Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions

Two applications of a radical trap based on a homolytic substitution reaction (SH2') are presented for the trapping of short-lived radical intermediates in organic reactions. The first example is a photochemical cyanomethylation catalyzed by a Ru complex. Two intermediate radicals in the radical chain propagation have been trapped and detected using mass spectrometry (MS), along with the starting materials, products and catalyst degradation fragments. Although qualitative, these results helped to elucidate the reaction mechanism. In the second example, the trapping method was applied to study the radical initiation catalyzed by a triethylboronoxygen mixture. In this case, the concentration of trapped radicals was sufficiently high to enable their detection by nuclear magnetic resonance (NMR). Quantitative measurements made it possible to characterize the radical flux in the system under different reaction conditions (including variations of solvent, temperature and concentration) where modelling was complicated by chain reactions and heterogeneous mass transfer

Was facial width-to-height ratio subject to sexual selection pressures? A life course approach

Sexual selection researchers have traditionally focused on adult sex differences; however, the schedule and pattern of sex-specific ontogeny can provide insights unobtainable from an exclusive focus on adults. Recently, it has been debated whether facial width-to-height ratio (fWHR; bi-zygomatic breadth divided by midface height) is a human secondary sexual characteristic (SSC). Here, we review current evidence, then address this debate using ontogenetic evidence, which has been under-explored in fWHR research. Facial measurements were collected from 3D surface images of males and females aged 3 to 40 (Study 1; US European-descent, n = 2449), and from 2D photographs of males and females aged 7 to 21 (Study 2; Bolivian Tsimane, n = 179), which were used to calculate three fWHR variants (which we call fWHRnasion, fWHRstomion, and fWHRbrow) and two other common facial masculinity ratios (facial width-to-lower-face-height ratio, fWHRlower, and cheekbone prominence). We test whether the observed pattern of facial development exhibits patterns indicative of SSCs, i.e., differential adolescent growth in either male or female facial morphology leading to an adult sex difference. Results showed that only fWHRlower exhibited both adult sex differences as well as the classic pattern of ontogeny for SSCs—greater lower-face growth in male adolescents relative to females. fWHRbrow was significantly wider among both pre- and post-pubertal males in the Bolivian Tsimane sample; post-hoc analyses revealed that the effect was driven by large sex differences in brow height, with females having higher placed brows than males across ages. In both samples, all fWHR measures were inversely associated with age; that is, human facial growth is characterized by greater relative elongation in the mid-face and lower face relative to facial width. This trend continues even into middle adulthood. BMI was also a positive predictor of most of the ratios across ages, with greater BMI associated with wider faces. Researchers collecting data on fWHR should target fWHRlower and fWHRbrow and should control for both age and BMI. Researchers should also compare ratio approaches with multivariate techniques, such as geometric morphometrics, to examine whether the latter have greater utility for understanding the evolution of facial sexual dimorphism

Unscreened Hartree-Fock calculations for metallic Fe, Co, Ni, and Cu from ab-initio Hamiltonians

Unscreened Hartree-Fock approximation (HFA) calculations for metallic Fe, Co, Ni, and Cu are presented, by using a quantum-chemical approach. We believe that these are the first HFA results to have been done for crystalline 3d transition metals. Our approach uses a linearized muffin-tin orbital calculation to determine Bloch functions for the Hartree one-particle Hamiltonian, and from these obtains maximally localized Wannier functions, using a method proposed by Marzari and Vanderbilt. Within this Wannier basis all relevant one-particle and two-particle Coulomb matrix elements are calculated. The resulting second-quantized multi-band Hamiltonian with ab-initio parameters is studied within the simplest many-body approximation, namely the unscreened, self-consistent HFA, which takes into account exact exchange and is free of self-interactions. Although the d-bands sit considerably lower within HFA than within the local (spin) density approximation L(S)DA, the exchange splitting and magnetic moments for ferromagnetic Fe, Co, and Ni are only slightly larger in HFA than what is obtained either experimentally or within LSDA. The HFA total energies are lower than the corresponding LSDA calculations. We believe that this same approach can be easily extended to include more sophisticated ab-initio many-body treatments of the electronic structure of solids.Comment: 11 papes, 7 figures, 5 table

Economics of some soil conservation practices

In applying conservation and fertility improvement plans, farmers have a choice between alternative combinations of land use, fertilizer applications and erosion control practices. Within limits, they may choose between different rotations and different fertilizer applications combined with different erosion control practices and still farm the land in accordance with the soil capabilities. While land use in accordance with soil capabilities and appropriate fertilization is basic to soil conservation, these measures need to be supplemented by supporting conservation practices such as contouring, sod waterways, mulching, drainage, flumes, etc., if soil is to be conserved and improved most efficiently. Successful conservation farming (that system which will increase total farm production, build up soil fertility, control erosion and maximize earnings) cannot be tailor-made to fit all farms but involves consideration of each individual\u27s situation. The farmer (and those working with him) must analyze his problem to determine his costs and returns for the farm as a whole under alternative combinations of crops, fertilization and supporting conservation measures to determine which system will best fit his capital position and abilities and still do the conservation job

SNPs associated with testosterone levels influence human facial morphology

Many factors influence human facial morphology, including genetics, age, nutrition, biomechanical forces, and endocrine factors. Moreover, facial features clearly differ between males and females, and these differences are driven primarily by the influence of sex hormones during growth and development. Specific genetic variants are known to influence circulating sex hormone levels in humans, which we hypothesize, in turn, affect facial features. In this study, we investigated the effects of testosterone-related genetic variants on facial morphology. We tested 32 genetic variants across 22 candidate genes related to levels of testosterone, sex hormone-binding globulin (SHGB) and dehydroepiandrosterone sulfate (DHEAS) in three cohorts of healthy individuals for which 3D facial surface images were available (Pittsburgh 3DFN, Penn State and ALSPAC cohorts; total n = 7418). Facial shape was described using a recently developed extension of the dense-surface correspondence approach, in which the 3D facial surface was partitioned into a set of 63 hierarchically organized modules. Each variant was tested against each of the facial surface modules in a multivariate genetic association-testing framework and meta-analyzed. Additionally, the association between these candidate SNPs and five facial ratios was investigated in the Pittsburgh 3DFN cohort. Two significant associations involving intronic variants of SHBG were found: both rs12150660 (p = 1.07E-07) and rs1799941 (p = 6.15E-06) showed an effect on mandible shape. Rs8023580 (an intronic variant of NR2F2-AS1) showed an association with the total and upper facial width to height ratios (p = 9.61E-04 and p = 7.35E-04, respectively). These results indicate that testosterone-related genetic variants affect normal-range facial morphology, and in particular, facial features known to exhibit strong sexual dimorphism in humans

Ampullary cancers harbor ELF3 tumor suppressor gene mutations and exhibit frequent WNT dysregulation

The ampulla of Vater is a complex cellular environment from which adenocarcinomas arise to form a group of histopathologically heterogenous tumors. To evaluate the molecular features of these tumors, 98 ampullary adenocarcinomas were evaluated and compared to 44 distal bile duct and 18 duodenal adenocarcinomas. Genomic analyses revealed mutations in the WNT signaling pathway among half of the patients and in all three adenocarcinomas irrespective of their origin and histological morphology. These tumors were characterized by a high frequency of inactivating mutations of ELF3, a high rate of microsatellite instability, and common focal deletions and amplifications, suggesting common attributes in the molecular pathogenesis are at play in these tumors. The high frequency of WNT pathway activating mutation, coupled with small-molecule inhibitors of β-catenin in clinical trials, suggests future treatment decisions for these patients may be guided by genomic analysis