Host-guest chemistry of polyhedral coordination cages

Chapter 1 – Introduction Chapter 2 – Synthesis, characterisation and manipulation of a three component self-assembled system Chapter 3 – Development and utilisation of a fluorescence displacement assay for guest screening Chapter 4 – Prediction of guest binding using molecular docking Chapter 5 – The use of pH changes to control guest binding in water Chapter 6 – Highly efficient catalysis of the Kemp Elimination in the cage cavit

Biological control of weeds in Australia: The last 120 years

The development of the field of biological control of weeds in Australia is described, from the first attempts in 1903 to the present day. The interest sparked by the obvious success of prickly pear program, apparent from 1930 to 1935, resulted in several programs during the next 20 years, followed by a decline in activity until the 1970s when activity increased enormously following the success of the skeleton weed program and the effective use of a plant pathogen for the first time. This momentum was maintained until the beginning of the present century with several successes and was marked by several important advances in genetic profiling, host-specificity testing, economic evaluation, conflict of interest resolution and the ecology of insect/plant interactions, including evaluation of the effectiveness of individual introductions. Biological control has proved to be a valuable and effective approach to weed management in Australia with 39% of all programs considered to produce complete or near-complete control, 30.5% partial control and an average benefit–cost ratio of 23:1. Funding for research has been variable with a decline from the late 1990s but with a significant increase again since 2020

Venous bullet embolism and subsequent endovascular retrieval – A case report and review of the literature

AbstractINTRODUCTIONVascular bullet embolism is a rare phenomenon with fewer than 200 cases reported in the literature.PRESENTATION OF CASEA 22 year-old male presented with a gunshot wound to the right lower quadrant. Imaging demonstrated a bullet lodged in his left lower quadrant. Upon operative exploration, a single hole was found in the right external iliac vein without injury into the left lower quadrant. The bullet was found to have migrated intravascularly from the right external to the left common iliac vein, and was subsequently removed endovascularly.DISCUSSIONBullet embolism occurs infrequently, with arterial more common than venous. Arterial embolization usually requires emergency operative intervention due to ischemia. While venous embolization is often asymptomatic, removal of the bullet is recommended to avoid delayed complications when possible.CONCLUSIONVenous bullet emboli should be removed endovascularly whenever technically possible

Highly selective CO2 vs. N2 adsorption in the cavity of a molecular coordination cage

Two M8L12 cubic coordination cages, as desolvated crystalline powders, preferentially adsorb CO2 over N2 with ideal selectivity CO2/N2 constants of 49 and 30 at 298 K. A binding site for CO2 is suggested by crystallographic location of CS2 within the cage cavity at an electropositive hydrogen-bond donor site, potentially explaining the high CO2/N2 selectivity compared to other materials with this level of porosity

Implementation of and Early Outcomes From Anal Cancer Screening at a Community-Engaged Health Care Facility Providing Care to Nigerian Men Who Have Sex With Men.

PurposeAnal cancer risk is substantially higher among HIV-infected men who have sex with men (MSM) as compared with other reproductive-age adults, but screening is rare across sub-Saharan Africa. We report the use of high-resolution anoscopy (HRA) as a first-line screening tool and the resulting early outcomes among MSM in Abuja, Nigeria.MethodsFrom August 2016 to August 2017, 424 MSM enrolled in an anal cancer screening substudy of TRUST/RV368, a combined HIV prevention and treatment cohort. HRA-directed biopsies were diagnosed by histology, and ablative treatment was offered for high-grade squamous intraepithelial lesions (HSIL). HRA proficiency was assessed by evaluating the detection of squamous intraepithelial lesions (SIL) over time and the proportion biopsied. Prevalence estimates of low-grade squamous intraepithelial lesions and HSIL with 95% CIs were calculated. Multinomial logistic regression was used to identify those at the highest risk of SIL.ResultsMedian age was 25 years (interquartile range [IQR], 22-29), median time since sexual debut was 8 years (IQR, 4-12), and 59% (95% CI, 54.2% to 63.6%) were HIV infected. Rate of detection of any SIL stabilized after 200 screenings, and less than 20% had two or more biopsies. Preliminary prevalence estimates of low-grade squamous intraepithelial lesions and HSIL were 50.0% (95% CI, 44.7% to 55.3%) and 6.3% (95% CI, 4.0% to 9.3%). HIV infection, at least 8 years since anal coital debut, concurrency, and external warts were independently statistically associated with SIL.ConclusionProficiency with HRA increased with experience over time. However, HSIL detection rates were low, potentially affected by obstructed views from internal warts and low biopsy rates, highlighting the need for ongoing evaluation and mentoring to validate this finding. HRA is a feasible first-line screening tool at an MSM-friendly health care facility. Years since anal coital debut and external warts could prioritize screening

High-fidelity conformation of graphene to SiO2 topographic features

Strain engineering of graphene through interaction with a patterned substrate offers the possibility of tailoring its electronic properties, but will require detailed understanding of how graphene's morphology is determined by the underlying substrate. However, previous experimental reports have drawn conflicting conclusions about the structure of graphene on SiO2. Here we show that high-resolution non-contact atomic force microscopy of SiO2 reveals roughness at the few-nm length scale unresolved in previous measurements, and scanning tunneling microscopy of graphene on SiO2 shows it to be slightly smoother than the supporting SiO2 substrate. Quantitative analysis of the competition between bending rigidity of the graphene and adhesion to the substrate explains the observed roughness of monolayer graphene on SiO2 as extrinsic, and provides a natural, intuitive description in terms of highly conformal adhesion. The analysis indicates that graphene adopts the conformation of the underlying substrate down to the smallest features with nearly 99% fidelity.Comment: 13 pages, 3 figures plus supplemental informatio

Mental health in UK Biobank: development, implementation and results from an online questionnaire completed by 157 366 participants

Background UK Biobank is a well-characterised cohort of over 500 000 participants that offers unique opportunities to investigate multiple diseases and risk factors. Aims An online mental health questionnaire completed by UK Biobank participants was expected to expand the potential for research into mental disorders. Method An expert working group designed the questionnaire, using established measures where possible, and consulting with a patient group regarding acceptability. Case definitions were defined using operational criteria for lifetime depression, mania, anxiety disorder, psychotic-like experiences and self-harm, as well as current post-traumatic stress and alcohol use disorders. Results 157 366 completed online questionnaires were available by August 2017. Comparison of self-reported diagnosed mental disorder with a contemporary study shows a similar prevalence, despite respondents being of higher average socioeconomic status than the general population across a range of indicators. Thirty-five per cent (55 750) of participants had at least one defined syndrome, of which lifetime depression was the most common at 24% (37 434). There was extensive comorbidity among the syndromes. Mental disorders were associated with high neuroticism score, adverse life events and long-term illness; addiction and bipolar affective disorder in particular were associated with measures of deprivation. Conclusions The questionnaire represents a very large mental health survey in itself, and the results presented here show high face validity, although caution is needed owing to selection bias. Built into UK Biobank, these data intersect with other health data to offer unparalleled potential for crosscutting biomedical research involving mental health

Pretreatment with phenoxybenzamine attenuates the radial artery's vasoconstrictor response to α-adrenergic stimuli

AbstractBackgroundAlthough the radial artery bypass conduit has excellent intermediate-term patency, it has a proclivity to vasospasm. We tested the hypothesis that brief pretreatment of a radial artery graft with the irreversible adrenergic antagonist phenoxybenzamine attenuates the vasoconstrictor response to the vasopressors phenylephrine and norepinephrine compared with the currently used papaverine/lidocaine.MethodsSegments of human radial artery grafts were obtained after a 30-minute intraoperative pretreatment with a solution containing 20 mL of heparinized blood, 0.4 mL of papaverine (30 mg/mL), and 1.6 mL of lidocaine (1%). The segments were transported to the laboratory and placed into a bath containing Krebs-Henseleit solution and 10, 100, or 1000 μmol/L phenoxybenzamine or vehicle. The segments were tested in organ chambers for contractile responses to increasing concentrations of phenylephrine and norepinephrine (0.5-15 μmol/L).ResultsContractile responses to 15 μmol/L phenylephrine in control radial artery segments averaged 44.2% ± 9.1% of the maximal contractile response to 30 mmol/L KCl. Papaverine/lidocaine modestly attenuated contraction to 15 μmol/L phenylephrine (32.1% ± 5.9%; P = .22), but 1000 μmol/L phenoxybenzamine completely abolished radial artery contraction (−7.2% ± 4.4%; P < .001). The effect of 10 and 100 μmol/L phenoxybenzamine on attenuating vasocontraction was intermediate between 1000 μmol/L phenoxybenzamine and papaverine/lidocaine. Responses to 15 μmol/L norepinephrine in control radial artery segments averaged 54.7% ± 7.5% of maximal contraction to 30 mmol/L KCl. Papaverine/lidocaine modestly attenuated the contraction response of radial artery segments (35.6% ± 5.1%; P = .04). In contrast, 1000 μmol/L phenoxybenzamine showed the greatest attenuation of norepinephrine-induced contraction (−10.5% ± 2.0%; P < .001).ConclusionsA brief pretreatment of the human radial artery bypass conduit with 1000 μmol/L phenoxybenzamine completely attenuates the vasoconstrictor responses to the widely used vasopressors norepinephrine and phenylephrine. Papaverine/lidocaine alone did not block vasoconstriction to these α-adrenergic agonists

CfAIR2: Near Infrared Light Curves of 94 Type Ia Supernovae

CfAIR2 is a large homogeneously reduced set of near-infrared (NIR) light curves for Type Ia supernovae (SN Ia) obtained with the 1.3m Peters Automated InfraRed Imaging TELescope (PAIRITEL). This data set includes 4607 measurements of 94 SN Ia and 4 additional SN Iax observed from 2005-2011 at the Fred Lawrence Whipple Observatory on Mount Hopkins, Arizona. CfAIR2 includes JHKs photometric measurements for 88 normal and 6 spectroscopically peculiar SN Ia in the nearby universe, with a median redshift of z~0.021 for the normal SN Ia. CfAIR2 data span the range from -13 days to +127 days from B-band maximum. More than half of the light curves begin before the time of maximum and the coverage typically contains ~13-18 epochs of observation, depending on the filter. We present extensive tests that verify the fidelity of the CfAIR2 data pipeline, including comparison to the excellent data of the Carnegie Supernova Project. CfAIR2 contributes to a firm local anchor for supernova cosmology studies in the NIR. Because SN Ia are more nearly standard candles in the NIR and are less vulnerable to the vexing problems of extinction by dust, CfAIR2 will help the supernova cosmology community develop more precise and accurate extragalactic distance probes to improve our knowledge of cosmological parameters, including dark energy and its potential time variation.Comment: 31 pages, 15 figures, 10 tables. Accepted to ApJS. v2 modified to more closely match journal versio

Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage.

The hollow cavities of coordination cages can provide an environment for enzyme-like catalytic reactions of small-molecule guests. Here, we report a new example (catalysis of the Kemp elimination reaction of benzisoxazole with hydroxide to form 2-cyanophenolate) in the cavity of a water-soluble M8L12 coordination cage, with two features of particular interest. First, the rate enhancement is among the largest observed to date: at pD 8.5, the value of kcat/kuncat is 2 × 10(5), due to the accumulation of a high concentration of partially desolvated hydroxide ions around the bound guest arising from ion-pairing with the 16+ cage. Second, the catalysis is based on two orthogonal interactions: (1) hydrophobic binding of benzisoxazole in the cavity and (2) polar binding of hydroxide ions to sites on the cage surface, both of which were established by competition experiments