Disclosing Early Excited State Relaxation Events in Prototypical Linear Carbon Chains

One-dimensional (1D) linear nanostructures comprising sp-hybridized carbon atoms, as derivatives of the prototypicalallotropeknown as carbyne, are predicted to possess outstanding mechanical,thermal, and electronic properties. Despite recent advances in theirsynthesis, their chemical and physical properties are still poorlyunderstood. Here, we investigate the photophysics of a prototypicalpolyyne (i.e., 1D chain with alternating single and triple carbonbonds) as the simplest model of finite carbon wire and as a prototypeof sp-carbon-based chains. We perform transient absorptionexperiments with high temporal resolution (<30 fs) on monodispersedhydrogen-capped hexayne H (C C)(6)Hsynthesized by laser ablation in liquid. With the support of computationalstudies based on ground state density functional theory (DFT) andexcited state time-dependent (TD)-DFT calculations, we provide a comprehensivedescription of the excited state relaxation processes at early timesfollowing photoexcitation. We show that the internal conversion froma bright high-energy singlet excited state to a low-lying singletdark state is ultrafast and takes place with a 200 fs time constant,followed by thermalization on the picosecond time scale and decayof the low-energy singlet state with hundreds of picoseconds timeconstant. We also show that the time scale of these processes doesnot depend on the end groups capping the sp-carbonchain. The understanding of the primary photoinduced events in polyynesis of key importance both for fundamental knowledge and for potentialoptoelectronic and light-harvesting applications of low-dimensionalnanostructured carbon-based materials

Unravelling the intricated photophysical behavior of 3-(pyridin-2-yl)triimidazotriazine AIE and RTP polymorphs

The development of purely organic materials showing multicolor fluorescent and phosphorescent behaviour represents a formidable challenge in view of practical applications. Herein the rich photophyisical behaviour of 3-(pyridin-2- yl)triimidazotriazine (TT-Py) organic molecule, comprising excitation-dependent fluorescence and phosphorescence under ambient conditions in both blended film and crystalline phase, is investigated by means of steady state, time resolved and ultrafast spectroscopies and interpreted on the basis of X-ray diffraction studies and DFT/TDDFT calculations. In particular, by proper excitation wavelength, dual fluorescence and dual phosphorescence of molecular origin can be observed together with low energy phosphorescences resulting from aggregate species. It is demonstrated that the multiple emission property is originated by the copresence, in the investigated system, of an extended polycyclic nitrogen-rich moiety (TT), strongly rigidified by p-p stacking interactions and short C\u2013H...N hydrogen bonds, and a fragment (Py) featuring partial conformational freedom

Environment-Driven Coherent Population Transfer Governs the Ultrafast Photophysics of Tryptophan

By combining UV transient absorption spectroscopy with sub-30-fs temporal resolution and CASPT2/MM calculations, we present a complete description of the primary photo-induced processes in solvated tryptophan. Our results shed new light on the role of the solvent in the relaxation dynamics of tryptophan. We unveil two consecutive coherent population transfer events involving the lowest two singlet excited states: a sub-50-fs non-adiabatic La-->Lb transfer through a conical intersection and a subsequent 220 fs reverse Lb-->La transfer due to solvent assisted adiabatic stabilization of the La state. Vibrational fingerprints in the transient absorption spectra provide compelling evidence of a vibronic coherence established between the two excited states from the earliest times after photoexcitation and lasting until the back-transfer to La is complete. The demonstration of response to the environment as a driver of coherent population dynamics among the excited states of tryptophan closes the long debate on its solvent-assisted relaxation mechanisms and extends its application as a local probe of protein dynamics to the ultrafast timescales

The RESET project: constructing a European tephra lattice for refined synchronisation of environmental and archaeological events during the last c. 100 ka

This paper introduces the aims and scope of the RESET project (. RESponse of humans to abrupt Environmental Transitions), a programme of research funded by the Natural Environment Research Council (UK) between 2008 and 2013; it also provides the context and rationale for papers included in a special volume of Quaternary Science Reviews that report some of the project's findings. RESET examined the chronological and correlation methods employed to establish causal links between the timing of abrupt environmental transitions (AETs) on the one hand, and of human dispersal and development on the other, with a focus on the Middle and Upper Palaeolithic periods. The period of interest is the Last Glacial cycle and the early Holocene (c. 100-8 ka), during which time a number of pronounced AETs occurred. A long-running topic of debate is the degree to which human history in Europe and the Mediterranean region during the Palaeolithic was shaped by these AETs, but this has proved difficult to assess because of poor dating control. In an attempt to move the science forward, RESET examined the potential that tephra isochrons, and in particular non-visible ash layers (cryptotephras), might offer for synchronising palaeo-records with a greater degree of finesse. New tephrostratigraphical data generated by the project augment previously-established tephra frameworks for the region, and underpin a more evolved tephra 'lattice' that links palaeo-records between Greenland, the European mainland, sub-marine sequences in the Mediterranean and North Africa. The paper also outlines the significance of other contributions to this special volume: collectively, these illustrate how the lattice was constructed, how it links with cognate tephra research in Europe and elsewhere, and how the evidence of tephra isochrons is beginning to challenge long-held views about the impacts of environmental change on humans during the Palaeolithic. © 2015 Elsevier Ltd.RESET was funded through Consortium Grants awarded by the Natural Environment Research Council, UK, to a collaborating team drawn from four institutions: Royal Holloway University of London (grant reference NE/E015905/1), the Natural History Museum, London (NE/E015913/1), Oxford University (NE/E015670/1) and the University of Southampton, including the National Oceanography Centre (NE/01531X/1). The authors also wish to record their deep gratitude to four members of the scientific community who formed a consultative advisory panel during the lifetime of the RESET project: Professor Barbara Wohlfarth (Stockholm University), Professor Jørgen Peder Steffensen (Niels Bohr Institute, Copenhagen), Dr. Martin Street (Romisch-Germanisches Zentralmuseum, Neuwied) and Professor Clive Oppenheimer (Cambridge University). They provided excellent advice at key stages of the work, which we greatly valued. We also thank Jenny Kynaston (Geography Department, Royal Holloway) for construction of several of the figures in this paper, and Debbie Barrett (Elsevier) and Colin Murray Wallace (Editor-in-Chief, QSR) for their considerable assistance in the production of this special volume.Peer Reviewe

Palaeogenomics of Upper Palaeolithic to Neolithic European hunter-gatherers

Modern humans have populated Europe for more than 45,000 years1,2. Our knowledge of the genetic relatedness and structure of ancient hunter-gatherers is however limited, owing to the scarceness and poor molecular preservation of human remains from that period3. Here we analyse 356 ancient hunter-gatherer genomes, including new genomic data for 116 individuals from 14 countries in western and central Eurasia, spanning between 35,000 and 5,000 years ago. We identify a genetic ancestry profile in individuals associated with Upper Palaeolithic Gravettian assemblages from western Europe that is distinct from contemporaneous groups related to this archaeological culture in central and southern Europe4, but resembles that of preceding individuals associated with the Aurignacian culture. This ancestry profile survived during the Last Glacial Maximum (25,000 to 19,000 years ago) in human populations from southwestern Europe associated with the Solutrean culture, and with the following Magdalenian culture that re-expanded northeastward after the Last Glacial Maximum. Conversely, we reveal a genetic turnover in southern Europe suggesting a local replacement of human groups around the time of the Last Glacial Maximum, accompanied by a north-to-south dispersal of populations associated with the Epigravettian culture. From at least 14,000 years ago, an ancestry related to this culture spread from the south across the rest of Europe, largely replacing the Magdalenian-associated gene pool. After a period of limited admixture that spanned the beginning of the Mesolithic, we find genetic interactions between western and eastern European hunter-gatherers, who were also characterized by marked differences in phenotypically relevant variants

Palaeogenomics of Upper Palaeolithic to Neolithic European hunter-gatherers

Modern humans have populated Europe for more than 45,000 years(1,2). Our knowledge of the genetic relatedness and structure of ancient hunter-gatherers is however limited, owing to the scarceness and poor molecular preservation of human remains from that period(3). Here we analyse 356 ancient hunter-gatherer genomes, including new genomic data for 116 individuals from 14 countries in western and central Eurasia, spanning between 35,000 and 5,000 years ago. We identify a genetic ancestry profile in individuals associated with Upper Palaeolithic Gravettian assemblages from western Europe that is distinct from contemporaneous groups related to this archaeological culture in central and southern Europe(4), but resembles that of preceding individuals associated with the Aurignacian culture. This ancestry profile survived during the Last Glacial Maximum (25,000 to 19,000 years ago) in human populations from southwestern Europe associated with the Solutrean culture, and with the following Magdalenian culture that re-expanded northeastward after the Last Glacial Maximum. Conversely, we reveal a genetic turnover in southern Europe suggesting a local replacement of human groups around the time of the Last Glacial Maximum, accompanied by a north-to-south dispersal of populations associated with the Epigravettian culture. From at least 14,000 years ago, an ancestry related to this culture spread from the south across the rest of Europe, largely replacing the Magdalenian-associated gene pool. After a period of limited admixture that spanned the beginning of the Mesolithic, we find genetic interactions between western and eastern European hunter-gatherers, who were also characterized by marked differences in phenotypically relevant variants.Molecular Technology and Informatics for Personalised Medicine and Healt

Two-Color Soft X-Ray Lasing in a High-Density Nickel-like Krypton Plasma

International audienc