Copper-Catalyzed Enantioselective Allylic Alkylation with a γ-Butyrolactone-Derived Silyl Ketene Acetal

Herein, we report a Cu‐catalyzed enantioselective allylic alkylation using a γ‐butyrolactone‐derived silyl ketene acetal. Critical to the development of this work was the identification of a novel mono‐picolinamide ligand with the appropriate steric and electronic properties to afford the desired products in high yield (up to 96 %) and high ee (up to 95 %). Aryl, aliphatic, and unsubstituted allylic chlorides bearing a broad range of functionality are well‐tolerated. Spectroscopic studies reveal that a Cu^I species is likely the active catalyst, and DFT calculations suggest ligand sterics play an important role in determining Cu coordination and thus catalyst geometry

On the evolution and environmental dependence of the star formation rate versus stellar mass relation since z ˜ 2.

This paper discusses the evolution of the correlation between galaxy star formation rates (SFRs) and stellar mass (M*) over the last ∼10 Gyr, particularly focusing on its environmental dependence. We first present the mid-infrared (MIR) properties of the Hα-selected galaxies in a rich cluster Cl 0939+4713 at z = 0.4. We use wide-field Spitzer/MIPS 24 μm data to show that the optically red Hα emitters, which are most prevalent in group-scale environments, tend to have higher SFRs and higher dust extinction than the majority population of blue Hα sources. With an MIR stacking analysis, we find that the median SFR of Hα emitters is higher in higher density environment at z = 0.4. We also find that star-forming galaxies in high-density environment tend to have higher specific SFR (SSFR), although the trend is much less significant compared to that of SFR. This increase of SSFR in high-density environment is not visible when we consider the SFR derived from Hα alone, suggesting that the dust attenuation in galaxies depends on environment; galaxies in high-density environment tend to be dustier (by up to ∼0.5 mag), probably reflecting a higher fraction of nucleated, dusty starbursts in higher density environments at z = 0.4. We then discuss the environmental dependence of the SFR–M* relation for star-forming galaxies since z ∼ 2, by compiling our comparable, narrow-band-selected, large Hα emitter samples in both distant cluster environments and field environments. We find that the SSFR of Hα-selected galaxies (at the fixed mass of log (M*/M⊙) = 10) rapidly evolves as (1 + z)3, but the SFR–M* relation is independent of the environment since z ∼ 2, as far as we rely on the Hα-based SFRs (with M*-dependent extinction correction). Even if we consider the possible environmental variation in the dust attenuation, we conclude that the difference in the SFR–M* relation between cluster and field star-forming galaxies is always small (≲0.2 dex level) at any time in the history of the Universe since z ∼ 2

First annotated draft genomes of nonmarine ostracods (Ostracoda, Crustacea) with different reproductive modes.

Ostracods are one of the oldest crustacean groups with an excellent fossil record and high importance for phylogenetic analyses but genome resources for this class are still lacking. We have successfully assembled and annotated the first reference genomes for three species of nonmarine ostracods; two with obligate sexual reproduction (Cyprideis torosa and Notodromas monacha) and the putative ancient asexual Darwinula stevensoni. This kind of genomic research has so far been impeded by the small size of most ostracods and the absence of genetic resources such as linkage maps or BAC libraries that were available for other crustaceans. For genome assembly, we used an Illumina-based sequencing technology, resulting in assemblies of similar sizes for the three species (335-382 Mb) and with scaffold numbers and their N50 (19-56 kb) in the same orders of magnitude. Gene annotations were guided by transcriptome data from each species. The three assemblies are relatively complete with BUSCO scores of 92-96. The number of predicted genes (13,771-17,776) is in the same range as Branchiopoda genomes but lower than in most malacostracan genomes. These three reference genomes from nonmarine ostracods provide the urgently needed basis to further develop ostracods as models for evolutionary and ecological research

On positivity of Ehrhart polynomials

Ehrhart discovered that the function that counts the number of lattice points in dilations of an integral polytope is a polynomial. We call the coefficients of this polynomial Ehrhart coefficients, and say a polytope is Ehrhart positive if all Ehrhart coefficients are positive (which is not true for all integral polytopes). The main purpose of this article is to survey interesting families of polytopes that are known to be Ehrhart positive and discuss the reasons from which their Ehrhart positivity follows. We also include examples of polytopes that have negative Ehrhart coefficients and polytopes that are conjectured to be Ehrhart positive, as well as pose a few relevant questions.Comment: 40 pages, 7 figures. To appear in in Recent Trends in Algebraic Combinatorics, a volume of the Association for Women in Mathematics Series, Springer International Publishin

A clinical and molecular characterisation of CRB1-associated maculopathy

To date, over 150 disease-associated variants in CRB1 have been described, resulting in a range of retinal disease phenotypes including Leber congenital amaurosis and retinitis pigmentosa. Despite this, no genotype–phenotype correlations are currently recognised. We performed a retrospective review of electronic patient records to identify patients with macular dystrophy due to bi-allelic variants in CRB1. In total, seven unrelated individuals were identified. The median age at presentation was 21 years, with a median acuity of 0.55 decimalised Snellen units (IQR = 0.43). The follow-up period ranged from 0 to 19 years (median = 2.0 years), with a median final decimalised Snellen acuity of 0.65 (IQR = 0.70). Fundoscopy revealed only a subtly altered foveal reflex, which evolved into a bull’s-eye pattern of outer retinal atrophy. Optical coherence tomography identified structural changes—intraretinal cysts in the early stages of disease, and later outer retinal atrophy. Genetic testing revealed that one rare allele (c.498_506del, p.(Ile167_Gly169del)) was present in all patients, with one patient being homozygous for the variant and six being heterozygous. In trans with this, one variant recurred twice (p.(Cys896Ter)), while the four remaining alleles were each observed once (p.(Pro1381Thr), p.(Ser478ProfsTer24), p.(Cys195Phe) and p.(Arg764Cys)). These findings show that the rare CRB1 variant, c.498_506del, is strongly associated with localised retinal dysfunction. The clinical findings are much milder than those observed with bi-allelic, loss-of-function variants in CRB1, suggesting this in-frame deletion acts as a hypomorphic allele. This is the most prevalent disease-causing CRB1 variant identified in the non-Asian population to date

Toll-like receptor 4 and high-mobility group box-1 are involved in ictogenesis and can be targeted to reduce seizures

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FOXP3 Expression Is Upregulated in CD4+T Cells in Progressive HIV-1 Infection and Is a Marker of Disease Severity

Understanding the role of different classes of T cells during HIV infection is critical to determining which responses correlate with protective immunity. To date, it is unclear whether alterations in regulatory T cell (Treg) function are contributory to progression of HIV infection.FOXP3 expression was measured by both qRT-PCR and by flow cytometry in HIV-infected individuals and uninfected controls together with expression of CD25, GITR and CTLA-4. Cultured peripheral blood mononuclear cells were stimulated with anti-CD3 and cell proliferation was assessed by CFSE dilution.HIV infected individuals had significantly higher frequencies of CD4(+)FOXP3(+) T cells (median of 8.11%; range 1.33%-26.27%) than healthy controls (median 3.72%; range 1.3-7.5%; P = 0.002), despite having lower absolute counts of CD4(+)FOXP3(+) T cells. There was a significant positive correlation between the frequency of CD4(+)FOXP3(+) T cells and viral load (rho = 0.593 P = 0.003) and a significant negative correlation with CD4 count (rho = -0.423 P = 0.044). 48% of our patients had CD4 counts below 200 cells/microl and these patients showed a marked elevation of FOXP3 percentage (median 10% range 4.07%-26.27%). Assessing the mechanism of increased FOXP3 frequency, we found that the high FOXP3 levels noted in HIV infected individuals dropped rapidly in unstimulated culture conditions but could be restimulated by T cell receptor stimulation. This suggests that the high FOXP3 expression in HIV infected patients is likely due to FOXP3 upregulation by individual CD4(+) T cells following antigenic or other stimulation.FOXP3 expression in the CD4(+) T cell population is a marker of severity of HIV infection and a potential prognostic marker of disease progression

Blue Genes : Synopsis of the workshop organized by ICM-CSIC and BAU to increase engagement and collaboration for Our Ocean and Waters

7 pagesOn October 27th, 2022, the Institut de Ciències del Mar (ICM-CSIC), a marine research institution located in Barcelona, and the College of Arts & Design of Barcelona (BAU), a higher-education centre specialized in arts and design, co-organized the first Blue Genes meeting. This meeting took place virtually in a 3-hour workshop format and counted with more than 50 participants from different locations. Its main goal was to explore in a co-creative way how to reinforce and empower the engagement of people, particularly teenagers and young adults, with our Ocean and Waters and increase networking and collaboration. This meeting was the first workshop of a series of planned activities under the Blue Genes initiativePeer reviewe