Biorefinery potential of sustainable municipal wastewater treatment using fast-growing willow.

The use of willow plantations can be a sustainable approach for treating primary municipal wastewater, potentially reducing both the environmental and economic burdens associated with conventional treatment. However, the impact of wastewater irrigation upon the willow biorefinery potential has not yet been established. To investigate this effect, three-year-old field grown willows were harvested from plots kept as either controls or irrigated with primary municipal wastewater effluent at 29.5 million L ha-1 yr-1. Biomass compositional analysis, ionic liquid pretreatment and enzymatic saccharification were assessed and differential abundance of persistent extractable phytochemicals was evaluated using untargeted metabolite profiling. Glucan significantly increased by 8% in wastewater treated trees, arabinose and galactose were significantly decreased by 8 and 29%, respectively, while xylose, mannose and lignin content were unaltered. Ionic liquid pretreatment and enzymatic saccharification efficiencies did not vary significantly, releasing >95% of the cell wall glucose and recovering 35% of the lignin. From a total of 213 phytochemical features, 83 were significantly depleted and 14 were significantly enriched due to wastewater irrigation, including flavonoids and lignan derivatives. Considered alongside increased biomass yield from wastewater irrigation (+200%), lignocellulosic bioenergy yields increased to 8.87 t glucose ha-1 yr-1 and 1.89 t ha-1 yr-1 recovered lignin, while net extractives yields increased to 1.48 t ha-1 yr-1, including phytochemicals of interest. The maintenance of glucose accessibility after low-cost ionic liquid pretreatment is promising evidence that sustainable lignocellulose bioenergy production can complement wastewater treatment. Untargeted metabolite assessment revealed some of the phytochemical toolkit employed by wastewater irrigated willows, including accumulation of flooding and salinity tolerance associated flavonoids glabraoside A and glabrene. The extractable phytochemicals underpin a novel high biomass phenotype in willow and, alongside lignocellulosic yields, could help enhance the economic feasibility of this clean wastewater treatment biotechnology through integration with sustainable biorefinery.

Evidence for the spontaneous formation of N-heterocyclic carbenes in imidazolium based ionic liquids.

We present a study of the reactions of aldehydes in ionic liquids which gives evidence for the spontaneous formation of N-heterocyclic carbenes in ionic liquids based on 1,3-dialkyl substituted imidazolium cations from the lack of a deuterium isotope effect on the reaction of these ionic liquids with aldehydes.

Solubility of alkali metal halides in the ionic liquid [C4C1im][OTf].

The solubilities of the metal halides LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbCl, CsCl, CsI, were measured at temperatures ranging from 298.15 to 378.15 K in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4C1im][OTf]). Li(+), Na(+) and K(+) salts with anions matching the ionic liquid have also been investigated to determine how well these cations dissolve in [C4C1im][OTf]. This study compares the influence of metal cation and halide anion on the solubility of salts within this ionic liquid. The highest solubility found was for iodide salts, and the lowest solubility for the three fluoride salts. There is no outstanding difference in the solubility of salts with matching anions in comparison to halide salts. The experimental data were correlated employing several phase equilibria models, including ideal mixtures, van't Hoff, the λh (Buchowski) equation, the modified Apelblat equation, and the non-random two-liquid model (NRTL). It was found that the van't Hoff model gave the best correlation results. On the basis of the experimental data the thermodynamic dissolution parameters (ΔH, ΔS, and ΔG) were determined for the studied systems together with computed gas phase metathesis parameters. Dissolution depends on the energy difference between enthalpies of fusion and dissolution of the solute salt. This demonstrates that overcoming the lattice energy of the solid matrix is the key to the solubility of inorganic salts in ionic liquids.

New experimental density data and soft-SAFT models of alkylimidazolium ([C(n)C1im]⁺) chloride (Cl⁻), methylsulfate ([MeSO4]⁻), and dimethylphosphate ([Me2PO4]⁻) based ionic liquids.

Ionic liquids have been shown to have application in several areas of importance in the context of sustainable industrial activity. One application of particular interest is the ability of certain ionic liquids to dissolve biomass. This clearly marks them as useful materials with application within biorefineries. In this contribution, we present new coarse-grained soft-SAFT models and experimental density data of chloride (Cl(-)), methylsulfate ([MeSO4](-)), and dimethylphosphate ([Me2PO4](-)) based ionic liquids which are relevant for biomass deconstruction processes. Model parameters were obtained by fitting to pure component temperature density data, and the models were subsequently tested by assessing their ability to accurately calculate viscosity and interfacial surface tension. We also developed models of mixtures of the ionic liquids with water and short-chain linear alcohols. We decomposed the contributions to the excess Gibbs energy of mixing to chemical and structural contributions, and used this to provide some insight into the driving forces for solubility of molecular species in these ionic liquids.

Understanding the polarity of ionic liquids.

The polarities of a wide range of ionic liquids have been determined using the Kamlet-Taft empirical polarity scales α, ß and π*, with the dye set Reichardt's Dye, N,N-diethyl-4-nitroaniline and 4-nitroaniline. These have been compared to measurements of these parameters with different dye sets and to different polarity scales. The results emphasise the importance of recognising the role that the nature of the solute plays in determining these scales. It is particularly noted that polarity scales based upon charged solutes can give very different values for the polarity of ionic liquids compared to those based upon neutral probes. Finally, the effects of commonplace impurities in ionic liquids are reported.

'Pointing' in the wrong direction--a case of diverticulitis presenting at the hip.

We report the case of a 73-year-old lady who was seen with an infected sinus leaking from the wound of a recently inserted right total hip joint prosthesis. Plain radiographs revealed gas shadows in the region of the wound. An intra-operative sinogram showed the sinus to be coming from a pelvic diverticular abscess and the hip to be an innocent bystander. Our case emphasises the importance of having a clear preoperative plan with relevant investigations before a radical operative procedure is undertaken, to avoid unnecessary risk to a non-infected hip prosthesis.

Piperylene sulfone: a labile and recyclable DMSO substitute.

The properties and uses of piperylene sulfone as a new, recyclable dipolar, aprotic solvent for conducting organic reactions are presented.

A simple guide to determine the magnification of radiographs and to improve the accuracy of preoperative templating.

Templates are used in the preoperative planning of many orthopaedic procedures. The magnification of the bones on preoperative radiographs can vary despite using standardised radiological techniques. Templates will give misleading measurements unless this magnification is quantified. A coin may be used to calculate the magnification, with significant improvement in the accuracy of templating (p = 0.05). A group of patients undergoing uncemented arthroplasty of the hip was at high risk for intraoperative fracture of the femur because the magnification of the radiograph was larger than that of the template.

A simple laser guide to reduce the screening time during the insertion of dynamic hip screws.

A simple laser pointer can be used to guide the radiographer to position the image intensifier during the insertion of a dynamic hip screw in the treatment of fractures of the trochanteric area of the proximal femur. This significantly reduces the screening time and, by implication, the amount of radiation for the theatre staff and patient.

Use of a laser guide to reduce screening time for the dynamic hip screw.

A prospective, randomized study was used to evaluate a laser guide to aim the image intensifier during the treatment of 52 patients with intertrochanteric fractures of the proximal femur using a dynamic hip screw. The laser guide reduces the fluoroscopic screening time by 40 per cent (P < 0.05). We conclude that laser aiming of the image intensifier has a role in training radiographers, and reducing the dosage of irradiation in theatre procedures.

Passive insufficiency of two-joint shoulder muscles.

This preliminary study examined the effects of full elbow flexion and full elbow extension on the end-point of active range of motion of shoulder flexion and shoulder extension respectively. The end-points were measured from lateral photographs of the right upper limbs of 30 men after they flexed and extended their shoulders with their elbows held in full flexion and full extension. Angular measurements showed that full elbow flexion limited shoulder flexion range of motion and that full elbow extension limited shoulder extension range of motion. The results indicated that passive muscle insufficiency of active shoulder flexion and extension was probably brought about by lengthening the triceps brachii and the biceps brachii muscles respectively. Clinicians are encouraged to considerthis passive insufficiency when measuring range of motion of shoulderflexion and extension and when implementing therapeutic interventions.

Dome osteotomy of the tibia for osteoarthritis of the knee.

Proximal tibial osteotomy is commonly performed for osteoarthritis of the knee with deformity. The results of 105 dome osteotomies have been reviewed at a minimum follow-up of one year and an average of 4.8 years. Before operation all the knees were painful, 50.5% severely; a further 45.7% disturbed sleep at night. At review 15.2% of knees were free of pain and 60% had only slight pain which did not restrict activity. The preoperative range of movement was maintained and there was only a slight tendency for radiological changes to progress, with actual improvement in some cases. No correlation was found between the correction of deformity to physiological valgus and the result. We cannot explain why tibial osteotomy produces such useful and sustained pain relief.

Tendon ruptures in the hand with particular reference to attrition ruptures in the carpal tunnel.

The mechanisms of tendon rupture in the hand are reviewed. Attrition ruptures of tendons in the carpal tunnel, other than those due to rheumatoid arthritis, are rare. A case is reported where Kienböck's avascular necrosis of the lunate caused rupture of flexor policis longus. This is the second case reported in the literature and serves as a model of attrition rupture.

Abnormal metacarpal heads in brachymesophalangy--report of a case and review of the literature.

A case of brachymesophalangy in which ossicles related to metacarpal heads became detached, causing joint locking, is presented. A distinction has been made by arthrography between this lesion and the loose bodies seen in osteochondritis dissecans, which were previously thought to be the origin of the ossicles and the cause of the locking.