Aggregation behavior in water of new imidazolium and pyrrolidinium alkycarboxylates protic ionic liquids

A novel class of anionic surfactants was prepared through the neutralization of pyrrolidine or imidazole by alkylcarboxylic acids. The compounds, namely the pyrrolidinium alkylcarboxylates ([Pyrr][CnH2n+1COO]) and imidazolium alkylcarboxylates ([Im][CnH2n+1COO]), were obtained as ionic liquids at room temperature. Their aggregation behavior has been examined as a function of the alkyl chain length (from n = 5 to 8) by surface tensiometry and conductivity. Decreases in the critical micelle concentration (cmc) were obtained, for both studied PIL families, when increasing the anionic alkyl chain length (n). Surprisingly, a large effect of the alkyl chain length was observed on the minimum surface area per surfactant molecule (Amin) and, hence the maximum surface excess concentration (Gmax) when the counterion was the pyrrolidinium cation. This unusual comportment has been interpreted in term of a balance between van der Waals and coulombic interactions. Conductimetric measurements permit determination of the degree of ionization of the micelle (a) and the molar conductivity (?M) of these surfactants as a function of n. The molar conductivities at infinite dilution in water (?8) of the [Pyrr]+ and [Im]+ cations have been then determined by using the classical Kohlraush equation. Observed change in the physicochemical, surface, and micellar properties of these new protonic ionic liquid surfactants can be linked to the nature of the cation. By comparison with classical anionic surfactants having inorganic counterions, pyrrolidinium alkylcarboxylates and imidazolium alkylcarboxylates exhibit a higher ability to aggregate in aqueous solution, demonstrating their potential applicability as surfactant.

Effect of accelerated rehabilitation on function after ankle sprain: randomised controlled trial

Objective: To compare an accelerated intervention incorporating early therapeutic exercise after acute ankle sprains with a standard protection, rest, ice, compression, and elevation intervention.

Design: Randomised controlled trial with blinded outcome assessor.

Setting: Accident and emergency department and university based sports injury clinic.

Participants: 101 patients with an acute grade 1 or 2 ankle sprain.

Interventions: Participants were randomised to an accelerated intervention with early therapeutic exercise (exercise group) or a standard protection, rest, ice, compression, and elevation intervention (standard group).

Main outcome measures: The primary outcome was subjective ankle function (lower extremity functional scale). Secondary outcomes were pain at rest and on activity, swelling, and physical activity at baseline and at one, two, three, and four weeks after injury. Ankle function and rate of reinjury were assessed at 16 weeks.

Results: An overall treatment effect was in favour of the exercise group (P=0.0077); this was significant at both week 1 (baseline adjusted difference in treatment 5.28, 98.75% confidence interval 0.31 to 10.26; P=0.008) and week 2 (4.92, 0.27 to 9.57; P=0.0083). Activity level was significantly higher in the exercise group as measured by time spent walking (1.2 hours, 95% confidence interval 0.9 to 1.4 v 1.6, 1.3 to 1.9), step count (5621 steps, 95% confidence interval 4399 to 6843 v 7886, 6357 to 9416), and time spent in light intensity activity (53 minutes, 95% confidence interval 44 to 60 v 76, 58 to 95). The groups did not differ at any other time point for pain at rest, pain on activity, or swelling. The reinjury rate was 4% (two in each group).

Conclusion: An accelerated exercise protocol during the first week after ankle sprain improved ankle function; the group receiving this intervention was more active during that week than the group receiving standard care.

Angiotensin-converting enzyme inhibitors and angiotensin receptor blockers in cancer progression and survival: a systematic review

Objective: To investigate the association between angiotensin-converting enzyme inhibitors (ACEIs) and angiotensin receptor blockers (ARBs) and disease progression and survival in cancer patients.

Methods: Using terms for cancer and ACEIs/ARBs, MEDLINE, EMBASE and Web of Science were systematically searched for observational/interventional studies that used clinically relevant outcomes for cancer progression and survival.

Results: Ten studies met the inclusion criteria. Two studies showed a significant improvement in overall survival (OS) with ACEI/ARB use among patients with advanced pancreatic (HR 0.52, 95% CI 0.29–0.88) and non-small cell lung cancer (HR 0.56, 95% CI 0.33–0.95). An improvement in progression-free survival (PFS) was also reported for pancreatic cancer patients (HR 0.58, 95% CI 0.34–0.95) and patients with renal cell carcinoma (HR 0.54, p = 0.02). ACEI/ARB use was protective against breast cancer recurrence (HR 0.60, 95% CI 0.37–0.96), colorectal cancer distant metastasis (OR 0.22, 95% CI 0.08–0.65) and prostate specific antigen (PSA) failure in prostate cancer patients (p = 0.034). One study observed a worse OS (HR 2.01, 95% CI 1.00–4.05) and PFS in ACEI users with multiple myeloma (p = 0.085) while another reported an increased risk of breast cancer recurrence (HR = 1.56, 95% CI 1.02–2.39).

Conclusion: There is some evidence to suggest that ACEI or ARB use may be associated with improved outcomes in cancer patients. Larger, more robust studies are required to explore this relationship further.

Effect of preventive primary care outreach on health related quality of life among older adults at risk of functional decline: Randomised controlled trial

Objective: To evaluate the impact of a provider initiated primary care outreach intervention compared with usual care among older adults at risk of functional decline. Design: Randomised controlled trial. Setting: Patients enrolled with 35 family physicians in five primary care networks in Hamilton, Ontario, Canada. Participants Patients: were eligible if they were 75 years of age or older and were not receiving home care services. Of 3166 potentially eligible patients, 2662 (84%) completed the validated postal questionnaire used to determine risk of functional decline. Of 1724 patients who met the risk criteria, 769 (45%) agreed to participate and 719 were randomised. Intervention: The 12 month intervention, provided by experienced home care nurses in 2004-6, consisted of a comprehensive initial assessment using the resident assessment instrument for home care; collaborative care planning with patients, their families, and family physicians; health promotion; and referral to community health and social support services. Main outcome measures: Quality adjusted life years (QALYs), use and costs of health and social services, functional status, self rated health, and mortality. Results: The mean difference in QALYs between intervention and control patients during the study period was not statistically significant (0.017, 95% confidence interval -0.022 to 0.056; P=0.388). The mean difference in overall cost of prescription drugs and services between the intervention and control groups was not statistically significant, (-$C165 (£107; €118; $162), 95% confidence interval -$C16 545 to $C16 214; P=0.984). Changes over 12 months in functional status and self rated health were not significantly different between the intervention and control groups. Ten patients died in each group. Conclusions: The results of this study do not support adoption of this preventive primary care intervention for this target population of high risk older adults. Trial registration: Clinical trials NCT00134836.

Hidden costs of control: four repetitions and an extension

We report four repetitions of Falk and Kosfeld's (Am. Econ. Rev. 96(5):1611-1630, 2006) low and medium control treatments with 476 subjects. Each repetition employs a sample drawn from a standard subject pool of students and demographics vary across samples. We largely confirm the existence of hidden costs of control but, contrary to the original study, hidden costs of control are usually not substantial enough to significantly undermine the effectiveness of economic incentives. Our subjects were asked, at the end of the experimental session, to complete a questionnaire in which they had to state their work motivation in hypothetical scenarios. Our questionnaires are identical to the ones administered in Falk and Kosfeld's (Am. Econ. Rev. 96(5):1611-1630, 2006) questionnaire study. In contrast to the game play data, our questionnaire data are similar to those of the original questionnaire study. In an attempt to solve this puzzle, we report an extension with 228 subjects where performance-contingent earnings are absent i.e. both principals and agents are paid according to a flat participation fee. We observe that hidden costs significantly outweigh benefits of control under hypothetical incentives.

Selective methane bromination over sulfated zirconia in SBA-15 catalysts

Methane activation via bromination can be a feasible route with selective synthesis of mono-bromomethane. It is known that the condensation of brominated products into higher hydrocarbons can result in coking and deactivation in the presence of di-bromomethane. In this study, selective production of methyl bromide was investigated over sulfated ZrO2 included SBA-15 structures. It was observed that the higher the ZrO2 amounts the higher the conversion, while the catalyst remained >99% selective for the monobrominated methane. Over 25 mol.% ZrO2 included SBA-15 catalyst with a BET surface area of 246 m(2)/g, methane was brominated with 69% conversion at 340 degrees C and only CH3Br was selectively produced. (C) 2009 Elsevier B.V. All rights reserved

An enantio-selective chromatographic stationary phase for S-ibuprofen prepared by stoichiometric molecular imprinting

Molecularly Imprinted Polymers (MIPs) against S-ibuprofen were synthesised using a tailor made functional monomer, 2-acrylamido-4-methylpyridine, following extensive pre-polymerisation studies of template-monomer complexation. An apparent association constant of 340 +/- 22 M-1 was calculated that was subsequently corrected to account for dimerisation of ibuprofen (K-dim = 320 +/- 95 M-1) resulting in an intrinsic association constant of 715 +/- 16 M-1, consistent with previously reported values. Using the synthesised imprinted polymer as a stationary phase, complete resolution of a racemic mixture of ibuprofen was achieved in predominantly aqueous mobile phases. An imprinting factor of 10 was observed, and was found to be in agreement with the difference in the average number of binding sites between MIP and blank polymers, calculated by staircase frontal chromatography. The imprinted polymers exhibited enhanced selectivity for the templated drug over structurally related NSAIDs. When applied as sorbents in solid-phase extraction of ibuprofen from commercial tablets, urine and blood serum samples, recoveries up to 92.2% were achieved. © The Royal Society of Chemistry 2012