Activation and discovery of earth-abundant metal catalysts using sodium tert-butoxide

First-row, earth-abundant metals offer an inexpensive and sustainable alternative to precious-metal catalysts. As such, iron and cobalt catalysts have garnered interest as replacements for alkene and alkyne hydrofunctionalization reactions. However, these have required the use of air- and moisture-sensitive catalysts and reagents, limiting both adoption by the non-expert as well as applicability, particularly in industrial settings. Here, we report a simple method for the use of earth-abundant metal catalysts by general activation with sodium tert-butoxide. Using only robust air- and moisture-stable reagents and pre-catalysts, both known and, significantly, novel catalytic activities have been successfully achieved, covering hydrosilylation, hydroboration, hydrovinylation, hydrogenation and [2π+2π] alkene cycloaddition. This activation method allows for the easy use of earth-abundant metals, including iron, cobalt, nickel and manganese, and represents a generic platform for the discovery and application of non-precious metal catalysis

Late Permian palaeomagnetic data east and west of the Urals

We studied Upper Permian redbeds from two areas, one between the Urals and the Volga River in the southeastern part of Baltica and the other in north Kazakhstan within the Ural-Mongol belt, which are about 900 km apart; a limited collection of Lower-Middle Triassic volcanics from north Kazakhstan was also studied. A high-temperature component that shows rectilinear decay to the origin was isolated from most samples of all three collections. For the Late Permian of north Kazakhstan, the area-mean direction of this component is D = 224.3°, I =−56.8°, k = 161, Α 95 = 2.7°, N = 18 sites, palaeopole at 53.4°N, 161.3°E; the fold test is positive. The Triassic result ( D = 55.9°, I =+69.1°, k = 208, Α 95 = 4.2°, N = 7 sites, pole at 57.0°N, 134.1°E) is confirmed by a positive reversal test. The corresponding palaeomagnetic poles from north Kazakhstan show good agreement with the APWP for Baltica, thus indicating no substantial motion between the two areas that are separated by the Urals. Our new mean Late Permian direction for SE Baltica ( D = 42.2°, I = 39.2°, k = 94, Α 95 = 3.5°, N = 17 sites; palaeopole at 45.6°N, 170.2°E) is confirmed as near-primary by a positive tilt test and the presence of dual-polarity directions. The corresponding pole also falls on the APWP of Baltica, but is far-sided with respect to the coeval reference poles, as the observed mean inclination is shallower than expected by 13°± 4°. In principle, lower-than-expected inclinations may be attributed to one or more of the following causes: relative tectonic displacements, quadrupole and octupole terms in the geomagnetic field, higher-order harmonics (incl. secular variation) of the same field, random scatter, non-removed overprints, or inclination error during remanence acquisition and/or diagenetic compaction. Our analysis shows that most mechanisms from the above list cannot explain the observed pattern, leaving as the most likely option that it must be accounted for by inclination shallowing. Comparison with selected coeval results from eastern Baltica (all within Russia) shows that all of them are biased in the same way. This implies that they cannot be used for analysis of geomagnetic field characteristics, such as non-dipole contributions, without a more adequate knowledge of the required correction for inclination shallowing.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/71899/1/j.1365-246X.2008.03727.x.pd

High frequency of BRCA1, but not CHEK2 or NBS1 (NBN), founder mutations in Russian ovarian cancer patients

<p>Abstract</p> <p>Background</p> <p>A significant portion of ovarian cancer (OC) cases is caused by germ-line mutations in BRCA1 or BRCA2 genes. BRCA testing is cheap in populations with founder effect and therefore recommended for all patients with OC diagnosis. Recurrent mutations constitute the vast majority of BRCA defects in Russia, however their impact in OC morbidity has not been yet systematically studied. Furthermore, Russian population is characterized by a relatively high frequency of CHEK2 and NBS1 (NBN) heterozygotes, but it remains unclear whether these two genes contribute to the OC risk.</p> <p>Methods</p> <p>The study included 354 OC patients from 2 distinct, geographically remote regions (290 from North-Western Russia (St.-Petersburg) and 64 from the south of the country (Krasnodar)). DNA samples were tested by allele-specific PCR for the presence of 8 founder mutations (BRCA1 5382insC, BRCA1 4153delA, BRCA1 185delAG, BRCA1 300T>G, BRCA2 6174delT, CHEK2 1100delC, CHEK2 IVS2+1G>A, NBS1 657del5). In addition, literature data on the occurrence of BRCA1, BRCA2, CHEK2 and NBS1 mutations in non-selected ovarian cancer patients were reviewed.</p> <p>Results</p> <p>BRCA1 5382insC allele was detected in 28/290 (9.7%) OC cases from the North-West and 11/64 (17.2%) OC patients from the South of Russia. In addition, 4 BRCA1 185delAG, 2 BRCA1 4153delA, 1 BRCA2 6174delT, 2 CHEK2 1100delC and 1 NBS1 657del5 mutation were detected. 1 patient from Krasnodar was heterozygous for both BRCA1 5382insC and NBS1 657del5 variants.</p> <p>Conclusion</p> <p>Founder BRCA1 mutations, especially BRCA1 5382insC variant, are responsible for substantial share of OC morbidity in Russia, therefore DNA testing has to be considered for every OC patient of Russian origin. Taken together with literature data, this study does not support the contribution of CHEK2 in OC risk, while the role of NBS1 heterozygosity may require further clarification.</p

Association between the NBS1 E185Q polymorphism and cancer risk: a meta-analysis

<p>Abstract</p> <p>Background</p> <p>NBS1 is a key DNA repair protein in the homologous recombination repair pathway and a signal modifier in the intra-S phase checkpoint that plays important roles in maintaining genomic stability. The <it>NBS1 </it>8360G>C (<it>Glu185Gln</it>) is one of the most commonly studied polymorphisms of the gene for their association with risk of cancers, but the results are conflicting.</p> <p>Methods</p> <p>We performed a meta-analysis using 16 eligible case-control studies (including 17 data sets) with a total of 9,734 patients and 10,325 controls to summarize the data on the association between the <it>NBS1 </it>8360G>C (E185Q) polymorphism and cancer risk.</p> <p>Results</p> <p>Compared with the common 8360GG genotype, the carriers of variant genotypes (i.e., 8360 GC/CC) had a 1.06-fold elevated risk of cancer (95% CI = 1.00–1.12, <it>P </it>= 0.05) in a dominant genetic model as estimated in a fixed effect model. However, the association was not found in an additive genetic model (CC <it>vs </it>GG) (odds ratio, OR = 0.98, 95% CI = 0.85–1.13, <it>P </it>= 0.78) nor in a recessive genetic model (CC <it>vs </it>GC +GG) (OR = 0.94, 95% CI = 0.82–1.07, <it>P </it>= 0.36). The effect of the 8360G>C (E185Q) polymorphism was further evaluated in stratification analysis. It was demonstrated that the increased risk of cancer associated with 8360G>C variant genotypes was more pronounced in the Caucasians (OR = 1.07, 95% CI = 1.01–1.14, <it>P </it>= 0.03).</p> <p>Conclusion</p> <p>Our meta-analysis suggests that the <it>NBS1 </it>E185Q variant genotypes (8360 <it>GC/CC</it>) might be associated with an increased risk of cancer, especially in Caucasians.</p

Oblique rift geometry of the West Siberian Basin: tectonic setting for the Siberian flood basalts

We use magnetic intensity data to determine the geometries of basalt-filled rifts of the West Siberian Basin. En echelon graben arrays suggest a component of right-lateral, north–south shear during east–west extension (present co-ordinates). Several major exposed faults at the basin margins, mainly within the Altaid orogenic belt, underwent right-lateral strike-slip in the Late Permian–Early Triassic interval. The combined datasets show that the Siberian flood basalts were erupted during right-lateral oblique extension between the Urals and the Siberian craton, centred on a triple junction in the NE of the West Siberian Basin