Sulfide Oxidation by 2,6-Bis[hydroxyl(methyl)amino]-4-morpholino-1,3,5-triazinatodioxomolybdenum(VI): Mechanistic Implications with DFT Calculations for a New Class of Molybdenum(VI) Complex.

Sulfide oxidation is accomplished by a new class of dioxomolybdenum(VI) catalyst (1) that uses the tridentate 2,6-bis[hydroxyl(methyl)amino]-4-morpholino-1,3,5-triazine ligand to form a five-coordinate molybdenum(VI) center. Resonance Raman spectra show that the dioxo groups on the Mo(VI) oxygens readily exchange with water in an acetonitrile media that allows 18O labeling of catalyst 1. The model oxidation reaction was the conversion of thioanisole (2) to the corresponding sulfoxide with 4% of 1 using an equimolar amount of H2O2 in MeCN-d3. Oxygen-18 labeling experiments with either 18O-labeled 1 or 18O-labeled H2O2 are consistent with a sulfide oxygenation pathway that uses a η1-Mo(OOH) hydroxoperoxyl species (3). The hypothesized intermediate 3 is initially formed in a proton transfer reaction between 1 and H2O2. Oxidation is hypothesized via nucleophilic attack of the sulfide on 3 that is supported from a Hammett linear free-energy relationship for para-derivatives of 2. A Hammett reactivity constant (ρ) of -1.2 ± 0.2 was obtained, which is consistent with other ρ values found in prior sulfide oxidation reactions by group 6 complexes. An Eyring plot of the 2 oxidation by 1 gives an Ea of 63.0 ± 5.2 kJ/mol, which is slightly higher than that of a similar oxidation of 2 by the molybdenum(VI) complex, oxodiperoxo (pyridine-2-carboxylato)molybdate(VI) bis(pyridine-2-carboxylic acid) monohydrate (5). Computational modeling with density functional theory (DFT) of the complete reaction profile gave enthalpy and entropy of activations (64 kJ/mol and -120 J/mol·K, respectively) within 1 standard deviation of the experimental values, further supporting the hypothesized mechanism.

Controlled Enantioselective Orientation of Chiral Molecules with an Optical Centrifuge.

We report on the first experimental demonstration of enantioselective rotational control of chiral molecules with a laser field. In our experiments, two enantiomers of propylene oxide are brought to accelerated unidirectional rotation by means of an optical centrifuge. Using Coulomb explosion imaging, we show that the centrifuged molecules acquire preferential orientation perpendicular to the plane of rotation, and that the direction of this orientation depends on the relative handedness of the enantiomer and the rotating centrifuge field. The observed effect is in agreement with theoretical predictions and is reproduced in numerical simulations of the centrifuge excitation followed by Coulomb explosion of the centrifuged molecules. The demonstrated technique opens new avenues in optical enantioselective control of chiral molecules with a plethora of potential applications in differentiation, separation, and purification of chiral mixtures.

No lasting legacy: no change in reporting of women's sports in the British print media with the London 2012 Olympics and Paralympics.

BACKGROUND: The proportion of media sports coverage devoted to women is reported at between 1 and 6%. Our survey examines and compares reporting patterns before and after the 2012 Olympics and Paralympics. METHODS: We collected data on sports coverage in six national newspapers on 3 weekend days in February and March 2012, and in February 2013; ∼5 months before the opening of the 2012 Olympic Games and 5 months after the closing of the Paralympic Games. RESULTS: In 2012, 39 of 876 articles in national newspapers (4.5%) related to women's sports, compared with 22 of 755 (2.9%) in 2013; a non-significant reduction in coverage [difference 1.54%, 95% confidence interval (CI) -0.28 to 3.36). In 2012, 24 of 647 pictures (3.7%) related to women's activities, compared with 10 of 738 (1.4%) in 2013; a significant reduction in coverage (difference 2.35%; 95% CI 0.68-4.03). The median area per article was significantly greater for men in both years. CONCLUSIONS: We found a continuing bias towards men's sport in the media analysed and no evidence of improvement either before or after the 2012 Olympics and Paralympics. Increased support of women's sport in the print media could benefit individuals and influence the health of the population.

Cyclic Allene Approach to the Manzamine Alkaloid Keramaphidin B.

We report an approach to the core of the manzamine alkaloid keramaphidin B that relies on the strain-promoted cycloaddition of an azacyclic allene with a pyrone trapping partner. The cycloaddition is tolerant of nitrile and primary amide functional groups and can be complemented with a subsequent retro-Diels-Alder step. These efforts demonstrate that strained cyclic allenes can be used to build significant structural complexity and should encourage further studies of these fleeting intermediates.

Arene C-H borylation strategy enabled by a non-classical boron cluster-based electrophile.

Introducing a tri-coordinate boron-based functional group (e.g., boronic ester) into an unactivated C-H bond in the absence of directing groups is an ongoing challenge in synthetic chemistry. Despite previous developments in transition metal-catalyzed and -free approaches, C-H borylation of sterically hindered arenes remains a largely unsolved problem to date. Here, we report a synthetic strategy of a two-step, precious metal-free electrophilic C-H borylation of sterically hindered alkyl- and haloarenes to generate aryl boronic esters. The first step relies on electrophilic aromatic substitution (EAS) induced by cage-opening of Cs2[closo-B10H10], forming a 6-Ar-nido-B10H13 product containing a B-C bond, followed by a cage deconstruction of arylated decaboranes promoted by diols. The combination of these two steps allows for the preparation of aryl boronic esters that are hardly accessible by current direct C-H borylation approaches. This reaction does not require any precious metals, highly-engineered ligands, pre-functionalized boron reagents, or inert conditions. In addition, the unique properties of a non-classical boron cluster electrophile intermediate, B10H13+, afford a regioselectivity with unique steric and electronic control without the undesirable side reactions.

Prevalence and risk factors of tuberculosis disease in South African correctional facilities in 2015.

SETTING: Sixteen South African correctional facilities.OBJECTIVE: To determine the prevalence of and risk factors for tuberculosis (TB) in South African correctional facilities using data collected during a TB screening program in South African correctional facilities in 2015.DESIGN: Inmates in 16 South African correctional facilities were screened for TB from January to December 2015. Inmates reporting ≥1 TB symptom or having an abnormal computer-assisted digital chest X-ray (CXR) provided sputum. Abnormal CXRs were interpreted by a radiologist. Sputum was tested for Mycobacterium tuberculosis using Xpert® MTB/RIF. Data from 16 South African correctional facilities were used in regression analysis, and prevalence estimates calculated for 12 South African correctional facilities with >30% screening coverage.RESULTS: In 12 South African correctional facilities included in the prevalence estimates, 837 inmates had TB disease (2653/100 000) as indicated by current TB treatment or screening-identified TB by radiologist or Xpert. Previous TB was associated with increased odds of screening-identified TB in HIV-positive inmates (OR 4.3, 95%CI 2.5-7.3). For HIV-negative inmates, previous TB (adjusted OR [aOR] 4.9, 95%CI 1.7-14.1) and self-reported symptoms vs. none (1 symptom, aOR 8.8, 95%CI 1.2-67.7; >2 symptoms, aOR 21.7, 95%CI 3.0-158.8) were independently associated with increased odds of screening-identified TB.CONCLUSIONS: Routine TB screening, including CXR, is needed in South African correctional facilities to identify and refer inmates with active TB.

Control of tsetse flies (Diptera: Glossinidae) with the aid of attractants.

A high degree of control of some Glossina spp. can be achieved by trapping. This is mainly because of their adenotrophic vivaparity, and consequently very low intrinsic rates of population increase. Calculations based on basic life table data have shown that it is only necessary to catch some 1-4% of the female population per day in order to achieve effective control. This is at least 8 times less than that required for Anopheles albimanus. Much attention has been given to the size and shape of traps. In general for the Palpalis Group of species, the vertically oriented biconical trap and its derivatives are highly effective, whereas for the Morsitans Group compact or horizontally oriented shapes are more attractive. Royal blue is highly attractive, and strongest landing responses are induced either on dark surfaces or those strongly reflective in the ultraviolet. Only carbon dioxide has been identified as an attractant for the Palpalis Group, but its use in traps is impractical. In contrast, a number of attractive compounds have been identified for the Morsitans Group, but there is much variation between species and within a species at various locations. A cocktail of all known attractants, except carbon dioxide, can increase trap captures of Glossina pallidipes by 15-20 times. Attractive substances in host breath include acetone, and in urine, 4-methyl phenol and 3-n-propyl phenol. The new generation of traps, or so-called targets, usually insecticide-impregnated that do not retain attracted flies, can be highly effective for controlling tsetse populations.(ABSTRACT TRUNCATED AT 250 WORDS)

Electrostatic layer-by-layer assembly of CdSe nanorod/polymer nanocomposite thin films.

Electrostatic layer-by-layer assembly was the basis for the synthesis of multilayer nanorod/polymer composite films. Cationic and water-soluble CdSe nanorods (NRs) were synthesized and partnered with anionic polymers including poly(sodium 4-styrenesulfonate) (PSS) and two polythiophene-based photoactive polymers, sodium poly[2-(3-thienyl)-ethoxy-4-butylsulfonate (PTEBS) and poly[3-(potassium-6-hexanoate)thiophene-2,5-diyl] (P3KHT). Controlled multilayer growth is shown through UV-vis spectroscopy, cross-sectional SEM and surface analytical techniques including atomic force microscopy. The formation of an intimate nanorod/conducting polymer bulk heterojunction is confirmed through cross-sectional SEM, TEM, and scanning Auger analysis. A series of photovoltaic devices was fabricated on ITO electrodes using CdSe NRs in combination with PTEBS or P3KHT. A thorough device analysis showed that performance was limited by low short circuit current although charge transfer was confirmed in the ELBL nanocomposite thin films.

Principles of the eradication or control of tsetse flies.

The success of attempts to control African trypanosomiasis afflicting both men and animals through the destruction of the tsetse vector depends on a realistic assessment of human and ecological factors in infested regions. The complete eradication of tsetse is at present possible only in limited areas, and elsewhere the advantages of periodic control campaigns have to be weighed carefully against their cost.

The Tsetse Research Laboratory.

The Tsetse Research Laboratory in Bristol was opened in December 1962, with the initial objective of developing techniques for rearing tsetse flies on a large scale outside Africa. Its work has, however, extended greatly since then. This article highlights the research undertaken at the Laboratory, not only on the breeding of tsetse flies but also on various aspects of their biology and control.

Productivity of Glossina morsitans morsitans Westwood maintained in the laboratory, with particular reference to the sterile-insect release method.

Glossina morsitans is of great economic importance in Africa and if a mass-rearing project were to be undertaken with a view to control by the release of sterilized males it would be necessary to know the productivity that could be obtained from this species in the laboratory. Data for life tables and age-specific fecundity schedules of G. m. morsitans fed on goats or lop-eared rabbits are used to calculate outputs of viable pupae or of young adult males that would be available for disposal.For control by the sterile-male method, it is likely that pupae bred in captivity would be the organisms of choice for field release. The weekly output of viable males could be 18-25% of the total adult stock. Some implications of these findings are discussed.

Transitional cell neoplasms of the urinary bladder. Can biologic potential be predicted from histologic grading?

The concept that most transitional cell neoplasms of the urinary bladder exist as either nonaggressive lesions of low cytologic grade or aggressive anaplastic cancers is gradually gaining acceptance. The extent to which the biological potential of these neoplasms is revealed in their pathologic features is the subject of this article. Using guidelines developed in experimental models, a series of 400 transitional cell neoplasms selected for long-term follow-up were classified into the WHO system. The results indicate that (1) almost all transitional cell tumors can be grouped into low and high grades at initial presentation; (2) the low grade lesions (usually designated transitional cell carcinoma, Grade I) are benign and should be called papillomas rather than carcinomas; (3) the risk of progression is not a function of the number of recurrences for these noninvasive, low-grade, papillary tumors; (4) the high-grade neoplasms are aggressive whether papillary or nodular and account for greater than 93% of tumor-related deaths; (5) patients with high-grade lesions have a reduced life expectancy even if progression does not occur; (6) depth of invasion and growth pattern are limited as predictive factors compared with histologic grade; (7) histologic grading of the initial tumor tissue can be highly predictive of outcome.

Rationale for intravesical chemotherapy in the treatment and prophylaxis of superficial transitional cell carcinoma.

1. A thorough evaluation of the urinary tract is an integral part of the initial management of a patient with transitional cell carcinoma. The site of all urothelial abnormalities must be determined and adequate histologic material obtained and reviewed. The urothelium not involved by obvious tumor should also be evaluated by either cytology or mucosal biopsies. All patients with high grade tumor should have a biopsy from the prostatic urethra. 2. The clinician should determine the risk of progression by evaluating the tumor grade, stage, and the presence or absence of carcinoma in situ. 3. The likelihood of a recurrence following endoscopic resection of a superficial bladder tumor ranges from 20% for a solitary low grade tumor to over 90% for a patient with multifocal high grade cancer. 4. The reasons for the high incidence of a subsequent tumor include new occurrences related to the continued contact of carcinogens with the susceptible urothelium, failure to completely resect all tumor, and possibly the implantation of tumor cells on the altered urothelial surface following endoscopic resection. 5. Intravesical instillation of antineoplastic agents is capable of reducing the incidence of a subsequent tumor when used for prophylaxis. These agents are also capable of eradicating residual tumor. 6. The clinician should determine whether intravesical therapy is being used for treatment or prophylaxis. 7. Thiotepa is a relatively inexpensive and safe intravesical chemotherapeutic agent which, when used for treatment of existing tumor, will provide a complete response rate of from 35 to 45%. There is a suggestion that it is more effective in low grade than high grade tumors. Prospective randomized trials indicate that patients receiving Thiotepa are less likely to develop a subsequent tumor in a given period of time than patients who do not receive intravesical therapy. 8. Mitomycin-C will provide a complete response rate in high risk patients from 35 to 50% when used for treatment of existing tumor. Approximately 15% of such patients will progress to muscle invasion if followed for approximately three years. There are few randomized trials using Mitomycin-C to determine its efficacy for prophylaxis. 9. BCG has been used for treatment and prophylaxis of superficial bladder cancer. It is relatively inexpensive. The side effects vary with the strain. Several strains have been used but they have not been compared in randomized trials. When used for treatment, the complete response rate ranges from 50 to 65%.(ABSTRACT TRUNCATED AT 400 WORDS)