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Identification of Ion-Pair Structures in Solution by Vibrational Stark Effects. - The journal of physical chemistry. B
Ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and non-metal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the Î½(Câ‰¡N) infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of non-metal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by 1) the solvent-dependence of ion-pair populations, 2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and 3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the Î½(Câ‰¡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.
Iodixanol Has a Favourable Fibrinolytic Profile Compared to Iohexol in Cardiac Patients Undergoing Elective Angiography: A Double-Blind, Randomized, Parallel Group Study. - PloS one
There is no consensus and a limited evidence base for choice of contrast agents (CA) in angiography. This study evaluated the impact of iohexol and iodixanol CA on fibrinolytic factors (tissue plasminogen activator [t-PA] and plasminogen activator inhibitor-1 [PAI-1]), as well as platelet-monocyte conjugates in cardiac patients undergoing elective angiography in a double-blind, randomised parallel group study.Patients (men, 50-70 years old; n = 12) were randomised to receive either iohexol (Omnipaque; n = 6) or iodixanol (Visipaque; n = 6) during elective angiography at Raigmore Hospital, Inverness, UK. Arterial and venous blood samples were drawn prior to CA delivery and following angiography. Assessment of platelet-monocyte conjugation, t-PA and PAI-1 antigen and activity was conducted in samples pre- and post-angiography.Plasma t-PA antigen was depressed equally in the study groups after angiography, but there was a greater reduction in PAI-1 antigen in the group receiving iodixanol. These findings corresponded to a substantial reduction in t-PA activity in patients receiving iohexol, with no change in those receiving iodixanol (P = 0.023 between the CA groups). Both CAs caused a reduction in platelet-monocyte conjugation, with no difference between the groups. No adverse events were reported during the trial.Avoiding reduced plasma t-PA activity might be an important consideration in choosing iodixanol over iohexol in patients at risk of thrombosis following angiography. The trial is registered on the ISRCTN register (ISRCTN51509735) and funded by the Coronary Thrombosis Trust and National Health Service (Highland) R&D Endowments. The funders had no influence over study design or reporting.Controlled-Trials.com ISRCTN51509735.
Correction: Evaluation of the Genetic Basis of Familial Aggregation of Pacemaker Implantation by a Large Next Generation Sequencing Panel. - PloS one
[This corrects the article DOI: 10.1371/journal.pone.0143588.].
Optimal Population-Level Infection Detection Strategies for Malaria Control and Elimination in a Spatial Model of Malaria Transmission. - PLoS computational biology
Mass campaigns with antimalarial drugs are potentially a powerful tool for local elimination of malaria, yet current diagnostic technologies are insufficiently sensitive to identify all individuals who harbor infections. At the same time, overtreatment of uninfected individuals increases the risk of accelerating emergence of drug resistance and losing community acceptance. Local heterogeneity in transmission intensity may allow campaign strategies that respond to index cases to successfully target subpatent infections while simultaneously limiting overtreatment. While selective targeting of hotspots of transmission has been proposed as a strategy for malaria control, such targeting has not been tested in the context of malaria elimination. Using household locations, demographics, and prevalence data from a survey of four health facility catchment areas in southern Zambia and an agent-based model of malaria transmission and immunity acquisition, a transmission intensity was fit to each household based on neighborhood age-dependent malaria prevalence. A set of individual infection trajectories was constructed for every household in each catchment area, accounting for heterogeneous exposure and immunity. Various campaign strategies-mass drug administration, mass screen and treat, focal mass drug administration, snowball reactive case detection, pooled sampling, and a hypothetical serological diagnostic-were simulated and evaluated for performance at finding infections, minimizing overtreatment, reducing clinical case counts, and interrupting transmission. For malaria control, presumptive treatment leads to substantial overtreatment without additional morbidity reduction under all but the highest transmission conditions. Compared with untargeted approaches, selective targeting of hotspots with drug campaigns is an ineffective tool for elimination due to limited sensitivity of available field diagnostics. Serological diagnosis is potentially an effective tool for malaria elimination but requires higher coverage to achieve similar results to mass distribution of presumptive treatment.
Polyhalogenated Indoles from the Red Alga Rhodophyllis membranacea: The First Isolation of Bromo-Chloro-Iodo Secondary Metabolites. - Journal of natural products
An unusual tetrahalogenated indole with the exceptionally rare inclusion of the three halogens bromine, chlorine, and iodine was found using mass spectrometry within a fraction of a semipurified extract obtained from the red alga Rhodophyllis membranacea. We report herein the isolation and structure elucidation, using a combination of NMR spectroscopy and mass spectrometry, of 11 new tetrahalogenated indoles (1-11), including four bromochloroiodoindoles (5-7, 10). Several were evaluated for cytotoxic and antifungal activities against the HL-60 promyelocytic cell line and Saccharomyces cerevisiae, respectively.
YouTube and 'psychiatry'. - BJPsych bulletin
YouTube is a video-sharing website that is increasingly used to share and disseminate health-related information, particularly among younger people. There are reports that social media sites, such as YouTube, are being used to communicate an anti-psychiatry message but this has never been confirmed in any published analysis of YouTube clip content. This descriptive study revealed that the representation of 'psychiatry' during summer 2012 was predominantly negative. A subsequent smaller re-analysis suggests that the negative portrayal of 'psychiatry' on YouTube is a stable phenomenon. The significance of this and how it could be addressed are discussed.
Evaluation of the Genetic Basis of Familial Aggregation of Pacemaker Implantation by a Large Next Generation Sequencing Panel. - PloS one
The etiology of conduction disturbances necessitating permanent pacemaker (PPM) implantation is often unknown, although familial aggregation of PPM (faPPM) suggests a possible genetic basis. We developed a pan-cardiovascular next generation sequencing (NGS) panel to genetically characterize a selected cohort of faPPM.We designed and validated a custom NGS panel targeting the coding and splicing regions of 246 genes with involvement in cardiac pathogenicity. We enrolled 112 PPM patients and selected nine (8%) with faPPM to be analyzed by NGS.Our NGS panel covers 95% of the intended target with an average of 229x read depth at a minimum of 15-fold depth, reaching a SNP true positive rate of 98%. The faPPM patients presented with isolated cardiac conduction disease (ICCD) or sick sinus syndrome (SSS) without overt structural heart disease or identifiable secondary etiology. Three patients (33.3%) had heterozygous deleterious variants previously reported in autosomal dominant cardiac diseases including CCD: LDB3 (p.D117N) and TRPM4 (p.G844D) variants in patient 4; TRPM4 (p.G844D) and ABCC9 (p.V734I) variants in patient 6; and SCN5A (p.T220I) and APOB (p.R3527Q) variants in patient 7.FaPPM occurred in 8% of our PPM clinic population. The employment of massive parallel sequencing for a large selected panel of cardiovascular genes identified a high percentage (33.3%) of the faPPM patients with deleterious variants previously reported in autosomal dominant cardiac diseases, suggesting that genetic variants may play a role in faPPM.
Polya's bees: A model of decentralized decision-making. - Science advances
How do social systems make decisions with no single individual in control? We observe that a variety of natural systems, including colonies of ants and bees and perhaps even neurons in the human brain, make decentralized decisions using common processes involving information search with positive feedback and consensus choice through quorum sensing. We model this process with an urn scheme that runs until hitting a threshold, and we characterize an inherent tradeoff between the speed and the accuracy of a decision. The proposed common mechanism provides a robust and effective means by which a decentralized system can navigate the speed-accuracy tradeoff and make reasonably good, quick decisions in a variety of environments. Additionally, consensus choice exhibits systemic risk aversion even while individuals are idiosyncratically risk-neutral. This too is adaptive. The model illustrates how natural systems make decentralized decisions, illuminating a mechanism that engineers of social and artificial systems could imitate.
Malaria surveillance in low-transmission areas of Zambia using reactive case detection. - Malaria journal
Repeat national household surveys suggest highly variable malaria transmission and increasing coverage of high-impact malaria interventions throughout Zambia. Many areas of very low malaria transmission, especially across southern and central regions, are driving efforts towards sub-national elimination.Reactive case detection (RCD) is conducted in Southern Province and urban areas of Lusaka in connection with confirmed incident malaria cases presenting to a community health worker (CHW) or clinic and suspected of being the result of local transmission. CHWs travel to the household of the incident malaria case and screen individuals living in adjacent houses in urban Lusaka and within 140 m in Southern Province for malaria infection using a rapid diagnostic test, treating those testing positive with artemether-lumefantrine.Reactive case detection improves access to health care and increases the capacity for the health system to identify malaria infections. The system is useful for targeting malaria interventions, and was instrumental for guiding focal indoor residual spraying in Lusaka during the 2014/2015 spray season. Variations to maximize impact of the current RCD protocol are being considered, including the use of anti-malarials with a longer lasting, post-treatment prophylaxis.The RCD system in Zambia is one example of a malaria elimination surveillance system which has increased access to health care within rural communities while leveraging community members to build malaria surveillance capacity.
Long-term Follow-up and Outcomes in Traumatic Macular Holes. - American journal of ophthalmology
To review presenting characteristics, clinical course, and long-term visual and anatomic outcomes of patients with traumatic macular holes at a tertiary referral center.Retrospective case series.Twenty-eight consecutive patients with traumatic macular holes at a single tertiary referral center were reviewed. In addition to visual acuities and treatments throughout the clinical course, specific dimensions of the macular hole, including diameters, height, configuration, shape, and the presence of a cuff of fluid, were examined using spectral-domain optical coherence tomography (OCT).Twenty-eight patients were identified with a mean initial visual acuity (VA) of logMAR 1.3 (20/400) and a mean follow-up of 2.2 years. Eleven holes (39.3%) closed spontaneously in median 5.7Â weeks. Eleven underwent vitrectomy with a median time to intervention of 35.1Â weeks. Median time to surgery for the 5 eyes with successful hole closure was 11.0Â weeks vs 56.3Â weeks for the 6 eyes that failed to close (PÂ = .02). VA improved in closed holes (P < .01), whether spontaneously (P < .01) or via vitrectomy (PÂ = .04), but VA did not improve in holes that did not close (PÂ = .22). There was no relation between initial OCT dimensions and final hole closure status, although there was a trend, which did not reach statistical significance, toward small dimensions for those that closed spontaneously.A fairly high spontaneous closure rate was observed, with a trend toward smaller OCT dimensions. We found no relationship between hole closure and the OCT characteristics of the hole. Surgical intervention was less successful at hole closure when elected after 3Â months.Copyright Â© 2015 Elsevier Inc. All rights reserved.
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