging. This work explores possible pathways for nanocomposite ordering via orientation distribution functions. We demonstrate how the immobilization of 2D materials via (pseudo)network formation is crucial to alignment based on evaporation. We show a modified affine deformation model that describes such evaporative methods. In this, a gel network develops enough yield stress and uniformly deforms as drying proceeds, along with the immobilized particles, causing an in-plane orientation. Herein, we tested the dominance of this approach by using a thermo-reversible gel for rapid montmorillonite (MMT) particle fixation. We researched gelatin/MMT as a model system to investigate the effects of high loadings, orientational order, and aspect ratio. The nacre-like nanocomposites showed a semiconstant order parameter (⟨P2⟩ ∼ 0.7) over increasing nanofiller content up to 64 vol % filler. This remarkable alignment resulted in continuously improved mechanical and water vapor barrier properties over unusually large filler fractions. Some variations in stiffness and diffusion properties were observed, possibly correlated to the applied drying conditions of the hybrid hydrogels. The affine deformation strategy holds promise for developing next-generation advanced materials with tailored properties even at (very) high filler loadings. Furthermore, a gelling approach offers the advantages of simplicity and versatility in the formulation of the components, which is useful for large-scale fabrication methods.

Systematic Study of the Nanostructures of Exfoliated Polymer Nanocomposites.

High-performance bioinspired materials have shown rapid development over the last decade. Examples are brick-and-mortar hierarchical structures, which are often achieved via solvent evaporation. Although good properties are claimed, most systems are composed of stacked or intercalated platelets. Exfoliation is a crucial step to give ultimate anisotropic properties, e.g., thermal, mechanical, and barrier properties. We propose a general framework for all the various types of micro-scale structures that should be distinguished for 2D filler nanocomposites. In particular, the exfoliated state is systematically explored by the immobilization of montmorillonite platelets via (gelatin) hydrogelation. Scattering techniques were used to evaluate this strategy at the level of the particle dispersion and the regularity of spatial arrangement. The gelatin/montmorillonite exfoliated nanostructures are fully controlled by the filler volume fraction since the observed gallery d-spacings perfectly fall onto the predicted values. Surprisingly, X-ray analysis also revealed short- and quasi long-range arrangement of the montmorillonite clay at high loading.

Design Rules for Binary Bisamide Gelators: toward Gels with Tailor-Made Structures and Properties.

This study intends to develop design rules for binary mixture of gelators that govern their assembly behavior and subsequently explore the impact of their supramolecular assembly patterns on the gels' rheological properties. To achieve these goals, nBA gelators with odd and even parities [n-methylene spacers between the amide groups (n = 5-10) and 17 carbons at each end] were blended at different ratios. Such bisamides with simple structures were selected to study because their different spacer lengths offer the possibility to have matching or non-matching hydrogen bonds. The results show that the assembly behavior of binary mixtures of bisamide gelators is the same in the solid and gel states. Binary mixtures of gelators, which only differ two methylene moieties in the spacer length, form compounds and co-assemble into fibers and sheets observed for (5BA)1(7BA)1 and (6BA)1(8BA)1 mixtures, respectively. Binary gelator mixtures of the same parity and a larger spacer length difference still lead to mixing for the odd parity couple (5BA)1(9BA)1), but to partial phase separation for the even parity mixture (6BA)1(10BA)1. Binary mixtures of gelators of different parities gave complete phase separation in the solid state, and self-sorted gels consisting of discrete fibers and sheets in the gels of (5BA)3(6BA)1 and (5BA)3(10BA)1. The even-even binary gels (20 wt %) consisting of co-assembled sheets show higher G' than odd-odd binary gels (20 wt %) consisting of co-assembled fibers. In general, the self-sorting of odd and even molecules into the separate primary structures results in a dramatic decrease of G' compared to the co-assembled gels (20 wt %), except for (5BA)1(9BA)1 gel (20 wt %). It might be due to larger woven spheres in (5BA)1(9BA)1 gel (20 wt %), which probably have a less entangled gel network.

Supramolecular Arrangement and Rheological Properties of Bisamide Gels.

We report a systematic study of the gelation behavior of nBA gelators in xylene, with odd and even n-methylene spacers between the amide groups (n = 5-10) and 17 carbons at each end. The melting temperatures (Tm0) of nBA gels are obtained from fitting our DSCN(T) model to the experimental DSC data. The found Tm0 of nBA gels is about 35 °C lower than Tm0 of the pure nBA gelators. This is reasonably well explained by a simple model combining theories of Flory-Huggins and Gibbs free energy of melting (FHM model). We attribute this depression to an increase in entropy upon melting of the gel due to mixing with the solvent. The odd-even alternation in Tm0 of nBA gels, which was also found for the nBA gelators, indicates that the solid structures inside the gels are somewhat similar. This was studied using XRD: similar 00l reflections were found in the XRD patterns of all nBA gels and their nBA gelators. For even nBA gels, the same reflections in the 19-25° (2θ) region confirm that the sheetlike supramolecular structure of the gels is analogous to the lamellar structure of the solid gelators. For odd nBA gels, a slight difference in the reflections around 20-25° (2θ) implies a somewhat different side-by-side packing of odd nBA gels compared to the solid state. This variation is found for all the odd gels, and indeed, they show distinctly different morphologies compared to the even nBA gels. The possible effect of this on the rheological properties is discussed using some inspiration from the Halpin-Tsai model for composites where nBA gels are considered to be analogous to composite materials. The change of the storage modulus (G') with the shape factor of woven fibers and sheets in nBA gels (20 wt %) indicates that a rheological odd-even effect might indeed be present.

The Glass Transition Temperature of Heterogeneous Biopolymer Systems.

Biopolymers are abundant, renewable, and biodegradable resources. However, bio-based materials often require toughening additives, like (co)polymers or small plasticizing molecules. Plasticization is monitored via the glass transition temperature versus diluent content. To describe this, several thermodynamic models exist; nevertheless, most expressions are phenomenological and lead to over-parametrization. They also fail to describe the influence of sample history and the degree of miscibility via structure-property relationships. We propose a new model to deal with semi-compatible systems: the generalized mean model, which can classify diluent segregation or partitioning. When the constant kGM is below unity, the addition of plasticizers has hardly any effect, and in some cases, even anti-plasticization is observed. On the other hand, when the kGM is above unity, the system is highly plasticized even for a small addition of the plasticizer compound, which indicates that the plasticizer locally has a higher concentration. To showcase the model, we studied Na-alginate films with increasing sizes of sugar alcohols. Our kGM analysis showed that blends have properties that depend on specific polymer interactions and morphological size effects. Finally, we also modeled other plasticized (bio)polymer systems from the literature, concluding that they all tend to have a heterogeneous nature.

Iron and Manganese Alginate for Rechargeable Battery Electrodes.

We present a sustainable, inherently safe battery chemistry that is based on widely available and cheap materials, that is, iron and manganese hosted in alginate bio-material known from the food and medical industry. The resulting battery can be recycled to allow circularity. The electrodes were synthesised by the alginate caging the multi-valent metals to form a hydrogel in an aqueous environment. Characterisation includes FTIR, XPS and Mössbauer spectroscopy. The electrochemical performance of the electrodes was investigated by performing cyclic voltammetry (CV) and (dis)charge experiments. Mn and Fe ions show good co-ordination with the alginic acid with higher oxidation states demonstrating complex bonding behaviour. The non-optimised iron and manganese alginate electrodes already exhibit a cycling efficiency of 98% and 69%, respectively. This work shows that Fe and Mn atomically disperse in a bio-based host material and can act as electrodes in an aqueous battery chemistry. While demonstrated at cell level, it is furthermore explained how these materials can form the basis for a (semi-solid) flow cell.

Molecular Arrangement and Thermal Properties of Bisamide Organogelators in the Solid State.

The crystal structure and phase behavior of bisamide gelators are investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy, X-ray diffraction (XRD), and molecular modeling, aiming at a better understanding of bisamide gel systems. A homologous series of bisamide model compounds (nBAs) was prepared with the (CH2)n spacer between the two amide groups, where n varies from 5 to 10, and with two symmetric C17 alkyl tails. With increasing spacer length, the thermal properties show a clear odd-even effect, which was characterized using our newly developed analytical model DSCN(T). Using XRD, all studied nBA compounds turn out to have a layer-like structure. The XRD patterns of the odd BA series are very similar but show marked differences compared to the XRD patterns of the even series, which in turn are very similar. The odd-membered 5BA molecules are nearly perpendicular to the stacked layers, as described by a pseudo-orthorhombic unit cell, whereas the even-membered 6BA molecules are tilted at an angle with respect to the layer normal, as described by a triclinic unit cell. In both the odd and even series, the inter-layer interaction is the van der Waals interaction. The 6BA hydrogen bonding scheme is very similar to that of Nylon 6,10 α, unlike the 5BA H bonding scheme. The packing of the C17 alkyl tails in the 5BA layers is similar to polyethylene, and unlike 6BA. The slightly higher crystalline density of 6BA (1.038 g cm-3) as compared to 5BA (1.018 g cm-3) explains the higher melting point, higher enthalpy of fusion, and the observed shift of N-H stretch bands to higher wave numbers. The structural differences observed between the odd and even BA series reflect the different structure-directing effect of parallel versus antiparallel amide hydrogen bonding motifs. These differences underlie the observed odd-even effect in the thermal properties of nBA compounds.

High-Strength Liquid Crystal Polymer-Graphene Oxide Nanocomposites from Water.

We report on the morphology and mechanical properties of nanocomposite films derived from aqueous, hybrid liquid crystalline mixtures of rodlike aggregates of a sulfonated, all-aromatic polyamide, poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT), and graphene oxide (GO) platelets. An isothermal step at 200 °C facilitates in situ partial thermal reduction of GO to reduced GO (rGO) in nanocomposite films. X-ray scattering studies reveal that PBDT-rGO nanocomposites exhibit both higher in-plane alignment of PBDT (the order parameter increases from 0.79 to 0.9 at 1.8 vol % rGO) and alignment along the casting direction (from 0.1 to 0.6 at 1.8 vol % rGO). From dynamic mechanical thermal analysis, the interaction between PBDT and rGO causes the ß-relaxation activation energy for PBDT to increase with rGO concentration. Modulus mapping of nanocomposites using atomic force microscopy demonstrates enhanced local stiffness, indicating reinforcement. From stress-strain analysis, the average Young's modulus increases from 16 to 37 GPa at 1.8 vol % rGO and the average tensile strength increases from 210 to 640 MPa. Despite polymer alignment along the casting direction, an average transverse tensile strength of 230 MPa is obtained.

Inter- and intra-observer reliability of patellar height measurements in patients with and without patellar instability on plain radiographs and magnetic resonance imaging.

INTRODUCTION: Many patella height indices exist in the literature. There is no single universally accepted radiological assessment for measuring patella height. The aims of this study were to determine which of the commonly used indices can most reliably measure patella height and compare the findings on both plain X-ray and magnetic resonance imaging (MRI) of the knee. METHODS: This case-controlled study compared patients with recurrent patella instability (patella group) to a control group. Two observers measured six validated patella height indices on X-ray and MRI of both groups at two separate time periods. Between-group and within-group statistical analysis was undertaken of the data. The inter- and intra-observer reliability was assessed using the intraclass correlation coefficient (ICC) and the kappa measure of agreement (k). RESULTS: Forty-four patients comprised the patella group and 50 patients the control group. There was a significant difference of most indices between the two groups (p < 0.05). There was a significant difference of most indices between the two imaging modalities (p < 0.05). The Insall-Salvati ratio had the greatest inter-observer reliability for both X-ray and MRI (ICC = 0.79 to 0.97; p < 0.001) (k = 0.50 to 1.00; p < 0.001). CONCLUSION: Patella height indices significantly differ when measured on X-ray as compared to MRI. This may infer that a different set of normative values are required for each radiological modality, which we have proposed in this study. Overall, the Insall-Salvati ratio performed best and shows a high degree of intra- and inter-observer reliability on both X-ray and MRI.

Inter- and intra-rater reliability of knee flexion angle measurements on X-ray and MRI.

Background: Range of motion (ROM) is an important aspect of orthopaedic patient assessment. It can be measured at the knee joint by determining the knee flexion angle (KFA) a patient can achieve at extremes of flexion and extension. As with any measurement, the accuracy and reliability of the method used determine its validity. The consistency of magnetic resonance imaging (MRI) scans as compared to the current gold standard of X-ray remains unknown in terms of KFA evaluation. The aim of this study was to assess and compare the reliability of measuring KFA between X-ray and MRI scans. Methods: This study included 80 patients (94 knees) who had attended a specialist knee clinic due to varying knee pathologies and undergone both X-ray and MRI scans. Lateral and T1-weighted sagittal imaging views (respectively) were used to measure KFA by two trained observers independently at two separate time points, 8 weeks apart. The data was then statistically analysed and intra- and inter-observer reliability calculated using the intraclass correlation coefficient (ICC). Results: The intra-observer reliability for X-ray was 0.96 (P<0.001) and that for MRI was 0.83 (P<0.001). The inter-observer reliability for X-ray was 0.99 (P<0.001) and that for MRI was 0.81 (P<0.001). All the intra-class correlation coefficients were graded as excellent in both the intra- and inter-observer reliability analysis. Overall, the mean KFA was notably higher on X-ray measurements than that on MRI scans. There was a statistically significant difference between Time 1 and Time 2 measurements (17.7° vs. 16.8°) for MRI data (P=0.022). No significant difference was found for X-ray measurements (46.4° vs. 45.6°) in this regard (P=0.182). Conclusions: Both X-ray and MRI allow KFA to be measured with an excellent degree of reliability. However, X-ray measurements were overall superior to that of MRI mainly due to the larger field of view of the visible on-screen image which more readily identifies the anatomical landmarks required to measure KFA.

Environmentally Sensitive Luminescence Reveals Spatial Confinement, Dynamics, and Their Molecular Weight Dependence in a Polymer Glass.

Polymer glasses have an irregular structure. Among the causes for such complexity are the chemically distinct chain end groups that are the most abundant irregularities in any linear polymer. In this work, we demonstrate that chain end induced defects allow polymer glasses to create confined environments capable of hosting small emissive molecules. Using environmentally sensitive luminescent complexes, we show that the size of these confinements depends on molecular weight and can dramatically affect the photoluminescence of free or covalently bound emissive complexes. We confirm the impact of chain end confinement on the bulk glass transition in poly(methyl acrylate) (pMA) and show that commonly observed T g changes induced by the chain ends should have a structural origin. Finally, we demonstrate that the size and placement of luminescent molecular probes in pMA can dramatically affect the probe luminescence and its temperature dependence, suggesting that polymer glass is a highly irregular and complex environment, marking its difference with conventional small molecule solvents. Considering the ubiquity of luminescent glassy materials, our work lays down a blueprint for designing them with structural considerations in mind, ones where packing density and chain end size are key factors.

The Effect of Magnetic Field on Catalytic Properties in Core-Shell Type Particles.

Magnetic field effects can provide a handle on steering chemical reactions and manipulating yields. The presence of a magnetic field can influence the energy levels of the active species by interacting with their spin states. Here we demonstrate the effect of a magnetic field on the electrocatalytic processes taking place on platinum-based nanoparticles in fuel cell conditions. We have identified a shift in the potentials representing hydrogen adsorption and desorption, present in all measurements recorded in the presence of a magnetic field. We argue that the changes in electrochemical behavior are a result of the interactions between the magnetic field and the unpaired spin states of hydrogen.

Observation of transition cascades in sheared liquid crystalline polymers.

We report on the shear rheology of liquid crystalline solutions composed of charged, rodlike polymers that form supramolecular assemblies dispersed in water. Under steady shear, we observe shear thickening behavior, followed by a hesitation in the viscosity accompanied by an extremely narrow range of negative first normal stress difference. The Peclet number (Pe, shear rate normalized by rod rotational diffusivity) for the onset of shear thickening is in agreement with previous, high-resolution numerical simulations of the Doi-Edwards-Hess kinetic theory. We interrogate these dynamic responses through shear step-down experiments, revealing a complex evolution of transient responses. Detailed analysis of the stress transients provides compelling evidence that the principal axis of the rod orientational distribution, the nematic director, undergoes a cascade of transitions and coexistence of periodic states known as kayaking, tumbling, and wagging, before transitioning to steady flow alignment above a critical shear rate.

Strong graphene oxide nanocomposites from aqueous hybrid liquid crystals.

Combining polymers with small amounts of stiff carbon-based nanofillers such as graphene or graphene oxide is expected to yield low-density nanocomposites with exceptional mechanical properties. However, such nanocomposites have remained elusive because of incompatibilities between fillers and polymers that are further compounded by processing difficulties. Here we report a water-based process to obtain highly reinforced nanocomposite films by simple mixing of two liquid crystalline solutions: a colloidal nematic phase comprised of graphene oxide platelets and a nematic phase formed by a rod-like high-performance aramid. Upon drying the resulting hybrid biaxial nematic phase, we obtain robust, structural nanocomposites reinforced with graphene oxide.

Irreversible Shear-Activated Gelation of a Liquid Crystalline Polyelectrolyte.

We report irreversible, shear-activated gelation in liquid crystalline solutions of a rigid polyelectrolyte that forms rodlike assemblies (rods) in salt-free solution. At rest, the liquid crystalline solutions are kinetically stable against gelation and exhibit low viscosities. Under steady shear at, or above, a critical shear rate, a physically cross-linked, nematic gel network forms due to linear growth and branching of the rods. Above a critical shear rate, the time scale of gelation can be tuned from hours to nearly instantaneously by varying the shear rate and solution concentration. The shear-activated gels are distinct in their structure and rheological properties from thermoreversible gels. At a fixed concentration, the induction time prior to gelation decreases exponentially with the shear rate. This result indicates that shear-activated thermalization of the electrostatically stabilized rods overcomes the energy barrier for rod-rod contact, enabling rod fusion and subsequent irreversible network formation.

A deconvolution protocol of the mechanical relaxation spectrum to identify and quantify individual polymer feature contributions to self-healing.

Starting from experimental macro-rheological data, we develop a fitting protocol that succeeded in the separation of the overlapping relaxation phenomena in the dissipative regime for a set of intrinsic healing polymers healing most effectively near their glass transition temperature Tg. To allow for a proper deconvolution, the rheological master curves are converted to a relaxation spectrum (H(τ)) and this is fitted using an optimized mechanical model, e.g. the Maxwell-Weichert model. The deconvolution of overlapping segmental mobility and reversible interactions is successfully demonstrated for a set of polyimide and polyamide polymers containing none, one and two reversible dynamic features near-Tg. Through the fitting parameters, the relaxation timescale of each feature and their apparent process enthalpies are obtained. The quantitative data obtained using the fitting protocol are then compared to macroscopic healing results. As a result, a clear correspondence between the energy stored by the system to accomplish reversible (e.g. H-bonds, π-π) and chain interdiffusion relaxation transitions and the healing efficiency of such polymers are obtained. The implementation of this protocol allows for a clearer identification of the relevant mechanisms in self-healing polymers and paves the way for the development of more efficiently healable polymeric systems.

The effect of lattice strain on catalytic activity.

We report on the effect of lattice strain in three different types of core-shell electrocatalyst particles on their catalytic activity towards the oxygen reduction reaction. We decouple the changes in catalytic activity with respect to a geometrical and an energetic contribution, both of electronic origin.

Rheological investigation of specific interactions in Na Alginate and Na MMT suspension.

Here we report on a study of a rheological behavior of sodium alginate and montmorillonite suspension. We find that viscoelastic behavior of this suspension is dramatically affected with increasing volume fraction of montmorillonite platelets. Addition of montmorillonite generally leads to gel formation, which is attributed to interactions of montmorillonite and alginate via H-bonding and attraction between the positive edges of the platelets and the anionic backbone of the biopolymer. A critical concentration for the measured system was observed at 20wt.% montmorillonite, where a crossover to a gel-like structure was detected. The observed gel has a rubber plateau, which develops further with higher montmorillonite concentration. In this physical gel the relaxation maximum was detected, which is associated with the breaking and reformation of the bonds between the platelets and the biopolymer. For this transient behavior, we find that a Maxwell type viscoelasticity quite well describes the relaxation time and the observed G'-G" crossover. We believe that this gel-like behavior plays an important role in formation of highly ordered nanostructures that develop during the drying of these bio-nanocomposite suspensions.