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Excess sugar consumption is an undisputed primary cause of type 2 diabetes. Alternative sweeteners have since been developed to counteract this issue, however some products such as artificially produced sweeteners are unfavored due to underlying health impacts and taste profile. In its place, rare sugars as have grown commercial interest as an alternative sweetener and psicose is top candidate. Psicose is a rare sugar with virtually zero calories since it is not metabolized after consumption. Current psicose manufacturing processes, due to thermodynamic limitations, are not cost efficient and produce low psicose yields. This study proposes an alternative pathway in which thermodynamic limitations are overcome to produce higher theoretical yields. Two key enzymes, a phosphatase and epimerase, are required for the proposed pathway. This study screens several enzymes, obtained from computational methods, for positive activity toward specific substrates present in the proposed psicose production pathway.

PURPOSE Cisplatin plus gemcitabine is a standard regimen for first-line treatment of advanced non–small-cell lung cancer (NSCLC). Phase II studies of pemetrexed plus platinum compounds have also shown activity in this setting. PATIENTS AND METHODS This noninferiority, phase III, randomized study compared the overall survival between treatment arms using a fixed margin method (hazard ratio [HR] < 1.176) in 1,725 chemotherapy-naive patients with stage IIIB or IV NSCLC and an Eastern Cooperative Oncology Group performance status of 0 to 1. Patients received cisplatin 75 mg/m2 on day 1 and gemcitabine 1,250 mg/m2 on days 1 and 8 (n = 863) or cisplatin 75 mg/m2 and pemetrexed 500 mg/m2 on day 1 (n = 862) every 3 weeks for up to six cycles. RESULTS Overall survival for cisplatin/pemetrexed was noninferior to cisplatin/gemcitabine (median survival, 10.3 v 10.3 months, respectively; HR = 0.94; 95% CI, 0.84 to 1.05). Overall survival was statistically superior for cisplatin/pemetrexed versus cisplatin/gemcitabine in patients with adenocarcinoma (n = 847; 12.6 v 10.9 months, respectively) and large-cell carcinoma histology (n = 153; 10.4 v 6.7 months, respectively). In contrast, in patients with squamous cell histology, there was a significant improvement in survival with cisplatin/gemcitabine versus cisplatin/pemetrexed (n = 473; 10.8 v 9.4 months, respectively). For cisplatin/pemetrexed, rates of grade 3 or 4 neutropenia, anemia, and thrombocytopenia ( P ≤ .001); febrile neutropenia ( P = .002); and alopecia ( P < .001) were significantly lower, whereas grade 3 or 4 nausea ( P = .004) was more common. CONCLUSION In advanced NSCLC, cisplatin/pemetrexed provides similar efficacy with better tolerability and more convenient administration than cisplatin/gemcitabine. This is the first prospective phase III study in NSCLC to show survival differences based on histologic type.

Colloidal 2D semiconductor nanocrystals, the analogue of solid-state quantum wells, have attracted strong interest in material science and physics. Molar quantities of suspended quantum objects with spectrally pure absorption and emission can be synthesized. For the visible region, CdSe nanoplatelets with atomically precise thickness and tailorable emission have been (almost) perfected. For the near-infrared region, PbS nanosheets (NSs) hold strong promise, but the photoluminescence quantum yield is low and many questions on the crystallinity, atomic structure, intriguing rectangular shape, and formation mechanism remain to be answered. Here, we report on a detailed investigation of the PbS NSs prepared with a lead thiocyanate single source precursor. Atomically resolved HAADF-STEM imaging reveals the presence of defects and small cubic domains in the deformed orthorhombic PbS crystal lattice. Moreover, variations in thickness are observed in the NSs, but only in steps of 2 PbS monolayers. To study the reaction mechanism, a synthesis at a lower temperature allowed for the study of reaction intermediates. Specifically, we studied the evolution of pseudo-crystalline templates toward mature, crystalline PbS NSs. We propose a self-induced templating mechanism based on an oleylamine-lead-thiocyanate (OLAM-Pb-SCN) complex with two Pb-SCN units as a building block; the interactions between the long-chain ligands regulate the crystal structure and possibly the lateral dimensions.

As recently highlighted by the SARS-CoV-2 pandemic, viruses have become an increasing burden for health, global economy, and environment. The control of transmission by contact with contaminated materials represents a major challenge, particularly in hospital environments. However, the current disinfection methods in hospital settings suffer from numerous drawbacks. As a result, several medical supplies that cannot be properly disinfected are not reused, leading to severe shortages and increasing amounts of waste, thus prompting the search for alternative solutions. In this work, we report that non-thermal plasma (NTP) can effectively inactivate SARS-CoV-2 from non-porous and porous materials commonly found in healthcare facilities. We demonstrated that 5 min treatment with a dielectric barrier discharge NTP can inactivate 100% of SARS-CoV-2 (Wuhan and Omicron strains) from plastic material. Using porcine respiratory coronavirus (surrogate for SARS-CoV-2) and coxsackievirus B3 (highly resistant non-enveloped virus), we tested the NTP virucidal activity on hospital materials and obtained complete inactivation after 5 and 10 min, respectively. We hypothesize that the produced reactive species and local acidification contribute to the overall virucidal effect of NTP. Our results demonstrate the potential of dielectric barrier discharge NTPs for the rapid, efficient, and low-cost disinfection of healthcare materials.

The magnitude of the 2022 multi-country monkeypox virus (MPXV) outbreak has surpassed any preceding outbreak. It is unclear whether asymptomatic or otherwise undiagnosed infections are fuelling this epidemic. In this study, we aimed to assess whether undiagnosed infections occurred among men attending a Belgian sexual health clinic in May 2022. We retrospectively screened 224 samples collected for gonorrhea and chlamydia testing using an MPXV PCR assay and identified MPXV-DNA-positive samples from four men. At the time of sampling, one man had a painful rash, and three men had reported no symptoms. Upon clinical examination 21-37 days later, these three men were free of clinical signs, and they reported not having experienced any symptoms. Serology confirmed MPXV exposure in all three men, and MPXV was cultured from two cases. These findings show that certain cases of monkeypox remain undiagnosed and suggest that testing and quarantining of individuals reporting symptoms may not suffice to contain the outbreak. Findings of unrecognized or asymptomatic monkeypox virus (MPXV) infections with replication-competent virus in humans suggest that a lack of recognized, clinical symptoms could play a role in virus transmission and the magnitude of the 2022 MPXV outbreak.

Single-molecule FRET experiments with human A2A adenosine receptor in its apo and agonist-bound states in lipid nanodiscs provide insights into its conformational dynamics and activation. The complex pharmacology of G-protein-coupled receptors (GPCRs) is defined by their multi-state conformational dynamics. Single-molecule Forster Resonance Energy Transfer (smFRET) is well suited to quantify dynamics for individual protein molecules; however, its application to GPCRs is challenging. Therefore, smFRET has been limited to studies of inter-receptor interactions in cellular membranes and receptors in detergent environments. Here, we performed smFRET experiments on functionally active human A(2A) adenosine receptor (A(2A)AR) molecules embedded in freely diffusing lipid nanodiscs to study their intramolecular conformational dynamics. We propose a dynamic model of A(2A)AR activation that involves a slow (>2 ms) exchange between the active-like and inactive-like conformations in both apo and antagonist-bound A(2A)AR, explaining the receptor's constitutive activity. For the agonist-bound A(2A)AR, we detected faster (390 +/- 80 mu s) ligand efficacy-dependent dynamics. Our work establishes a general smFRET platform for GPCR investigations that can potentially be used for drug screening and/or mechanism-of-action studies. A.L., A.B., and V.B. are thankful for the Ministry of Science and Higher Education of the Russian Federation (agreement #075-03-2023-106, project FSMG-2020-0003). IM acknowledges the UHasselt Special Research Fund. Measurements of surface expression and Gs-signaling were supported by the Russian Science Foundation (project no. 22-74- 10036; https://rscf.ru/project/22-74-10036/). Computational simulations were supported by the National Natural Science Foundation of China, grant #32250410316 (to PO). We acknowledge the Advanced Optical Microscopy Centre at Hasselt University for support with microscopy experiments. Microscopy was made possible by the Research Foundation Flanders (FWO, projects G0B4915, G0B9922N, and G0H3716N).

A real-time image reconstruction method for scanning transmission electron microscopy (STEM) is proposed. With an algorithm requiring only the center of mass of the diffraction pattern at one probe position at a time, it is able to update the resulting image each time a new probe position is visited without storing any intermediate diffraction patterns. The results show clear features at high spatial frequency, such as atomic column positions. It is also demonstrated that some common post-processing methods, such as band-pass filtering, can be directly integrated in the real-time processing flow. Compared with other reconstruction methods, the proposed method produces high-quality reconstructions with good noise robustness at extremely low memory and computational requirements. An efficient, interactive open source implementation of the concept is further presented, which is compatible with frame-based, as well as event-based camera/file types. This method provides the attractive feature of immediate feedback that microscope operators have become used to, for example, conventional high-angle annular dark field STEM imaging, allowing for rapid decision-making and fine-tuning to obtain the best possible images for beam-sensitive samples at the lowest possible dose.

While metal halide perovskites (MHPs) have shown great potential for various optoelectronic applications, their widespread adoption in commercial photovoltaic cells or photo-sensors is currently restricted, given that MHPs such as CsPbI3 and FAPbI(3) spontaneously transition to an optically inactive non-perovskite phase at ambient conditions. Herein, we put forward an accurate first-principles procedure to obtain fundamental insight into this phase stability conundrum. To this end, we computationally predict the Helmholtz free energy, composed of the electronic ground state energy and thermal corrections, as this is the fundamental quantity describing the phase stability in polymorphic materials. By adopting the random phase approximation method as a wave function-based method that intrinsically accounts for many-body electron correlation effects as a benchmark for the ground state energy, we validate the performance of different exchange-correlation functionals and dispersion methods. The thermal corrections, accessed through the vibrational density of states, are accessed through molecular dynamics simulations, using a phase-transferable machine learning potential to accurately account for the MHPs' anharmonicity and mitigate size effects. The here proposed procedure is critically validated on CsPbI3, which is a challenging material as its phase stability changes slowly with varying temperature. We demonstrate that our procedure is essential to reproduce the experimental transition temperature, as choosing an inadequate functional can easily miss the transition temperature by more than 100 K. These results demonstrate that the here validated methodology is ideally suited to understand how factors such as strain engineering, surface functionalization, or compositional engineering could help to phase-stabilize MHPs for targeted applications.

JJL received funding from the Research Foundation Flanders (grant nr. 12P1819N). The project received funding from the Research Foundation Flanders (grants nrs, G018919N, W001919N). JVDH and TWC received funding from DOB Ecology. JA received funding from the University of Helsinki, Faculty of Science (MICROCLIM, grant nr. 7510145) and Academy of Finland Flagship (grant no. 337552). PDF, CM and PV received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (ERC Starting Grant FORMICA 757833). JK received funding from the Arctic Interactions at the University of Oulu and Academy of Finland (318930, Profi 4), Maaja vesitekniikan tuki ry., Tiina and Antti Herlin Foundation, Nordenskiold Samfundet and Societas pro Fauna et Flora Fennica. MK received funding from the Czech Science Foundation (grant nr. 20-28119S) and the Czech Academy of Sciences (grant nr. RVO 67985939). TWC received funding from National Geographic Society grant no. 9480-14 and WW-240R-17. MA received funding from CISSC (program ICRP (grant nr:2397) and INSF (grant nr: 96005914). The Royal Botanic Garden Edinburgh is supported by the Scottish Government's Rural and Environment Science and Analytical Services Division. JMA received funding from the Funding Org. Qatar Petroleum (grant nr. QUEX-CAS-QP-RD-18/19). JMA received funding from the European Union's Horizon 2020 research and innovation program (grant no. 678841) and from the Swiss National Science Foundation (grant no. 31003A_176044). JA was supported by research grants LTAUSA19137 (program INTER-EXCELLENCE, subprogram INTER-ACTION) provided by Czech Ministry of Education, Youth and Sports and 20-05840Y of the Czech Science Foundation. AA was supported by the Ministry of Science and Higher Education of the Russian Federation (grant FSRZ-2020-0014). SN, UAT, JJA, and JvO received funding from the Independent Research Fund Denmark (7027-00133B). LvdB, KT, MYB and RC acknowledge funding from the German Research Foundation within the Priority Program SPP-1803 'EarthShape: Earth Surface Shaping by Biota' (grant TI 338/14-1&2 and BA 3843/6-1). PB was supported by grant project VEGA of the Ministry of Education of the Slovak Republic and the Slovak Academy of Sciences No. 2/0132/18. Forest Research received funding from the Forestry Commission (climate change research programme). JCB acknowledges the support of Universidad Javeriana. JLBA received funding from the Direccion General de Cambio Climatico del Gobierno de Aragon; JLBA acknowledges fieldwork assistance by Ana Acin, the Ordesa y Monte Perdido National Park, and the Servicio de Medio Ambiente de Soria de la Junta de Castilla y Leon. RGB and MPB received funding from BECC - Biodiversity and Ecosystem services in a Changing Climate. MPB received funding from The European Union's Horizon 2020 research and innovation program under the Marie Skodowska-Curie Grant Agreement No. 657627 and The Swedish Research Council FORMAS - future research leaders No. 2016-01187. JB received funding from the Czech Academy of Sciences (grant nr. RVO 67985939). NB received funding from the SNF (grant numbers 40FA40_154245, 20FI21_148992, 20FI20_173691, 407340_172433) and from the EU (contract no. 774124). ICOS EU research infrastructure. EU FP7 NitroEurope. EU FP7 ECLAIRE. The authors from Biological Dynamics of Forest Fragments Project, PDBFF, Instituto Nacional de Pesquisas da Amazonia, Brazil were supported by the MCTI/CNPq/FNDCT - AcAo Transversal no68/2013 - Programa de Grande Escala da Biosfera-Atmosfera na Amazonia - LBA; Project 'Como as florestas da Amazonia Central respondem as variacoes climaticas? Efeitos sobre dinamica florestal e sinergia com a fragmentacAo florestal'. This is the study 829 of the BDFFP Technical Series. to The EUCFLUX Cooperative Research Program and Forest Science and Research Institute-IPEF. NC acknowledges funding by Stelvio National Park. JC was funded by the Spanish government grant CGL2016-78093-R. ANID-FONDECYT 1181745 AND INSTITUTO ANTARTICO CHILENO (INACH FR-0418). SC received funding from the German Research Foundation (grant no. DFG- FZT 118, 202548816). The National Science Foundation, Poland (grant no. UMO-2017/27/B/ST10/02228), within the framework of the 'Carbon dioxide uptake potential of sphagnum peatlands in the context of atmospheric optical parameters and climate changes' (KUSCO2) project. SLC received funding from the South African National Research Foundation and the Australian Research Council. FM, M, KU and MU received funding from Slovak Research and Development Agency (no. APVV-19-0319). Instituto Antartico Chileno (INACH_RT-48_16), Iniciativa Cientifica Milenio Nucleo Milenio de Salmonidos Invasores INVASAL, Institute of Ecology and Biodiversity (IEB), CONICYT PIA APOYO CCTE AFB170008. PC is supported by NERC core funding to the BAS 'Biodiversity, Evolution and Adaptation Team. EJC received funding from the Norwegian Research Council (grant number 230970). GND was supported by NERC E3 doctoral training partnership grant (NE/L002558/1) at the University of Edinburgh and the Carnegie Trust for the Universities of Scotland. Monitoring stations on Livingston Island, Antarctica, were funded by different research projects of the Gobern of Spain (PERMAPLANET CTM2009-10165-E; ANTARPERMA CTM2011-15565-E; PERMASNOW CTM2014-52021-R), and the PERMATHERMAL arrangement between the University of Alcala and the Spanish Polar Committee. GN received funding from the Autonomous Province of Bolzano (ITA). The infrastructure, part of the UK Environmental Change Network, was funded historically in part by ScotNature and NERC National Capability LTS-S: UK-SCAPE; NE/R016429/1). JD was supported by the Czech Science Foundation (GA17-19376S) and MSMT (LTAUSA18007). ED received funding from the Kempe Foundation (JCK-1112 and JCK-1822). The infrastructure was supported by the Ministry of Education, Youth and Sports of the Czech Republic within the National Sustainability Programme I (NPU I), grant number LO1415 and by the project for national infrastructure support CzeCOS/ICOS Reg. No. LM2015061. NE received funding from the German Research Foundation (DFG- FZT 118, 202548816). BE received funding from the GLORIA-EU project no EVK2-CT2000-00056, the Autonomous Province of Bolzano (ITA), from the Tiroler Wissenschaftsfonds and from the University of Innsbruck. RME was supported by funding to the SAFE Project from the Sime Darby Foundation. OF received funding from the German Research Foundation (DFG- FZT 118, 202548816). EFP was supported by the Jardin Botanico Atlantico (SV-20-GIJON-JBA). MF was funded by the German Federal Ministry of Education and Research (BMBF) in the context of The Future Okavango (Grant No. 01LL0912) and SASSCAL (01LG1201M; 01LG1201N) projects. EFL received funding from ANID PIA / BASAL FB210006. RAG received funding from Fondecyt 11170516, CONICYT PIA AFB170008 and ANID PIA / BASAL FB210006. MBG received funding from National Parks (DYNBIO, #1656/2015) and The Spanish Research Agency (VULBIMON, #CGL2017-90040-R). MG received funding from the Swiss National Science Foundation (ICOS-CH Phase 2 20FI20_173691). FG received funding from the German Research Foundation (DFG- FZT 118, 202548816). KG and TS received funding from the UK Biotechnology and Biological Research Council (grant = 206/D16053). SG was supported by the Research Foundation Flanders (FWO) (project G0H1517N). KJ and PH received funding from the EU Horizon2020 INFRAIA project eLTER-PLUS (871128), the project LTER-CWN (FFG, F&E Infrastrukturforderung, project number 858024) and the Austrian Climate Research Program (ACRP7 - CentForCSink - KR14AC7K11960). SH and ARB received funding through iDiv funded by the German Research Foundation (DFG- FZT 118, 202548816). LH received funding from the Czech Science Foundation (grant nr. 20-28119S) and the Czech Academy of Sciences (grant nr. RVO 67985939). MH received funding from the Baden-Wurttemberg Ministry of Science, Research and Arts via the project DRIeR (Drought impacts, processes and resilience: making the in-visible visible). LH received funding from International Polar Year, Weston Foundation, and ArcticNet. DH received funding from Natural Sciences and Engineering Council (Canada) (RGPIN-06691). TTH received funding from Independent Research Fund Denmark (grant no. 8021-00423B) and Villum Foundation (grant no. 17523). Ministry of Education, Youth and Sports of the Czech Republic (projects LM2015078, VAN2020/01 and CZ.02.1.01/0.0/0.0/16_013/0001708). KH, CG and CJD received funding from Bolin Centre for Climate Research, Stockholm University and from the Swedish research council Formas [grant n:o 2014-00530 to KH]. JJ received funding from the Funding Org. Swedish Forest Society Foundation (grant nr. 2018-485-Steg 2 2017) and Swedish Research Council FORMAS (grant nr. 2018-00792). AJ received funding from the German Federal Ministry of Education and Research BMBF (Grant Nr. FKZ 031B0516C SUSALPS) and the Oberfrankenstiftung (Grant Nr. OFS FP00237). ISJ received funding from the Energy Research Fund (NYR-11 - 2019, NYR-18 - 2020). TJ was supported by a UK NERC Independent Research Fellowship (grant number: NE/S01537X/1). RJ received funding from National Science Centre of Poland (grant number: 2016/21/B/ST10/02271) and Polish National Centre for Research and Development (grant number: Pol-Nor/203258/31/2013). VK received funding from the Czech Academy of Sciences (grant nr. RVO 67985939). AAK received funding from MoEFCC, Govt of India (AICOPTAX project F. No. 22018/12/2015/RE/Tax). NK received funding from FORMAS (grants nr. 2018-01781, 2018-02700, 2019-00836), VR, support from the research infrastructure ICOS-SE. BK received funding from the National Research, Development and Innovation Fund of Hungary (grant nr. K128441). Ministry of Education, Youth and Sports of the Czech Republic (projects LM2015078 and CZ.02.1.01/0.0/0.0/16_013/0001708). Project B1-RNM-163-UGR-18-Programa Operativo FEDER 2018, partially funded data collection. Norwegian Research Council (NORKLIMA grants #184912 and #244525) awarded to Vigdis Vandvik. MM received funding from the Czech Science Foundation (grant nr. 20-28119S) and the Czech Academy of Sciences (grant nr. RVO 67985939). Project CONICYT-PAI 79170119 and ANID-MPG 190029 awarded to Roy Mackenzie. This work was partly funded by project MIUR PON Cluster OT4CLIMA. RM received funding from the SNF project number 407340_172433. FM received funding from the Stelvio National Park. PM received funding from AIAS-COFUND fellowship programme supported by the Marie Skodowska- Curie actions under the European Union's Seventh Framework Pro-gramme for Research, Technological development and Demonstration (grant agreement no 609033) and the Aarhus University Research Foundation, Denmark. RM received funding from the Ministry of Education, Youth and Sports of the Czech Republic (project LTT17033). SM and VM received funding from EU FP6 NitroEurope (grant nr. 17841), EU FP7 ECLAIRE (grant nr. 282910), the Ministry of Education and Science of Ukraine (projects nr. 505, 550, 574, 602), GEF-UNEP funded "Toward INMS" project (grant nr. NEC05348) and ENI CBC BSB PONTOS (grant nr. BSB 889). The authors from Biological Dynamics of Forest Fragments Project, PDBFF, Instituto Nacional de Pesquisas da Amazonia, Brazil were supported by the MCTI/CNPq/FNDCT - AcAo Transversal no68/2013 - Programa de Grande Escala da Biosfera-Atmosfera na Amazonia - LBA; Project 'Como as florestas da Amazonia Central respondem as variacoes climaticas? Efeitos sobre dinamica florestal e sinergia com a fragmentacAo florestal'. FJRM was financially supported by the Netherlands Organization for Scientific Research (VICI grant 016.VICI.170.072) and Research Foundation Flanders (FWO-SBO grant S000619N). STM received funding from New Frontiers in Research Fund-Exploration (grant nr. NFRF-2018-02043) and NSERC Discovery. MMR received funding from the Australian Research Council Discovery Early Career Research Award (grant nr. DE180100570). JAM received funding from the National Science Foundation (DEB 1557094), International Center for Advanced Renewable Energy and Sustainability (I-CARES) at Washington University in St. Louis, ForestGEO, and Tyson Research Center. IM-S was funded by the UK Natural Environment Research Council through the ShrubTundra Project (NE/M016323/1). MBN received funding from FORMAS, VR, Kempe Foundations support from the research infrastructures ICOS and SITES. MDN received funding from CONICET (grant nr. PIP 112-201501-00609). Spanish Ministry of Science grant PID2019-110521GB-I00 and Catalan government grant 2017-1005. French National Research Agency (ANR) in the frame of the Cluster of Excellence COTE (project HydroBeech, ANR-10-LABX-45). VLIR-OUS, under the Institutional University Coorperation programme (IUC) with Mountains of the Moon University. Project LAS III 77/2017/B entitled: \"Estimation of net carbon dioxide fluxes exchanged between the forest ecosystem on post-agricultural land and between the tornado-damaged forest area and the atmosphere using spectroscopic and numerical methods\", source of funding: General Directorate of State Forests, Warsaw, Poland. Max Planck Society (Germany), RFBR, Krasnoyarsk Territory and Krasnoyarsk Regional Fund of Science, project number 20-45-242908. Estonian Research Council (PRG609), and the European Regional Development Fund (Centre of Excellence EcolChange). Canada-Denmark Arctic Research Station Early Career Scientist Exchange Program, from Polar knowledge Canada (POLAR) and the Danish Agency for Science and Higher Education. AP received funding from Fondecyt 1180205, CONICYT PIA AFB170008 and ANID PIA / BASAL FB210006. MP received funding from the Funding Org. Knut and Alice Wallenberg Foundation (grant nr. 2015.0047), and acknowledges funding from the Swedish Research Council (VR) with contributing research institutes to both the SITES and ICOS Sweden infrastructures. JP and RO were funded by the Spanish Ministry of Science grant PID2019-110521GB-I00, the fundacion Ramon Areces grant ELEMENTAL-CLIMATE, and the Catalan government grant 2017-1005. MPB received funding from the Svalbard Environmental Protection Fund (grant project number 15/128) and the Research Council of Norway (Arctic Field Grant, project number 269957). RP received funding from the Ministry of Education, Youth and Sports of the Czech Republic (grant INTER-TRANSFER nr. LTT20017). LTSER Zone Atelier Alpes; Federation FREE-Alpes. RP received funding from a Humboldt Fellowship for Experienced Researchers. Prokushkin AS and Zyryanov VI contribution has been supported by the RFBR grant #18-05-60203-Arktika. RPu received founding from the Polish National Science Centre (grant project number 2017/27/B/NZ8/00316). ODYSSEE project (ANR-13-ISV7-0004, PN-II-ID-JRP-RO-FR-2012). KR was supported through an Australian Government Research Training Program Scholarship. Fieldwork was supported by the Global Challenges program at the University of Wollongong, the ARC the Australian Antarctic Division and INACH. DR was funded by the project SUBANTECO IPEV 136 (French Polar Institute Paul-Emile Victor), Zone Atelier CNRS Antarctique et Terres Australes, SAD Region Bretagne (Project INFLICT), BiodivERsa 2019-2020 BioDivClim call 'ASICS' (ANR-20-EBI5-0004). SAR received funding from the Australian Research Council. NSF grant #1556772 to the University of Notre Dame. Pavia University (Italy). OR received funding from EU-LEAP-Agri (RAMSES II), EU-DESIRA (CASSECS), EU-H2020 (SustainSahel), AGROPOLIS and TOTAL Foundations (DSCATT), CGIAR (GLDC). AR was supported by the Russian Science Foundation (Grant 18-74-10048). Parc national des Ecrins. JS received funding from Vetenskapsradet grant nr (No: 2014-04270), ALTER-net multi-site grant, River LIFE project (LIFE08 NAT/S/000266), Flexpeil. Helmholtz Association long-term research program TERENO (Terrestrial Environmental Observatories). PS received funding from the Polish Ministry of Science and Higher Education (grant nr. N N305 304840). AS acknowledges funding by ETH Zurich project FEVER ETH-27 19-1. LSC received funding from NSERC Canada Graduate Scholarship (Doctoral) Program; LSC was also supported by ArcticNet-NCE (insert grant #). Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (141513/2017-9); FundacAo Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro (E26/200.84/2019). ZS received funding from the SRDA (grants nos. APVV-16-0325 and APVV-20-0365) and from the ERDF (grant no. ITMS 313011S735, CE LignoSilva). JS, MB and CA received funding from core budget of ETH Zurich. State excellence Program M-V \"WETSCAPES\". AfricanBioServices project funded by the EU Horizon 2020 grant number 641918. The authors from KIT/IMK-IFU acknowledge the funding received within the German Terrestrial Environmental Observatories (TERENO) research program of the Helmholtz Association and from the Bavarian Ministry of the Environment and Public Health (UGV06080204000). Deutsche Forschungsgemeinschaft (DFG, German Research Foundation), project number 192626868, in the framework of the collaborative German-Indonesian research project CRC 990 (SFB): 'EFForTS, Ecological and Socioeconomic Functions of Tropical Lowland Rainforest Transformation Systems (Sumatra, Indonesia)'. MS received funding from the Ministry of Education, Youth and Sports of the Czech Republic (grant nr. INTER-TRANSFER LTT19018). TT received funding from the Swedish National Space Board (SNSB Dnr 95/16) and the CASSECS project supported by the European Union. HJDT received funding from the UK Natural Environment Research Council (NERC doctoral training partnership grant NE/L002558/1). German Science Foundation (DFG) GraKo 2010 \"Response\". PDT received funding from the MEMOIRE project (PN-III-P1-1.1-PD2016-0925). Arctic Challenge for Sustainability II (ArCS II; JPMXD1420318865). JU received funding from Czech Science Foundation (grant nr. 21-11487S). TU received funding from the Romanian Ministry of Education and Research (CCCDI - UEFISCDI -project PN-III-P2-2.1-PED-2019-4924 and PN2019-2022/19270201-Ctr. 25N BIODIVERS 3-BIOSERV). AV acknowledge funding from RSF, project 21-14-00209. GFV received funding from the Dutch Research Council NWO (Veni grant, no. 863.14.013). Australian Research Council Discovery Early Career Research Award DE140101611. FGAV received funding from the Portuguese Science Foundation (FCT) under CEECIND/02509/2018, CESAM (UIDP/50017/2020+UIDB/50017/2020), FCT/MCTES through national funds, and the co-funding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. Ordesa y Monte Perdido National Park. MVI received funding from the Spanish Ministry of Science and Innovation through a doctoral grant (FPU17/05869). JW received funding from the Czech Science Foundation (grant nr. 20-28119S) and the Czech Academy of Sciences (grant nr. RVO 67985939). CR and SW received funding from the Swiss Federal Office for the Environment (FOEN) and the de Giacomi foundation. YY received funding from the National Natural Science Foundation of China (Grant no. 41861134039 and 41941015). ZY received funding from the National Natural Science Foundation of China (grant nr. 41877458). FZ received funding from the Swiss National Science Foundation (grant nr. 172198 and 193645). PZ received funding from the Funding Org. Knut and Alice Wallenberg Foundation (grant no. 2015.0047). JL received funding from (i) the Agence Nationale de la Recherche (ANR), under the framework of the young investigators (JCJC) funding instrument (ANR JCJC Grant project NoANR-19-CE32-0005-01: IMPRINT) (ii) the Centre National de la Recherche Scientifique (CNRS) (Defi INFINITI 2018: MORFO); and the Structure Federative de Recherche (SFR) Condorcet (FR CNRS 3417: CREUSE). Fieldwork in the Arctic got facilitated by funding from the EU INTERACT program. SN, UAT, JJA and JvO would like to thank the field team of the Vegetation Dynamics group for their efforts and hard work. We acknowledge Dominique Tristan for letting access to the field. For the logistic support the crew of INACH and Gabriel de Castilla Station team on Deception Island. We thank the Inuvialuit and Kluane First Nations for the opportunity to work on their land. MAdP acknowledges fieldwork assistance and logistics support to Unidad de Tecnologia Marina CSIC, and the crew of Juan Carlos I and Gabriel de Castilla Spanish Antarctic Stations, as well as to the different colleagues from UAH that helped on the instrument maintenance. ERF acknowledges fieldwork assistance by Martin Heggli. MBG acknowledges fieldwork and technical assistance by P Abadia, C Benede, P Bravo, J Gomez, M Grasa, R Jimenez, H Miranda, B Ponz, J Revilla and P Tejero and the Ordesa and Monte Perdido National Park staff. LH acknowledges field assistance by John Jacobs, Andrew Trant, Robert Way, Darroch Whitaker; we acknowledge the Inuit of Nunatsiavut, and the Co-management Board of Torngat Mountains National Park for their support of this project and acknowledge that the field research was conducted on their traditional lands. We thank our many bear guides, especially Boonie, Eli, Herman, John and Maria Merkuratsuk. AAK acknowledges field support of Akhtar Malik, Rameez Ahmad. Part of microclimatic records from Saxony was funded by the Saxon Switzerland National Park Administration. Tyson Research Center. JP acknowledges field support of Emmanuel Malet (Edytem) and Rangers of Reserves Naturelles de Haute-Savoie (ASTERS). Practical help: Roel H. Janssen, N. Huig, E. Bakker, Schools in the tepaseforsoket, Forskar fredag, Erik Herberg. The support by the Bavarian Forest National Park administration is highly appreciated. LvdB acknowledges CONAF and onsite support from the park rangers from PN Pan de Azucar, PN La Campana, PN Nahuelbuta and from communidad agricola Quebrada de Talca. JL and FS acknowledge Manuel Nicolas and all forest officers from the Office National des Forets (ONF) who are in charge of the RENECOFOR network and who provided help and local support for the installation and maintenance of temperature loggers in the field., Research in global change ecology relies heavily on global climatic grids derived from estimates of air temperature in open areas at around 2 m above the ground. These climatic grids do not reflect conditions below vegetation canopies and near the ground surface, where critical ecosystem functions occur and most terrestrial species reside. Here, we provide global maps of soil temperature and bioclimatic variables at a 1-km2 resolution for 0–5 and 5–15 cm soil depth. These maps were created by calculating the difference (i.e. offset) between in situ soil temperature measurements, based on time series from over 1200 1-km2 p ixels ( summarized f rom 8 519 u nique t emperature sensors) across all the world's major terrestrial biomes, and coarse-grained air temperature estimates from ERA5-Land (an atmospheric reanalysis by the European Centre for Medium-Range Weather Forecasts). We show that mean annual soil temperature differs markedly from the corresponding gridded air temperature, by up to 10°C (mean = 3.0 ± 2.1°C), with substantial variation across biomes and seasons. Over the year, soils in cold and/or dry biomes are substantially warmer (+3.6 ± 2.3°C) than gridded air temperature, whereas soils in warm and humid environments are on average slightly cooler (−0.7 ± 2.3°C). The observed substantial and biome-specific offsets emphasize that the projected impacts of climate and climate change on near-surface biodiversity and ecosystem functioning are inaccurately assessed when air rather than soil temperature is used, especially in cold environments. The global soil-related bioclimatic variables provided here are an important step forward for any application in ecology and related disciplines. Nevertheless, we highlight the need to fill remaining geographic gaps by collecting more in situ measurements of microclimate conditions to further enhance the spatiotemporal resolution of global soil temperature products for ecological applications., FWO G018919N W001919N 12P1819N, DOB Ecology, University of Helsinki, Faculty of Science (MICROCLIM) 7510145, European Research Council (ERC) FORMICA 757833, Arctic Interactions at the University of Oulu, Academy of Finland 318930 337552, Maaja vesitekniikan tuki ry., Tiina and Antti Herlin Foundation, Nordenskiold Samfundet, Societas pro Fauna et Flora Fennica, Grant Agency of the Czech Republic 20-28119S 20-05840Y GA17-19376S 21-11487S, Czech Academy of Sciences RVO 67985939, National Geographic Society 9480-14 WW-240R-17, CISSC (program ICRP) 2397, Iran National Science Foundation (INSF) 96005914, Scottish Government's Rural and Environment Science and Analytical Services Division, Qatar Petroleum QUEX-CAS-QP-RD-18/19, European Union's Horizon 2020 research and innovation program 678841, Swiss National Science Foundation (SNSF), European Commission 172198 193645 31003A_176044, Ministry of Education, Youth & Sports - Czech Republic LTAUSA19137, Ministry of Science and Higher Education of the Russian Federation FSRZ-2020-0014, Independent Research Fund Denmark 8021-00423B 7027-00133B, German Research Foundation (DFG) DFG- FZT 118 202548816 TI 338/14-1 TI 338/14-2 BA 3843/6-1, grant project VEGA of the Ministry of Education of the Slovak Republic Slovak Academy of Sciences 2/0132/18, Forestry Commission, Universidad Javeriana, Direccion General de Cambio Climatico del Gobierno de Aragon, European Union's Horizon 2020 research and innovation program under the Marie Skodowska-Curie Grant 657627 SNF 407340_172433 40FA40_154245 20FI21_148992 20FI20_173691, European Commission 17841 774124, MCTI/CNPq/FNDCT 68/2013, Project 'Como as florestas da Amazonia Central respondem as variacoes climaticas? Efeitos sobre dinamica florestal e sinergia com a fragmentacAo florestal', Spanish Government, European Commission CGL2016-78093-R, ANID-FONDECYT 1181745, National Science Foundation, Poland UMO-2017/27/B/ST10/02228, National Research Foundation - South Africa, Australian Research Council, Slovak Research and Development Agency APVV-19-0319, Instituto Antartico Chileno INACH_RT-48_16 INACH FR-0418, Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) PIA APOYO CCTE AFB170008 PIA AFB170008, UK Research & Innovation (UKRI), Natural Environment Research Council (NERC), Research Council of Norway, European Commission 230970, NERC E3 doctoral training partnership grant at the University of Edinburgh NE/L002558/1, Carnegie Trust for the Universities of Scotland, Gobern of Spain PERMAPLANET CTM2009-10165-E ANTARPERMA CTM2011-15565-E PERMASNOW CTM2014-52021-R, University of Alcala, Spanish Polar Committee, Autonomous Province of Bolzano (ITA), ScotNature, NERC National Capability LTS-S: UK-SCAPE NE/R016429/1, Ministry of Education, Youth & Sports - Czech Republic LTAUSA18007, Kempe Foundation JCK-1112 JCK-1822, Ministry of Education, Youth and Sports of the Czech Republic within the National Sustainability Programme I (NPU I) LO1415, project for national infrastructure support CzeCOS/ICOS LM2015061 GLORIA-EU EVK2-CT2000-00056, Tiroler Wissenschaftsfonds, University of Innsbruck, Sime Darby Foundation, Jardin Botanico Atlantico SV-20-GIJON-JBA, Federal Ministry of Education & Research (BMBF) 01LL0912 01LG1201M 01LG1201N, Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT FONDECYT 11170516 1180205, ANID PIA / BASAL FB210006, National Parks (DYNBIO) 1656/2015, Spanish Research Agency (VULBIMON) CGL2017-90040-R, Swiss National Science Foundation (SNSF) 20FI20_173691, Biotechnology and Biological Sciences Research Council (BBSRC) 206/D16053 FWO G0H1517N, EU Horizon2020 INFRAIA project eLTER-PLUS 871128, project LTER-CWN (FFG, F&E Infrastrukturforderung) 858024, Austrian Climate Research Program ACRP7 - CentForCSink - KR14AC7K11960, iDiv by the German Research Foundation DFG- FZT 118 202548816, Baden-Wurttemberg Ministry of Science, Research and Arts, Weston Foundation, ArcticNet, Natural Sciences and Engineering Research Council of Canada (NSERC) RGPIN-06691, Villum Foundation 17523, Ministry of Education, Youth & Sports - Czech Republic LM2015078 VAN2020/01 CZ.02.1.01/0.0/0.0/16_013/0001708 LTT17033 LTT20017 INTER-TRANSFER LTT19018, Bolin Centre for Climate Research, Stockholm University, Swedish Research Council Swedish Research Council Formas 2014-00530 2018-00792 2016-01187, Swedish Forest Society Foundation 2018-485-Steg 2 2017, Federal Ministry of Education & Research (BMBF) FKZ 031B0516C SUSALPS, Oberfrankenstiftung OFS FP00237, Energy Research Fund NYR-11 - 2019 NYR-18 - 2020, UK NERC Independent Research Fellowship NE/S01537X/1, National Science Centre, Poland 2016/21/B/ST10/02271, Polish National Centre for Research and Development Pol-Nor/203258/31/2013, MoEFCC, Govt of India (AICOPTAX project) 22018/12/2015/RE/Tax, Swedish Research Council Formas 2018-01781 2018-02700 2019-00836, research infrastructure ICOS-SE, National Research, Development and Innovation Fund of Hungary K128441, Programa Operativo FEDER 2018 B1-RNM-163-UGR-18, Norwegian Research Council (NORKLIMA grants) 184912 244525, CONICYT-PAI 79170119, ANID-MPG 190029, project MIUR PON Cluster OT4CLIMA, Stelvio National Park, AIAS-COFUND fellowship programme - Marie Skodowska- Curie actions under the European Union's Seventh Framework Pro-gramme for Research, Technological development and Demonstration 609033, Aarhus University Research Foundation, Denmark, EU FP6 NitroEurope 17841, EU FP7 ECLAIRE 282910, Ministry of Education and Science of Ukraine 505 550 574 602, GEF-UNEP NEC05348, ENI CBC BSB PONTOS BSB 889, Netherlands Organization for Scientific Research (NWO) 016.VICI.170.072, New Frontiers in Research Fund-Exploration NFRF-2018-02043, Natural Sciences and Engineering Research Council of Canada (NSERC), Australian Research Council DE180100570, National Science Foundation (NSF) DEB 1557094, International Center for Advanced Renewable Energy and Sustainability (I-CARES) at Washington University in St. Louis, Smithsonian Institution Smithsonian Tropical Research Institute, Tyson Research Center, UK Natural Environment Research Council through the ShrubTundra Project NE/M016323/1, Swedish Research Council Formas Swedish Research Council, Kempe Foundations - research infrastructure ICOS Kempe Foundations - research infrastructure SITES, Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) PIP 112-201501-00609, Spanish Government PID2019-110521GB-I00, Catalan government 2017-1005, French National Research Agency (ANR) ANR-10-LABX-45, General Directorate of State Forests, Warsaw, Poland, Max Planck Society, Russian Foundation for Basic Research (RFBR), Krasnoyarsk Territory Krasnoyarsk Regional Fund of Science 20-45-242908, Estonian Research Council PRG609, Knut & Alice Wallenberg Foundation 2015.0047, Swedish Research Council, fundacion Ramon Areces grant ELEMENTAL-CLIMATE, Svalbard Environmental Protection Fund 15/128, Research Council of Norway 269957, Humboldt Fellowship for Experienced Researchers, Russian Foundation for Basic Research (RFBR) 18-05-60203-Arktika, Polish National Science Centre 2017/27/B/NZ8/00316, ODYSSEE project (PN-II-ID-JRP-RO-FR-2012) ANR-13-ISV7-0004, Australian Government, Department of Industry, Innovation and Science, Global Challenges program at the University of Wollongong, ARC the Australian Antarctic Division, INACH, project SUBANTECO IPEV 136 (French Polar Institute Paul-Emile Victor), Zone Atelier CNRS Antarctique et Terres Australes, SAD Region Bretagne (Project INFLICT), BiodivERsa 2019-2020 BioDivClim call 'ASICS' ANR-20-EBI5-0004, National Science Foundation (NSF) 1556772, EU-LEAP-Agri (RAMSES II) EU-DESIRA (CASSECS) EU-H2020 (SustainSahel), AGROPOLIS, Total SA, CGIAR, Russian Science Foundation (RSF) 18-74-10048, Swedish Research Council 2014-04270, ALTER-net multi-site grant, River LIFE project LIFE08 NAT/S/000266, Flexpeil, Ministry of Science and Higher Education, Poland N N305 304840, ETH Zurich FEVER ETH-27 19-1, NSERC Canada Graduate Scholarship (Doctoral) Program, ArcticNet-NCE, Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPQ) 141513/2017-9, Fundacao Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio De Janeiro (FAPERJ) E26/200.84/2019, SRDA APVV-16-0325 APVV-20-0365, ERDF (CE LignoSilva) ITMS 313011S735, ETH Zurich, EU Horizon 2020 641918, German Terrestrial Environmental Observatories (TERENO) research program of the Helmholtz Association, Bavarian Ministry of the Environment and Public Health UGV06080204000 German Research Foundation (DFG) 192626868, Swedish National Space Board (SNSB) 95/16, CASSECS project by the European Union, Natural Environment Research Council (NERC) NE/L002558/1, MEMOIRE project PN-III-P1-1.1-PD2016-0925, Arctic Challenge for Sustainability II (ArCS II) JPMXD1420318865, Consiliul National al Cercetarii Stiintifice (CNCS), Unitatea Executiva pentru Finantarea Invatamantului Superior, a Cercetarii, Dezvoltarii si Inovarii (UEFISCDI) PN-III-P2-2.1-PED-2019-4924 PN2019-2022/19270201, 25N BIODIVERS 3-BIOSERV, Russian Science Foundation (RSF) 21-14-00209., Netherlands Organization for Scientific Research (NWO) 863.14.013, Australian Research Council DE140101611, Portuguese Foundation for Science and Technology CEECIND/02509/2018 CESAM UIDP/50017/2020+UIDB/50017/2020, Portuguese Foundation for Science and Technology European Commission, FEDER, within the PT2020 Partnership Agreement, Compete 2020, Spanish Government FPU17/05869, Swiss Federal Office for the Environment (FOEN), Giacomi foundation, National Natural Science Foundation of China (NSFC) 41861134039 41941015 41877458, French National Research Agency (ANR) ANR-19-CE32-0005-01 Centre National de la Recherche Scientifique (CNRS), Structure Federative de Recherche (SFR) Condorcet (FR CNRS 3417: CREUSE), EU INTERACT program, Inuit of Nunatsiavut, Co-management Board of Torngat Mountains National Park, Saxon Switzerland National Park Administration, Bavarian Forest National Park administration, BECC - Biodiversity and Ecosystem services in a Changing Climate, Research Foundation Flanders (FWO-SBO) S000619N

ispartof: ADVANCED ENERGY MATERIALS status: Published online

We report the in-situ formation of germanium vacancy (GeV) centres in nanocrystalline diamond (NCD) using chemical vapor deposition (CVD) technique. Commercial Ge wafers are used as the solid dopant source and as substrate. The hydrogen-rich plasma (1% CH4 in H2, 3000 W and 45 Torr, ASTeX 6500 series deposition system) etches the Ge substrate and introduces the GeV complex in the NCD layer. As the melting proximity of Ge and CVD diamond growth temperature introduces limitations; the NCD depositions are restricted to (720 ± 20)°C. Scanning electron microscopy reveal randomly facetted film morphology and Raman measurements confirm diamond formation under the chosen deposition conditions. We discuss an additional challenge, the absence of carbide layer at the Ge-NCD interface, potentially limiting film adhesion to the Ge substrate but at the same time demonstrate self-delaminating free-standing multicrystalline diamond films. Qualitative analysis using time of flight secondary mass ion spectroscopy confirms Ge incorporation, and room temperature photoluminescence (PL) measurements confirm local GeV ensemble formation in diamond films as indicated by the 602 nm PL peak. We also discuss the challenges in using NCD, present low-temperature (10K) PL results and assign strain to explain GeV peak shifts in such material.

Inorganic chiral nanoparticles are attracting more and more attention due to their peculiar optical properties and potential biological applications, such as bioimaging, therapeutics, and diagnostics. Among inorganic chiral nanoparticles, gold chiral nanostructures were demonstrated to be very interesting in this context, with good physical chemical stability and also the possibility to decorate the surface, improving biomedical application as the interaction with the bio-systems. Gold (Au) nanostructures were synthesized according to a seed-mediated procedure which envisages the use of cetyltrimethylammonium bromide (CTAB) as the capping agent and L- and D-cysteine to promote chirality. Au nanostructures have been demonstrated to have opposite circular dichroism signals depending on the amino acid enantiomer used during the synthesis. Then, a procedure to decorate the Au surface with penicillamine, a drug used for the treatment of Wilson's disease, was developed. The composite material of gold nanoparticles/penicillamine was characterized using electron microscopy, and the penicillamine functionalization was monitored by means of UV-Visible, Raman, and infrared spectroscopy, highlighting the formation of the Au-S bond. Furthermore, electron circular dichroism was used to monitor the chirality of the synthesized nanostructures and it was demonstrated that both penicillamine enantiomers can be successfully bonded with both the enantiomers of the gold nanostructures without affecting gold nanoparticles' chirality. The effective modification of nanostructures' surfaces via penicillamine introduction allowed us to address the important issue of controlling chirality and surface properties in the chiral nano-system. ispartof: NANOMATERIALS vol:13 issue:9 ispartof: location:Switzerland status: published

The Amaryllidaceae species are well-known as a rich source of bioactive compounds in nature. Although Hymenocallis littoralis has been studied for decades, its polar components were rarely explored. The current phytochemical investigation of Amaryllidaceae alkaloids from H. littoralis led to the identification of three previously undescribed compounds: O-demethyl-norlycoramine (1), (-)-2-epi-pseudolycorine (2) and (+)-2-epi-pseudolycorine (3), together with eight known compounds: 6α-hydroxyhippeastidine (4), 6β-hydroxyhippeastidine (5), lycorine (6), 2-epi-lycorine (7), zephyranthine (8), ungeremine (9), pancratistatin (10) and 9-O-demethyl-7-O-methyllycorenine (11). Among the eight previously reported compounds, five were isolated from H. littoralis for the first time (compounds 4, 5, 7, 8, and 9). Compounds 1, 4, 5, 7, 8, and 11 exhibited weak anti-SARS-CoV-2 activity (EC50 = 40-77 µM) at non-cytotoxic concentrations. Assessment of cytotoxicity on the Vero-E6 cell line revealed lycorine and pancratistatin as cytotoxic substances with CC50 values of 1.2 µM and 0.13 µM, respectively. The preliminary structure-activity relationship for the lycorine-type alkaloids in this study was further investigated, and as a result ring C appears to play a crucial role in their anti-SARS-CoV-2 activity. ispartof: MOLECULES vol:28 issue:7 ispartof: location:Switzerland status: published

Prolyl carboxypeptidase (PRCP) is involved in metabolic disorders by hydrolyzing anorexigenic peptides. A link between serum PRCP activity and obesity has been reported, but its origin/source is still unclear. Previously proven correlations between human serum PRCP activity and the amount of adipose tissue may suggest that adipose tissue is an important source of circulating PRCP. We investigated PRCP activity in visceral, subcutaneous adipose tissue (VAT and SCAT), skeletal muscle tissue and serum of lean and obese men with or without type 2 diabetes (T2D). Correlations between PRCP activity, metabolic and biochemical parameters and immune cell populations were assessed. PRCP activity was the highest in VAT, compared to SCAT, and was very low in skeletal muscle tissue in the overall group. Serum PRCP activity was significantly higher in T2-diabetic obese men, compared to lean and obese non-diabetic men, and was positively correlated with glycemic control. A positive correlation was observed between serum PRCP activity and VAT immune cell populations, which might indicate that circulating PRCP activity is deriving rather from the immune fraction than from adipocytes. In conclusion, PRCP activity was observed in human adipose tissue for the first time and serum PRCP activity is correlated with T2D in obese men. This research was funded by the Research Foundation Flanders (grant numbers FWO-SB 1S22417N and FWO-SBO S001017N) and by a GOA BOF 2015 grant of the University of Antwerp (No. 30729; www.uantwerp.be). Part of this work was supported by internal resources from Hasselt University. This study was financed by The Netherlands Organization for Scientific Research (NWO) (Veni 916.12.056), The Netherlands Heart Foundation (2013T143) and a Seventh Framework Program (FP7) Grant (CIG 322070). We thank University Biobank Limburg (UBiLim, Jessa Hospital, Belgium) for their technical support in sample handling and storage. Conflicts of Interest: The authors declare no conflict of interest.

Background Fecal metabolomic profiles differ between pediatric inflammatory bowel disease (IBD) patients and controls and may provide new insights in the pathophysiology of IBD. The role of amino acids, however, is not fully elucidated. We aimed to assess fecal amino acid profiles in pediatric IBD. Methods In this case-control study, treatment-naïve, newly diagnosed pediatric IBD patients and a non-IBD control group, matched based on sex and age, were included in 2 tertiary centres. Fecal amino acid profiles were assessed using a targeted high-performance liquid chromatography technique. A random forest classifier method was used to develop a prediction model differentiating IBD from controls and predicting IBD phenotype. The association between IBD localization and amino acid concentrations was tested with ordinal regression models. Results We included 78 newly diagnosed IBD patients (40 Crohn’s disease [CD], 38 ulcerative colitis [UC]) and 105 controls. Patients with IBD could be differentiated from controls with an accuracy of 82% (sensitivity 63%, specificity 97%). Twenty-nine out of the 42 measured unique amino acids were included in the prediction model. Increased levels of tryptophan, taurine, alanine, ornithine, valine, histidine, and leucine were the most differentiating features. Children with CD and UC could be differentiated from the controls with an accuracy of 80% and 90%, respectively. Inflammatory bowel disease phenotype could not be predicted. Tryptophan, valine, and histidine levels were positively associated with more extended disease in UC patients (P < .05). Conclusions Fecal amino acids may enhance understanding of the role of host-microbial interactions in the pathophysiology of IBD and may evolve into biomarkers for pediatric IBD diagnostic and personalized medicine.

Hyperpolarization using signal amplification by reversible exchange (SABRE) relies on target molecules and parahydrogen coordinating to a transition metal catalyst. Identification of this coordinated state becomes increasingly important, especially since bio-relevant targets such as pyruvate and amino acids exhibiting multiple binding sites are becoming compatible with SABRE. In this report, we present a fingerprinting method to discriminate and identify ligand binding sites without requiring the presence of a sensitive or isotope-labeled heteroatom. Adding a small concentration of protons to a deuterated medium, spontaneous 1H/D scrambling of exchangeable protons encodes the ligands each with an isotopological fingerprint. By use of rapid 2D zero quantum NMR, the binding sites are decoded from the hydrides in less than a minute. The new methodology is explained and demonstrated on Ir mixed complexes with pyridine, benzylamine, and ammonia as common N-functional ligands. ispartof: Journal Of Physical Chemistry Letters vol:13 issue:15 pages:3516-3522 ispartof: location:United States status: published

Formic acid is one of the key components in green chemistry being involved in energy storage, production of chemical intermediates and fuel components. Therefore the knowledge of its stability is of crucial importance and a systematic study of its decomposition is needed. The kinetics of formic acid decomposition to hydrogen and carbon dioxide was investigated in a laboratory-scale fixed bed reactor at 150–225 °C and atmospheric pressure. Palladium nanoparticles deposited on porous active carbon Sibunit were used as the heterogeneous catalyst. The catalyst was characterized by nitrogen physisorption and high-resolution transmission electron microscopy. The average palladium nanoparticle size was 5–6 nm. The impacts of mass transfer resistance and formic acid dimerization were negligible under the reaction conditions. Prolonged experiments revealed that the catalyst had a good stability. Hydrogen and carbon dioxide were the absolutely dominant reaction products, whereas the amounts of carbon monoxide and water were negligible. The experimental data were described with three kinetic models: first order kinetics, two-step adsorption-reaction model and multistep adsorption-decomposition model of formic acid. The multistep model gave the best description of the data.

We aimed to identify serum metabolites related to abnormal glucose metabolism (AGM) among women with gestational diabetes mellitus (GDM). The study recruited 50 women diagnosed with GDM during mid-late pregnancy and 50 non-GDM matchees in a Singapore birth cohort. At the 5-year post-partum follow-up, we applied an untargeted approach to investigate the profiles of serum metabolites among all participants. We first employed OPLS-DA and logistic regression to discriminate women with and without follow-up AGM, and then applied area under the curve (AUC) to assess the incremental indicative value of metabolic signatures on AGM. We identified 23 candidate metabolites that were associated with postpartum AGM among all participants. We then narrowed down to five metabolites [p-cresol sulfate, linoleic acid, glycocholic acid, lysoPC(16:1) and lysoPC(20:3)] specifically associating with both GDM and postpartum AGM. The combined metabolites in addition to traditional risks showed a higher indicative value in AUC (0.92–0.94 vs. 0.74 of traditional risks and 0.77 of baseline diagnostic biomarkers) and R2 (0.67–0.70 vs. 0.25 of traditional risks and 0.32 of baseline diagnostic biomarkers) in terms of AGM indication, compared with the traditional risks model and traditional risks and diagnostic biomarkers combined model. These metabolic signatures significantly increased the AUC value of AGM indication in addition to traditional risks, and might shed light on the pathophysiology underlying the transition from GDM to AGM.

The addition of polypropylene fibers has been shown to reduce the fire spalling propensity of concrete. This has been proven in many fire tests; but, very few large scale tests exist showing the fu ...

Background Inhibition of the microsomal prostaglandin (PG) E2 synthase (mPGES-1) introduces a promising anti-inflammatory treatment approach by specifically reducing PGE2 . The microvasculature is a central target organ for early manifestations of cardiovascular disease. Therefore, a better understanding of the prostaglandin system and characterising the effects of mPGES-1 inhibition in this vascular bed are of interest. Experimental approach The effects of mPGES-1 inhibition on constriction and relaxation of resistance arteries (O100-400μm) from patients with end stage kidney disease (ESKD) and controls (Non-ESKD) were studied using wire-myography in combination with immunological and mass-spectrometry based analyses. Key results Inhibition of mPGES-1 in arteries from ESKD patients and Non-ESKD controls significantly reduced adrenergic vasoconstriction, which was not affected by the COX-2 inhibitors NS-398 and Etoricoxib or the COX-1/COX-2 inhibitor Indomethacin, tested in Non-ESKD controls. Correspondingly, a significant increase of acetylcholine-induced dilatation was observed for mPGES-1 inhibition only. In IL-1β treated arteries, inhibition of mPGES-1 significantly reduced PGE2 levels while PGI2 levels remained unchanged. In contrast, COX-2 inhibition blocked the formation of both prostaglandins. Blockage of PGI2 signaling with an IP receptor antagonist did not restore the reduced constriction, neither did blocking of PGE2 -EP4 or signaling through PPARγ. A biphasic effect was observed for PGE2 , inducing dilatation at nmol and constriction at μmol concentrations. Immunohistochemistry demonstrated expression of mPGES-1, COX-1, PGIS, weak expression for COX-2 as well as receptor expression for PGE2 (EP1-4), thromboxane (TP) and PGI2 (IP) in ESKD and Non-ESKD. Conclusion Our study demonstrates vasodilating effects following mPGES-1 inhibition in human microvasculature and suggests that several pathways besides shunting to PGI2 may be involved.

Previous research suggests that everyday expressions are commonly used in students’ descriptions of nutrient uptake. This study investigate a classroom context in year 5 with a focus on signs of scientific meaning-making about nutrient uptake with an animation as a resource in two different schools. In one of the schools there was also a teacher review. The aim of this study is to investigate the pedagogical affordances of scientific terms and everyday expressions in the animation and in classroom teaching. Further, students’ signs of scientific meaning-making at the meso and submicro organizational level in group discussions and written descriptions are analyzed and if taking part of a teacher review influenced the students’ use of scientific terms and everyday expressions.The results show that the students who had a teacher review use everyday expressions at the meso and submicro level to a greater extent than the students who did not have an teacher review. The everyday expressions are often used as a kind of translation from the scientific terms in the students’ drawings.

Fresh-market tomatoes are produced on a raised-bed plasticulture system that relies heavily on soil-applied preplant fumigants for the management of soilborne pathogens, nematodes, and weeds. Since the transition from methyl bromide to alternative fumigants, growers have experienced a resurgence of several soilborne pests and pathogens, including root-knot nematode caused by Meloidogyne spp. and Fusarium wilt caused by Fusarium oxysporum f. sp. lycopersici race 3. This resurgence is attributed to the inability of the alternative fumigants to effectively disperse through the soil in the same manner as methyl bromide. Two supplemental fumigation strategies, the application of chloropicrin (PIC) below bed edges (herein “supplemental PIC”) and broadcast deep-shank applications of 1,3-dichloropropene (1,3-D), were evaluated in conjunction with standard raised-bed applications of Pic-Clor 60, Pic-Clor 80, and Pic 100 covered with a virtually impermeable film or a totally impermeable film. Large-plot replicated studies were conducted in two separate commercial tomato fields with a history of production losses caused by root-knot nematode and Fusarium wilt. Deep-shank 1,3-D applications significantly reduced the recovery of root-knot and total parasitic nematodes across field sites before the preparation of raised beds. Both supplemental PIC and deep-shank 1,3-D reduced root-knot galling and Fusarium wilt incidence, but the latter supplemental treatment statistically had the greatest impact. Fumigant applied within raised beds or plastic film had no significant effect on root-knot galling or Fusarium wilt. Although both supplemental fumigation strategies had a significant effect on pest and disease pressure, neither statistically improved tomato yields based on small subplot harvests. Controlled laboratory experiments confirmed the fungicidal activity of 1,3-D against F. oxysporum f. sp. lycopersici, with 75, 90, 95, and 99% lethal doses corresponding to estimated field application rates of 56.1, 93.5, 121.6, and 184.7 liters/ha, respectively. The results demonstrate how fumigant placement can improve pest and disease control activity with current fumigant alternatives to methyl bromide and further support the broader pesticidal activity of some chemical fumigants.

Kidney transplant candidates (KTCs) who are HLA highly sensitized (calculated panel-reactive alloantibodies >95%) have poor access to deceased kidney transplantation. In this single-center prospective study, 13 highly sensitized desensitization-naive KTCs received IV tocilizumab (8 mg/kg) every 4 weeks. We evaluated tolerability as well as immune responses, that is, T cell, B cell, T follicular helper (Tfh) subsets, blood cytokines (IL-6, soluble IL-6 receptor-sIL-6R-, IL-21), blood chemokines (CXCL10, CXCL13), and anti-HLA alloantibodies. Tocilizumab treatment was well-tolerated except in one patient who presented spondylodiscitis, raising a note of caution. Regarding immune parameters, there were no significant changes of percentages of lymphocyte subsets, that is, CD3+ , CD3+ /CD4+ , CD3+ /CD8+ T cells, and NK cells. This was also the case for Tfh cell subsets, B cells, mature B cells, plasma cells, pre-germinal center (GC) B cells, and post-GC B cells, whereas we observed a significant increase in naive B cells (p = .02) and a significant decrease in plasmablasts (p = .046) over the tocilizumab treatment course. CXCL10, CXCL13, IL-21, total IgG, IgA, and IgM levels did not significantly change during tocilizumab therapy; conversely, there was a significant increase in IL-6 levels (p = .03) and a huge increase in sIL-6R (p = .00004). There was a marginal effect on anti-HLA alloantibodies (class I and class II). To conclude in highly sensitized KTCs, tocilizumab as a monotherapy limited B cell maturation; however, it had almost no effect on anti-HLA alloantibodies.

BACKGROUND AND AIMS: Increased fatty acid (FA) flux from adipose tissue to the liver contributes to the development of NAFLD. Because free FAs are key lipotoxic triggers accelerating disease progression, inhibiting adipose triglyceride lipase (ATGL)/patatin-like phospholipase domain containing 2 (PNPLA2), the main enzyme driving lipolysis, may attenuate steatohepatitis. APPROACH AND RESULTS: Hepatocyte-specific ATGL knockout (ATGL LKO) mice were challenged with methionine-choline-deficient (MCD) or high-fat high-carbohydrate (HFHC) diet. Serum biochemistry, hepatic lipid content and liver histology were assessed. Mechanistically, hepatic gene and protein expression of lipid metabolism, inflammation, fibrosis, apoptosis, and endoplasmic reticulum (ER) stress markers were investigated. DNA binding activity for peroxisome proliferator-activated receptor (PPAR) α and PPARδ was measured. After short hairpin RNA-mediated ATGL knockdown, HepG2 cells were treated with lipopolysaccharide (LPS) or oleic acid:palmitic acid 2:1 (OP21) to explore the direct role of ATGL in inflammation in vitro. On MCD and HFHC challenge, ATGL LKO mice showed reduced PPARα and increased PPARδ DNA binding activity when compared with challenged wild-type (WT) mice. Despite histologically and biochemically pronounced hepatic steatosis, dietary-challenged ATGL LKO mice showed lower hepatic inflammation, reflected by the reduced number of Galectin3/MAC-2 and myeloperoxidase-positive cells and low mRNA expression levels of inflammatory markers (such as IL-1β and F4/80) when compared with WT mice. In line with this, protein levels of the ER stress markers protein kinase R-like endoplasmic reticulum kinase and inositol-requiring enzyme 1α were reduced in ATGL LKO mice fed with MCD diet. Accordingly, pretreatment of LPS-treated HepG2 cells with the PPARδ agonist GW0742 suppressed mRNA expression of inflammatory markers. Additionally, ATGL knockdown in HepG2 cells attenuated LPS/OP21-induced expression of proinflammatory cytokines and chemokines such as chemokine (C-X-C motif) ligand 5, chemokine (C-C motif) ligand (Ccl) 2, and Ccl5. CONCLUSIONS: Low hepatic lipolysis and increased PPARδ activity in ATGL/PNPLA2 deficiency may counteract hepatic inflammation and ER stress despite increased steatosis. Therefore, lowering hepatocyte lipolysis through ATGL inhibition represents a promising therapeutic strategy for the treatment of steatohepatitis. ispartof: HEPATOLOGY vol:75 issue:1 pages:125-139 ispartof: location:United States status: published

Electrolytic formic acid synthesis delivers green formic acid at the right concentration for emerging applications.

Plants produce many secondary metabolites showing considerable inter- and intraspecific diversity of concentration and composition as a strategy to cope with environmental stresses. The evolution of plant defenses against herbivores and pathogens can be unraveled by understanding the mechanisms underlying chemical diversity. Pyrrolizidine alkaloids are a class of secondary metabolites with high diversity. We performed a qualitative and quantitative analysis of 80 pyrrolizidine alkaloids with liquid chromatography-tandem mass spectrometry of leaves from 17 Jacobaea species including one to three populations per species with 4–10 individuals per population grown under controlled conditions in a climate chamber. We observed large inter- and intraspecific variation in pyrrolizidine alkaloid concentration and composition, which were both species-specific. Furthermore, we sequenced 11 plastid and three nuclear regions to reconstruct the phylogeny of the 17 Jacobaea species. Ancestral state reconstruction at the species level showed mainly random distributions of individual pyrrolizidine alkaloids. We found little evidence for phylogenetic signals, as nine out of 80 pyrrolizidine alkaloids showed a significant phylogenetic signal for Pagel's λ statistics only, whereas no significance was detected for Blomberg's K measure. We speculate that this high pyrrolizidine alkaloid diversity is the result of the upregulation and downregulation of specific pyrrolizidine alkaloids depending on ecological needs rather than gains and losses of particular pyrrolizidine alkaloid biosynthesis genes during evolution.

Hydroconversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydoxymethyl)furan (BHMF) was studied over mono- and bimetallic supported catalysts. It was found that monometallic Ni/SiO2 catalysts exhibited superior performance with a total yield of BHMF of up to 99 wt%. This excellent performance may be attributed to higher Ni dispersion and low acidity of the support. Dimethyl sulfoxide (DMSO) is often present in HMF, due to the route used for its synthesis. DMSO adsorption caused a clear reduction of Ni/SiO2 performance for the HMF hydrodeoxygenation reaction. Characterization of the spent catalysts was performed using HAADF-STEM-EDX, Raman, ICP, and XPS spectroscopies, and showed the presence of sulfur and graphitic carbon, which could explain the deactivation.

The reuse of construction components is considered as a higher value process in a Circular Economy (CE) than recycling. However, this is not yet widely adopted as many barriers still prevent the successful integration of the concept. The ISO20887 standard advocates that the implementation of construction standards will benefit circular reuse. Yet, these standards still need to be developed. To better understand the views of the construction sector, a survey was sent to the network of the Green Deal on Circular Construction (GDCC), led by Circular Flanders. The survey (number of recipients = 629, response rate = 16%) investigates the current implementation of Design for Disassembly and the reuse of construction components. Additionally, it investigates the respondents’ view on how a further morphological standardisation of components and connections, as well as standardisation of procedures can facilitate this reuse of construction components. The result is a concrete set of action points and corresponding actors who need to take responsibility. The stakeholders point out that there is no legal framework for component reuse. Yet, this framework can only be created through their largescale cooperation to create the needed construction standards that will truly enable the circular reuse of components.

ispartof: Chemcatchem status: Published online

Large polarons are known to form in lead halide perovskites (LHPs). Photoinduced isolated polarons at low densities have been well-researched, but many-body interactions at elevated polaron densities, exceeding the Mott criterion (i.e., Mott polaron density), have remained elusive. Here, employing ultrafast terahertz spectroscopy, we identify a stable Mott polaron state in LHPs at which the polaron wavefunctions start to overlap. The Mott polaron density is determined to be ∼1018 cm-3, in good agreement with theoretical calculations based on the Feynman polaron model. The electronic phase transition across the Mott density is found to be universal in LHPs and independent of the constituent ions. Exceeding the Mott polaron density, excess photoinjected charge carriers annihilate quickly within tens to hundreds of picoseconds, before reaching the stable and long-lived Mott state. These results have considerable implications for LHP-based devices and for understanding exotic phenomena reported in LHPs. ispartof: ACS ENERGY LETTERS vol:8 issue:1 pages:420-428 ispartof: location:United States status: published

The ever-increasing energy demand from the world population has made the intensive use of fossil fuels an overarching threat to global environment and human health. An appealing alternative is offered by sunlight-assisted photoelectrochemical water splitting to yield carbon-free hydrogen fuel, but kinetic limitations associated to the oxygen evolution reaction (OER) render the development of cost-effective, eco-friendly and stable electrocatalysts an imperative issue. In the present work, OER catalysts based on graphitic carbon nitride (g-C3N4) were deposited on conducting glass substrates by a simple decantation procedure, followed by functionalization with low amounts of nanostructured CoO and CoFe2O4 by radio frequency (RF)-sputtering, and final annealing under inert atmosphere. A combination of advanced characterization tools was used to investigate the interplay between material features and electrochemical performances. The obtained results highlighted the formation of a p-n junction for the g-C3N4-CoO system, whereas a Z-scheme junction accounted for the remarkable performance enhancement yielded by g-C3N4-CoFe2O4. The intimate contact between the system components also afforded an improved electrocatalyst stability in comparison to various bare and functionalized g-C3N4-based systems. These findings emphasize the importance of tailoring g-C3N4 chemico-physical properties through the dispersion of complementary catalysts to fully exploit its applicative potential.

Epitaxial stabilization of thermodynamically metastable phases and advances in atomic control of complex oxide thin-film growth can be used effectively for realizing novel phenomena and as an alternative for bulk synthesis under extreme thermodynamic conditions. Here, we investigate infinite layer (IL) based cuprate superlattices, where 7–8 unit cells of Sr 0.6 Ca 0.4 Cu O 2 (SCCO) are sandwiched between ultrathin spacer layers of SrTi O 3 (STO), SrRu O 3 , or BaCu O 2 (BCO) and only observe superconductivity in the pure [SCCO/BCO] superlattice (SL) without spacer layers. Apparently, the insertion of an additional STO spacer layer in the latter SL prevents the occurrence of superconductivity. The observed superconductivity in [SCCO/BCO] SL is discussed in terms of a structural model involving the interplay between the Cu O 2 plane and the CuO chain similar to the bulk Y Ba 2 Cu 3 O 7 superconductor. The structural origin was found by the identification of a metastable IL- BaCu O 2 variant, which deviates highly from its parent bulk crystal structure and exhibits a relatively larger out-of-plane lattice parameter (around 7 Å ) when sandwiched with SCCO in the form of [SCCO/BCO] SL. However, this variant is absent when STO spacer layers are introduced between SCCO and BCO layers. X-ray absorption spectra of the Cu L edge for BCO exhibits a slightly higher energy satellite peak as compared to the 3 d 9 L Zhang-Rice character observed in SCCO. This result indicates the existence of contrasting plane and chain-type Cu-O blocks in SCCO and BCO, respectively, which is further corroborated using annular bright field scanning transmission electron microscopy imaging. This work unravels an unexpected structure of BCO which helps in realizing superconductivity in [SCCO/BCO] SL and provides a wider perspective in the growth and design of cuprate-based hybrid structures.

Graphitic carbon nitride (gCN) is a promising n-type semiconductor widely investigated for photo-assisted water splitting, but less studied for the (photo)electrochemical degradation of aqueous organic pollutants. In these fields, attractive perspectives for advancements are offered by a proper engineering of the material properties, e.g., by depositing gCN onto conductive and porous scaffolds, tailoring its nanoscale morphology, and functionalizing it with suitable cocatalysts. The present study reports on a simple and easily controllable synthesis of gCN flakes on Ni foam substrates by electrophoretic deposition (EPD), and on their eventual decoration with Co-based cocatalysts [CoO, CoFe2O4, cobalt phosphate (CoPi)] via radio frequency (RF)-sputtering or electrodeposition. After examining the influence of processing conditions on the material characteristics, the developed systems are comparatively investigated as (photo)anodes for water splitting and photoelectrocatalysts for the degradation of a recalcitrant water pollutant [potassium hydrogen phthalate (KHP)]. The obtained results highlight that while gCN decoration with Co-based cocatalysts boosts water splitting performances, bare gCN as such is more efficient in KHP abatement, due to the occurrence of a different reaction mechanism. The related insights, provided by a multi-technique characterization, may provide valuable guidelines for the implementation of active nanomaterials in environmental remediation and sustainable solar-to-chemical energy conversion.