Tribological evaluation of a novel hybrid for repair of articular cartilage defects

The friction and wear properties of silica/poly(tetrahydrofuran)/poly(ε-caprolactone) (SiO2/PTHF/PCL-diCOOH) hybrid materials that are proposed as cartilage tissue engineering materials were investigated against living articular cartilage. A testing rig was designed to allow testing against fresh bovine cartilage. The friction force and wear were compared for five compositions of the hybrid biomaterial articulating against freshly harvested bovine cartilage in diluted bovine calf serum. Under a non-migrating contact, the friction force increased and hence shear force applied to the opposing articular cartilage also increased, resulting in minor damage to the cartilage surface. This worse case testing scenario was used to discriminate between material formulations and revealed the increase in friction and damaged area was lowest for the hybrid containing the most silica. Further friction and wear tests on one hybrid formulation with an elastic modulus closest to that of cartilage were then conducted in a custom incubator system. This demonstrated that over a five day period the friction force, cell viability and glucosaminoglycan (GAG) release into the lubricant were similar between a cartilage-cartilage interface and the hybrid-cartilage interface, supporting the use of these materials for cartilage repair. These results demonstrate how tribology testing can play a part in the development of new materials for chondral tissue engineering

A selected ion flow tube study of the ion-molecule reactions of monochloroethene, trichloroethene and tetrachloroethene

Data for the rate coefficients and product cations of the reactions of a large number of atomic and small molecular cations with monochloroethene, trichloroethene and tetrachloroethene in a selected ion flow tube at 298 K are reported. The recombination energy of the ions range from 6.27 eV (H$_3$O$^+$) through to 21.56 eV (Ne$^+$). Collisional rate coefficients are calculated by modified average dipole orientation theory and compared with experimental values. Thermochemistry and mass balance predict the most feasible neutral products. Together with previously reported results for the three isomers of dichloroethene (J. Phys. Chem. A., 2006, 110, 5760), the fragment ion branching ratios have been compared with those from threshold photoelectron photoion coincidence spectroscopy over the photon energy range 9-22 eV to determine the importance or otherwise of long-range charge transfer. For ions with recombination energy in excess of the ionisation energy of the chloroethene, charge transfer is energetically allowed. The similarity of the branching ratios from the two experiments suggest that long-range charge transfer is dominant. For ions with recombination energy less than the ionisation energy, charge transfer is not allowed; chemical reaction can only occur following formation of an ion-molecule complex, where steric effects are more significant. The products that are now formed and their percentage yield is a complex interplay between the number and position of the chlorine atoms with respect to the C=C bond, where inductive and conjugation effects can be important

High-throughput measurement methodologies for developing nutrient-dense crops

With the development of nutrient-dense crops comes the need for analytical methodologies to enable rapid and accurate analysis of the micronutrients of interest. The analysis of provitamin A carotenoids (pVACs) and the minerals iron (Fe) and zinc (Zn) are the focus of this chapter with the considerations and commonly employed methods discussed. When analyzing samples there are various considerations to minimise analyte degradation (in the case of provitamin A) and reduce possible contamination from external sources (for Fe and Zn). Spectroscopic and chromatographic analyses are the most common analysis approaches utilised when screening for carotenoids. Spectroscopic analyses including near-infrared spectroscopy (NIRS) and iCheck are rapid and require minimal samples preparation and provide fast analysis times. The carotenoids present in the sample is dependent on the crop analyzed and resulting number and concentration of carotenoids present will impact the final decision on suitable analysis techniques. For example, in crops with high concentrations of non-pVACs, chromatographic analysis is necessary in order to accurately quantify the micronutrients. This process is able to accurately identify and quantify individual carotenoids, but requires extensive sample preparation and often long chromatographic separation analysis. When analyzing the minerals Fe and Zn, these same techniques are not suitable, but it is still important to ensure careful sample preparation to deliver accurate analytical results. Degradation of these micronutrients is not a concern, however, possible contamination from soil/ dust/ insects can lead to inaccurate results. Commonly employed analysis such as atomic absorption spectroscopy (AAS) and Inductively Coupled Plasma-Optical Emission Spectrometry ICP-OES or Inductively Coupled Plasma-Mass spectrometry (ICP-MS) require sample digestion prior to analysis and highly pure reagents and gases. These techniques are able to analyze multiple elements and have high accuracy and sensitivity but require specialised facilities and highly trained staff. The use of high-throughput analyses to complement these high-accuracy methods include colorimetric and X-ray flourescence (XRF) technologies. These approaches enable much higher throughput with simple sample preparation and enable screening for micronutrient concentration without the need for specialised facilities.Keywords: Screening, Analysis, Carotenoid, Provitamin A, Iron, Zinc, Micronutrient analysi

Focused Local Search for Random 3-Satisfiability

A local search algorithm solving an NP-complete optimisation problem can be viewed as a stochastic process moving in an 'energy landscape' towards eventually finding an optimal solution. For the random 3-satisfiability problem, the heuristic of focusing the local moves on the presently unsatisfiedclauses is known to be very effective: the time to solution has been observed to grow only linearly in the number of variables, for a given clauses-to-variables ratio $\alpha$ sufficiently far below the critical satisfiability threshold $\alpha_c \approx 4.27$. We present numerical results on the behaviour of three focused local search algorithms for this problem, considering in particular the characteristics of a focused variant of the simple Metropolis dynamics. We estimate the optimal value for the ``temperature'' parameter $\eta$ for this algorithm, such that its linear-time regime extends as close to $\alpha_c$ as possible. Similar parameter optimisation is performed also for the well-known WalkSAT algorithm and for the less studied, but very well performing Focused Record-to-Record Travel method. We observe that with an appropriate choice of parameters, the linear time regime for each of these algorithms seems to extend well into ratios $\alpha > 4.2$ -- much further than has so far been generally assumed. We discuss the statistics of solution times for the algorithms, relate their performance to the process of ``whitening'', and present some conjectures on the shape of their computational phase diagrams.Comment: 20 pages, lots of figure

The derivation of the formyl-group oxygen of chlorophyll b in higher plants from molecular oxygen.

The mechanism of formation of the formyl group of chlorophyll b has long been obscure but, in this paper, the origin of the 7-formyl-group oxygen of chlorophyll b in higher plants was determined by greening etiolated maize leaves, excised from dark-grown plants, by illumination under white light in the presence of either H218O or 18O2 and examining the newly synthesized chlorophylls by mass spectroscopy. To minimize the possible loss of 18O label from the 7-formyl substituent by reversible formation of chlorophyll b-71-gem-diol (hydrate) with unlabelled water in the cell, the formyl group was reduced to a hydroxymethyl group during extraction with methanol containing NaBH4: chlorophyll a remained unchanged during this rapid reductive extraction process. Mass spectra of chlorophyll a and [7-hydroxymethyl]-chlorophyll b extracted from leaves greened in the presence of either H218O or 18O2 revealed that 18O was incorporated only from molecular oxygen but into both chlorophylls: the mass spectra were consistent with molecular oxygen providing an oxygen atom not only for incorporation into the 7-formyl group of chlorophyll b but also for the well-documented incorporation into the 131-oxo group of both chlorophylls a and b [see Walker, C. J., Mansfield, K. E., Smith, K. M. & Castelfranco, P. A. (1989) Biochem. J. 257, 599–602]. The incorporation of isotope led to as much as 77% enrichment of the 131-oxo group of chlorophyll a: assuming identical incorporation into the 131 oxygen of chlorophyll b, then enrichment of the 7-formyl oxygen was as much as 93%. Isotope dilution by re-incorporation of photosynthetically produced oxygen from unlabelled water was negligible as shown by a greening experiment in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea. The high enrichment using 18O2, and the absence of labelling by H218O, unequivocally demonstrates that molecular oxygen is the sole precursor of the 7-formyl oxygen of chlorophyll b in higher plants and strongly suggests a single pathway for the formation of the chlorophyll b formyl group involving the participation of an oxygenase-type enzyme

Thermal analysis in oxidative and pyrolysis conditions of alkaline earth metals picolinates using the techniques:TG-DSC, DSC, MWTA, HSM and EGA (TG-DSC-FTIR and HSM-MS)

Made available in DSpace on 2019-10-06T15:58:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-10-01Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)University of HuddersfieldSynthesis, characterization, thermal stability and pyrolysis of some alkaline earth picolinates M(C6H5NO2)2⋅nH2O (where M = Mg(II), Ca(II), Sr(II) and Ba(II) and n = di (Mg), mono (Ca), hemi three (Sr) hydrated) were investigated using a range of techniques including simultaneous thermogravimetry and differential scanning calorimetry (TG–DSC), evolved gas analysis (EGA), differential scanning calorimetry (DSC), Hot-Stage microscopy (HSM), powder X-ray diffractometry (PXRD), complexometry with EDTA and elemental analysis (EA). The TG-DSC curves show that the hydrated compounds dehydrate in a single step of mass loss and the thermal stability of the anhydrous compound is little influenced from the atmosphere used. On the other hand, the mechanisms of thermal decomposition are profoundly influenced by the atmosphere used, as can also be observed in the EGA data. In addition, a comparison between two calorimetric techniques, Microwave Thermal Analysis (MWTA) and DSC, was made which showed similar profiles. Two evolved gas analysis (EGA) techniques: TG-DSC coupled to FTIR and HSM coupled to a quadrupole mass spectrometer (MS) were also used to provide additional information about the pyrolysis mechanism.Universidade Estadual Paulista (UNESP) Instituto de QuímicaThermal Methods Research Unit Department of Chemistry University of Huddersfield, HuddersfieldInstituto Federal de Educação Ciência e Tecnologia do Paraná (IFPR)Instituto Federal de Educação Ciência e Tecnologia de Rondônia (IFRO)Universidade Estadual Paulista (UNESP) Faculdade de Ciências Departamento de QuímicaUniversidade Estadual Paulista (UNESP) Instituto de QuímicaUniversidade Estadual Paulista (UNESP) Faculdade de Ciências Departamento de Químic

Investigation of shock waves in explosive blasts using fibre optic pressure sensors

The published version of this article may be accessed at the link below. Copyright @ IOP Publishing, 2006.We describe miniature all-optical pressure sensors, fabricated by wafer etching techniques, less than 1 mm(2) in overall cross-section with rise times in the mu s regime and pressure ranges typically 900 kPa (9 bar). Their performance is suitable for experimental studies of the pressure-time history for test models exposed to shocks initiated by an explosive charge. The small size and fast response of the sensors promises higher quality data than has been previously available from conventional electrical sensors, with potential improvements to numerical models of blast effects. Results from blast tests are presented in which up to six sensors were multiplexed, embedded within test models in a range of orientations relative to the shock front.Support from the UK Engineering&Physical Sciences Research Council and Dstl Fort Halstead through the MoD Joint Grants Scheme are acknowledged. WN MacPherson is supported by an EPSRC Advanced Research Fellowship

Quality of care in adult patients with inflammatory bowel disease transferring between healthcare providers: multicentre audit

Background: Inflammatory bowel disease (IBD) predominantly affects young adults at critical socioeconomic periods of their lives. There are no studies examining the process of transfer of care for adult patients with IBD changing healthcare providers. Our aims were to assess the quality of referral information provided when patients with an established IBD diagnosis transfer care between heathcare providers and to assess the impact of referral quality on patient outcome. / Methods: Retrospective data pertaining to IBD transfer of care referrals were collected from 16 hospitals across London over a 2-month period. Data were collected on patient demographics, source and content of referral and cross-referenced with an established transfer of care checklist. Patient outcome within the 6 months following transfer was also documented. / Results: 154 cases were identified, over half of which transferred due to patient relocation. Details included in transfer letters were in many cases incomplete. In over 70% of cases, the letter came from primary care, including when a tertiary opinion was sought. Although referrals from primary care contained fewer patient data points, there was no association with poor patient outcomes at 6 months. / Conclusion: This is the first study examining the quality of transfer of care in adult patients with IBD. We highlighted a significant and underreported issue and found that the majority of referrals were led by primary care. Though the inclusion in the referral of fewer data points was not associated with poor outcomes, we highlighted an area where gastroenterologists might take more responsibility to provide smooth and robust transfer of care