Blueshift and intramolecular tunneling of NH[sub 3] umbrella mode in [sup 4]He[sub n] clusters

International audienceWe present diffusion Monte Carlo calculations of the ground and first excited vibrational states of NH(3) (4)He(n) for n< or =40. We use the potential energy surface developed by one of us [M. P. Hodges and R. J. Wheatley, J. Chem. Phys. 114, 8836 (2001)], which includes the umbrella mode coordinate of NH(3). Using quantum Monte Carlo calculations of excited states, we show that this potential is able to reproduce qualitatively the experimentally observed effects of the helium environment, namely, a blueshift of the umbrella mode frequency and a reduction of the tunneling splittings in ground and first excited vibrational states of the molecule. These basic features are found to result regardless of whether dynamical approximations or exact calculations are employed

A single crystal study of CPO-27 and UTSA-74 for nitric oxide storage and release

Funding: UK EPSRC EP/K005499/1, EP/K503162, and EP/L017008/1).Single crystal CPO-27-Mg, -Zn and its structural isomer UTSA-74 have been prepared through use of acid modulators; salicylic acid and benzoic acid, respectively. Salicylic acid directed the synthesis of CPO-27-Mg/Zn whereas benzoic acid the synthesis of UTSA-74. Through “in-house” SCXRD, DMF was seen to bind to the Zn2+ and water to the Mg2+ metal sites in CPO-27-M. Although the synthesis conditions were analogous for UTSA-74, DMF is too large to bind due to the proximity of the binding sites. A dissolution–recrystallisation transformation was examined from UTSA-74 to CPO-27-Zn. The release of nitric oxide was measured for each material.PostprintPeer reviewe

Using Water Chemistry, Isotopes and Microbiology to Evaluate Groundwater Sources, Flow Paths and Geochemical Reactions in the Death Valley Flow System, USA

AbstractSprings of Ash Meadows and Furnace Creek (near or in Death Valley, CA) have nearly constant flow, temperature, chemistry, and similar δ2H and δ18O signatures. These factors indicate shared water sources and/or analogous geochemical reactions along similar flow paths. DNA-based (16S rRNA gene) microbial diversity assessments further illuminate these relationships. Whereas, all Ash Meadows springs share related archaeal populations, variations in carbon-14 (Crystal Spring) and strontium isotopes, Na+, SO2-, and methane concentrations (Big Spring), correspond with microbial differences within and between the two discharge areas. Similar geochemical signatures linking Ash Meadows and Furnace Creek springs appear to support a distinct end member at Big Spring in Ash Meadows, which is also supported by coincident enrichment in microbial methanogens and methanotrophs. Conversely, DNA libraries from a deep carbonate well (878 m) located between Ash Meadows and Furnace Creek (BLM-1), indicate no shared microbial diversity between Ash Meadows or Furnace Creek springs

Thermal rearrangement of thiocarbonyl-stabilised triphenylphosphonium ylides leading to (Z)-1-diphenylphosphino-2-(phenylsulfenyl)alkenes and their coordination chemistry

While thiocarbonyl-stabilised phosphonium ylides generally react upon flash vacuum pyrolysis by extrusion of Ph3PS to give alkynes in an analogous way to their carbonyl-stabilised analogues, two examples with a hydrogen atom on the ylidic carbon are found to undergo a quite different process. The net transfer of a phenyl group from P to S gives (Z)-configured 1-diphenylphosphino-2-(phenylsulfenyl)alkenes in a novel isomerisation process via intermediate λ5-1,2-thiaphosphetes. These prove to be versatile hemilabile ligands with a total of seven complexes prepared involving five different transition metals. Four of these have been characterised by X-ray diffraction with two involving the bidentate ligand forming a five-membered ring metallacycle and two with the ligand coordinating to the metal only through phosphorus.Publisher PDFPeer reviewe

The prevalence of intrusive memories in adult depression: A meta-analysis

Background Intrusive memories have typically been associated with post-traumatic stress disorder (PTSD) but some studies have suggested they can also occur in depression-alone. Objective This meta-analysis aimed to estimate the prevalence of intrusive memories in adult depression and to explore methodological and other factors that may moderate this prevalence. Method The databases PsycINFO, PsycARTICLES, MedLine, PubMed, CINAHL and Embase were searched for relevant articles, published up to and including July 2016. Studies measuring point prevalence of intrusive memories in adults aged 18 years or above with depression were included and assessed for quality. Meta-analysis was completed under a random effects model. Results Seven studies measuring point prevalence of intrusive memories in adult depression were included. The overall pooled prevalence estimate calculated was 76.0% (95% CI 59.4 – 89.4%), reducing to 66.0% (95% CI 51.0 – 79.5%) when restricted to intrusive memories experienced within the week prior to assessment. Heterogeneity was high. Between-groups analyses indicated that adults with depression are as likely to experience intrusive memories as adults with PTSD, and more likely to experience intrusive memories than healthy controls (risk ratio of 2.94, 95% CI 1.53 – 5.67). Limitations The strength of conclusions is limited by the small number of studies included. Consideration of the relationship between depression, intrusive memories and trauma exposure is required. Conclusions Intrusive memories are experienced by a large majority of adults with depression and may therefore be an important target for cognitive intervention. Larger scale measurement of clinical outcome is needed with identification of individual factors predicting treatment response

Safety, tolerability, and immunogenicity of influenza vaccination with a high-density microarray patch: Results from a randomized, controlled phase I clinical trial.

BACKGROUND: The Vaxxas high-density microarray patch (HD-MAP) consists of a high density of microprojections coated with vaccine for delivery into the skin. Microarray patches (MAPs) offer the possibility of improved vaccine thermostability as well as the potential to be safer, more acceptable, easier to use, and more cost-effective for the administration of vaccines than injection by needle and syringe (N&S). Here, we report a phase I trial using the Vaxxas HD-MAP to deliver a monovalent influenza vaccine that was to the best of our knowledge the first clinical trial to evaluate the safety, tolerability, and immunogenicity of lower doses of influenza vaccine delivered by MAPs. METHODS AND FINDINGS: HD-MAPs were coated with a monovalent, split inactivated influenza virus vaccine containing A/Singapore/GP1908/2015 H1N1 haemagglutinin (HA). Between February 2018 and March 2018, 60 healthy adults (age 18-35 years) in Melbourne, Australia were enrolled into part A of the study and vaccinated with either: HD-MAPs delivering 15 μg of A/Singapore/GP1908/2015 H1N1 HA antigen (A-Sing) to the volar forearm (FA); uncoated HD-MAPs; intramuscular (IM) injection of commercially available quadrivalent influenza vaccine (QIV) containing A/Singapore/GP1908/2015 H1N1 HA (15 μg/dose); or IM injection of H1N1 HA antigen (15 μg/dose). After 22 days' follow-up and assessment of the safety data, a further 150 healthy adults were enrolled and randomly assigned to 1 of 9 treatment groups. Participants (20 per group) were vaccinated with HD-MAPs delivering doses of 15, 10, 5, 2.5, or 0 μg of HA to the FA or 15 μg HA to the upper arm (UA), or IM injection of QIV. The primary objectives of the study were safety and tolerability. Secondary objectives were to assess the immunogenicity of the influenza vaccine delivered by HD-MAP. Primary and secondary objectives were assessed for up to 60 days post-vaccination. Clinical staff and participants were blind as to which HD-MAP treatment was administered and to administration of IM-QIV-15 or IM-A/Sing-15. All laboratory investigators were blind to treatment and participant allocation. Two further groups in part B (5 participants per group), not included in the main safety and immunological analysis, received HD-MAPs delivering 15 μg HA or uncoated HD-MAPs applied to the forearm. Biopsies were taken on days 1 and 4 for analysis of the cellular composition from the HD-MAP application sites. The vaccine coated onto HD-MAPs was antigenically stable when stored at 40°C for at least 12 months. HD-MAP vaccination was safe and well tolerated; any systemic or local adverse events (AEs) were mild or moderate. Observed systemic AEs were mostly headache or myalgia, and local AEs were application-site reactions, usually erythema. HD-MAP administration of 2.5 μg HA induced haemagglutination inhibition (HAI) and microneutralisation (MN) titres that were not significantly different to those induced by 15 μg HA injected IM (IM-QIV-15). HD-MAP delivery resulted in enhanced humoral responses compared with IM injection with higher HAI geometric mean titres (GMTs) at day 8 in the MAP-UA-15 (GMT 242.5, 95% CI 133.2-441.5), MAP-FA-15 (GMT 218.6, 95% CI 111.9-427.0), and MAP-FA-10 (GMT 437.1, 95% CI 254.3-751.3) groups compared with IM-QIV-15 (GMT 82.8, 95% CI 42.4-161.8), p = 0.02, p = 0.04, p < 0.001 for MAP-UA-15, MAP-FA-15, and MAP-FA-10, respectively. Higher titres were also observed at day 22 in the MAP-FA-10 (GMT 485.0, 95% CI 301.5-780.2, p = 0.001) and MAP-UA-15 (367.6, 95% CI 197.9-682.7, p = 0.02) groups compared with the IM-QIV-15 group (GMT 139.3, 95% CI 79.3-244.5). Results from a panel of exploratory immunoassays (antibody-dependent cellular cytotoxicity, CD4+ T-cell cytokine production, memory B cell (MBC) activation, and recognition of non-vaccine strains) indicated that, overall, Vaxxas HD-MAP delivery induced immune responses that were similar to, or higher than, those induced by IM injection of QIV. The small group sizes and use of a monovalent influenza vaccine were limitations of the study. CONCLUSIONS: Influenza vaccine coated onto the HD-MAP was stable stored at temperatures up to 40°C. Vaccination using the HD-MAP was safe and well tolerated and resulted in immune responses that were similar to or significantly enhanced compared with IM injection. Using the HD-MAP, a 2.5 μg dose (1/6 of the standard dose) induced HAI and MN titres similar to those induced by 15 μg HA injected IM. TRIAL REGISTRATION: Australian New Zealand Clinical Trials Registry (ANZCTR.org.au), trial ID 108 ACTRN12618000112268/U1111-1207-3550

ZANATLIJE U SPLITU POČETKOM XVIII STOLJEĆA

The authors would like to acknowledge the financial support from the EPSRC industrial CASE award (grant EP/N50936X/1).Here we demonstrate the synthesis and structural characterisation of a novel copper MOF: STAM-NMe2, developed using the linker 5-dimethylamino isophthalic acid. The material is a member of the STAM series of MOFs, with a Kagome lattice structure and contains two types of pore system. The structure was investigated using single crystal X-ray diffraction, variable temperature powder X-ray diffraction was used to determine the thermal stability of the MOF, and nitrogen BET adsorption was employed to determine the porosity of the material.PostprintPeer reviewe

Microarray patch delivery of un-adjuvanted influenza vaccine induces potent and broad-spectrum immune responses in a phase I clinical trial

Microarray patches (MAPs) offer the possibility of improved vaccine thermostability and dose-sparing potential as well as the potential to be safer, more acceptable, easier to use and more cost-effective for the administration of vaccines than injection by needle and syringe. Here, we report a phase I trial (ACTRN12618000112268/ U1111-1207-3550) using the Vaxxas high-density MAP (HD-MAP) to deliver a monovalent influenza vaccine to evaluate the safety, tolerability, and immunogenicity of lower doses of influenza vaccine delivered by MAPs. To the best of our knowledge, this is the first study determining dose reduction potential using MAPs in humans. Monovalent, split inactivated influenza virus vaccine containing A/Singapore/GP1908/ 2015 [H1N1] haemagglutinin (HA) was delivered by MAP into the volar forearm or upper arm, or given intramuscularly (IM) once. Participants (20 per group) received HD-MAPs delivering doses of 15, 10, 5, 2.5 or 0 µg of HA or an IM injection of quadrivalent influenza vaccine (QIV). In two subgroups, skin biopsies were taken on days 1 (pre-vaccination) and 4 for analysis of the cellular composition from the HD-MAP application sites. All laboratory investigators were blind to treatment and participant allocation. The primary objectives of the study were safety and tolerability. Secondary objectives included immunogenicity and dose de-escalation assessments of the influenza vaccine delivered by HD-MAP. Both objectives were assessed for up to 60 days post-vaccination. Please click Download on the upper right corner to see the full abstract

The seeds of commerce: a network analysis-based approach to the Romano-British transport system

Communication routes are an important subject in the study of the human past. They allowed interactions between communities and the dispersal of goods and ideas. Their study, therefore, can shed light on the way in which communities inhabited the landscape, related to each other and were affected by macro-regional trends. Many methods, such as archaeomorphological analysis and Least Cost Route modelling (LCR), have been devised and are routinely employed for the reconstruction of ancient routes. Their analysis in terms of communication, trade or historical significance, however, has usually been left unexplored. This is probably due to the connected nature of routes, which form communication networks: these are shaped by interconnected nodes and extend over territories surpassing the regional scale in such a way that even a change in a single node or link can affect the whole network. Consequently, the partial reconstruction of communication networks provided by the aforementioned methods does not usually allow a holistic analysis. In this paper the relatively well understood British Roman road network is employed to explore the analytical possibilities offered by a combination of Social Network Analysis, Spatial Network Analysis and spatial interpolation-based distribution analysis. The British road network has been reconstructed using published data but also a variation of LCR in which cost surfaces are derived from cultural data obtained from large-scale cultural inventories. The distribution of introduced food plants during the Roman period serve as an excellent proxy for the study of trade along the network and its historical consequences. This multi-period archaeobotanical dataset has some evident advantages to other types of material remains: archaeobotanical remains are not reused as, for example, amphorae and, accordingly, they reflect a distribution pattern based on consumption or commerce. Some of them are imported (as they cannot be produced locally) and, consequently, their distribution would be applied through usage of the main routes. The results suggest a continuous inflow of exotics but highlight their changing transport routes, their differential access and the particular weight of certain nodal sites in the development of this commerce with direct impact on urbanisation and the overall economy of Britannia. The Roman road network acted as a major factor in the distribution of sites, their political and economic importance and their permanence or disappearance as global economic trends changed over time

How well do computer-generated faces tap face expertise?

The use of computer-generated (CG) stimuli in face processing research is proliferating due to the ease with which faces can be generated, standardised and manipulated. However there has been surprisingly little research into whether CG faces are processed in the same way as photographs of real faces. The present study assessed how well CG faces tap face identity expertise by investigating whether two indicators of face expertise are reduced for CG faces when compared to face photographs. These indicators were accuracy for identification of own-race faces and the other-race effect (ORE)-the well-established finding that own-race faces are recognised more accurately than other-race faces. In Experiment 1 Caucasian and Asian participants completed a recognition memory task for own- and other-race real and CG faces. Overall accuracy for own-race faces was dramatically reduced for CG compared to real faces and the ORE was significantly and substantially attenuated for CG faces. Experiment 2 investigated perceptual discrimination for own- and other-race real and CG faces with Caucasian and Asian participants. Here again, accuracy for own-race faces was significantly reduced for CG compared to real faces. However the ORE was not affected by format. Together these results signal that CG faces of the type tested here do not fully tap face expertise. Technological advancement may, in the future, produce CG faces that are equivalent to real photographs. Until then caution is advised when interpreting results obtained using CG faces