Past human expansions shaped the spatial pattern of Neanderthal ancestry.

The worldwide expansion of modern humans () started before the extinction of Neanderthals (). Both species coexisted and interbred, leading to slightly higher introgression in East Asians than in Europeans. This distinct ancestry level has been argued to result from selection, but range expansions of modern humans could provide an alternative explanation.

Ancient mitochondrial diversity reveals population homogeneity in Neolithic Greece and identifies population dynamics along the Danubian expansion axis.

The aim of the study is to investigate mitochondrial diversity in Neolithic Greece and its relation to hunter-gatherers and farmers who populated the Danubian Neolithic expansion axis. We sequenced 42 mitochondrial palaeogenomes from Greece and analysed them together with European set of 328 mtDNA sequences dating from the Early to the Final Neolithic and 319 modern sequences. To test for population continuity through time in Greece, we use an original structured population continuity test that simulates DNA from different periods by explicitly considering the spatial and temporal dynamics of populations.

Robust coherent spin centers from stable azafullerene radicals entrapped in cycloparaphenylene rings.

Molecular entities with robust spin-1/2 are natural two-level quantum systems for realizing qubits and are key ingredients of emerging quantum technologies such as quantum computing. Here we show that robust and abundant spin-1/2 species can be created in the solid state from spin-active azafullerene CN cages supramolecularly hosted in crystals of [10]cycloparaphenylene ([10]CPP) nanohoops. This is achieved a two-stage thermally-assisted homolysis of the parent diamagnetic [10]CPP⊃(CN)⊂[10]CPP supramolecular complex.

Spatially explicit paleogenomic simulations support cohabitation with limited admixture between Bronze Age Central European populations.

The Bronze Age is a complex period of social, cultural and economic changes. Recent paleogenomic studies have documented a large and rapid genetic change in early Bronze Age populations from Central Europe. However, the detailed demographic and genetic processes involved in this change are still debated.

A Long-Lived Azafullerenyl Radical Stabilized by Supramolecular Shielding with a [10]Cycloparaphenylene.

A major handicap towards the exploitation of radicals is their inherent instability. In the paramagnetic azafullerenyl radical C N , the unpaired electron is strongly localized next to the nitrogen atom, which induces dimerization to diamagnetic bis(azafullerene), (C N) . Conventional stabilization by introducing steric hindrance around the radical is inapplicable here because of the concave fullerene geometry.

Determining addition pathways and stable isomers for CF functionalization of endohedral Gd@C.

Using density functional theory approaches, we follow the sequential addition of CF functional groups to the surface of the metallic endofullerene species Gd@C. The presence of gadolinium in the interior of the cage strongly influences the addition sequence. The calculations are able to successfully identify end points in the addition sequence at Gd@C(CF) , = 3 and two isomers at = 5, in predictive agreement with experiment.

Isolation and structure determination of missing fullerenes Gd@C(CF) through trifluoromethylation.

Our trifluoromethyl functionalization method enables the dissolution and isolation of missing metallofullerenes of Gd@C(CF) . After multi-stage high-performance liquid chromatography purification, Gd@C(CF) and two regioisomers of Gd@C(CF) are isolated. X-ray crystallographic analysis reveals that all of the isolated metallofullerenes react with CF groups on pentagons of the -symmetry C cages.

Bayesian estimation of partial population continuity using ancient DNA and spatially explicit simulations.

The retrieval of ancient DNA from osteological material provides direct evidence of human genetic diversity in the past. Ancient DNA samples are often used to investigate whether there was population continuity in the settlement history of an area. Methods based on the serial coalescent algorithm have been developed to test whether the population continuity hypothesis can be statistically rejected by analysing DNA samples from the same region but of different ages.

Crystalline functionalized endohedral C metallofullerides.

Endohedral metallofullerenes have been extensively studied since the first experimental observation of La@C in a laser-vaporized supersonic beam in 1985. However, most of these studies have focused on metallofullerenes larger than C such as (metal)@C, and there are no reported purified C-based monomeric metallofullerenes, except for [Li@C](SbCl) salt. Pure (metal)@C compounds have not been obtained because of their extremely high chemical reactivity.

Electronic Communication between two [10]cycloparaphenylenes and Bis(azafullerene) (C N) Induced by Cooperative Complexation.

The complex of [10]cycloparaphenylene ([10]CPP) with bis(azafullerene) (C N) is investigated experimentally and computationally. Two [10]CPP rings are bound to the dimeric azafullerene giving [10]CPP⊃(C N) ⊂[10]CPP. Photophysical and redox properties support an electronic interaction between the components especially when the second [10]CPP is bound.

Investigating population continuity with ancient DNA under a spatially explicit simulation framework.

Background: Recent advances in sequencing technologies have allowed for the retrieval of ancient DNA data (aDNA) from skeletal remains, providing direct genetic snapshots from diverse periods of human prehistory. Comparing samples taken in the same region but at different times, hereafter called "serial samples", may indicate whether there is continuity in the peopling history of that area or whether an immigration of a genetically different population has occurred between the two sampling times. However, the exploration of genetic relationships between serial samples generally ignores their geographical locations and the spatiotemporal dynamics of populations.

Effect of the fluorination technique on the surface-fluorination patterning of double-walled carbon nanotubes.

Double-walled carbon nanotubes (DWCNTs) are fluorinated using (1) fluorine F at 200 °C, (2) gaseous BrF at room temperature, and (3) CF radio-frequency plasma functionalization. These have been comparatively studied using transmission electron microscopy and infrared, Raman, X-ray photoelectron, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. A formation of covalent C-F bonds and a considerable reduction in the intensity of radial breathing modes from the outer shells of DWCNTs are observed for all samples.

Ab initio infrared vibrational modes for neutral and charged small fullerenes (C20, C24, C26, C28, C30 and C60).

We calculate the infrared (IR) absorption spectra using DFT B3LYP(6-311G) for a range of small closed-cage fullerenes, Cn, n=20, 24, 26, 28, 30 and 60, in both neutral and multiple positive and negative charge states. The results are of use, notably, for direct comparison with observed IR absorption in the interstellar medium. Frequencies fall typically into two ranges, with C-C stretch modes around 1100-1500 cm(-1) (6.