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This publication contains information on the individualization of instruction in high school chemistry in the form of a case study. The subject of the case study is the P. K. Yonge Laboratory School of the University of Florida, Gainesville. The instructional model, however, was also field-tested in 18 schools during 1971-72 and 1972-73. The publication is divided into five sections: foreword, history, individualized chemistry program, how to begin individualizing instruction, and individualized chemistry field study and results. In the foreword, individualized instruction is defined as not consisting of study packets, audio-tutorial programs, self-pacing, systems approach, and instructional or behavioral objectives. A four-part operational definition of individualized instruction as exemplified in the reported chemistry program is then presented. (PEB)

Provides historical background on Pasteur's resolution of an optically active compound, and describes an undergraduate laboratory experiment in which optically active compounds are separated. (MLH)

Compared were student attitudes toward scientists and science at the beginning and end of an introductory college chemistry course at The Pennsylvania State University. The relationship between grade achievement and student attitude was also investigated. The relationships within subgroups based on class rank in high school, high school science and mathematics background, and various other factors were considered. The investigator constructed an attitude measurement scale of 44 items. The split-half procedure employing the Spearman-Brown formula and the test-retest method were used to determine instrument reliability. A median score technique was used to rank attitudes. Four hundred sixty-seven students were pre- and post-tested during the fall term of 1966. Results showed that student attitudes were less favorable at the termination of the course than at the beginning. Significant correlations were noted relative to grade achievement and attitude, and pre-attitude scores and grade achievement. (BC)

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

New Zealand blackcurrant (NZBC) extract is a rich source of anthocyanins and in order to exert physiological effects, the anthocyanin-derived metabolites need to be bioavailable in vivo. We examined the plasma uptake of selected phenolic acids following NZBC extract supplementation alongside maintaining a habitual diet (i.e. not restricting habitual polyphenol intake). Twenty healthy volunteers (nine females, age: 28 ± 7 years, height 1.73 ± 0.09 m, body mass 73 ± 11 kg) consumed a 300 mg NZBC extract capsule (CurraNZ®; anthocyanin content 105 mg) following an overnight fast. Venous blood samples were taken pre and 1, 1.5, 2, 3, 4, 5, and 6 h post-ingestion of the capsule. Reversed-phase high-performance liquid chromatography (HPLC) was used for analysis of two dihydroxybenzoic acids [i.e. vanillic acid (VA) and protocatechuic acid (PCA)] and one trihydroxybenzoic acid [i.e. gallic acid (GA)] in plasma following NZBC extract supplementation. Habitual anthocyanin intake was 168 (95%CI:68–404) mg⋅day−1 and no associations were observed between this and VA, PCA, and GA plasma uptake by the NZBC extract intake. Plasma time-concentration curves revealed that GA, and PCA were most abundant at 4, and 1.5 h post-ingestion, representing a 261% and 320% increase above baseline, respectively, with VA remaining unchanged. This is the first study to demonstrate that an NZBC extract supplement increases the plasma uptake of phenolic acids GA, and PCA even when a habitual diet is followed in the days preceding the experimental trial, although inter-individual variability is apparent.

Describes the use of a TV program to review regularly assigned homework in a chemistry class designed for students with a weak chemistry and/or math background. Presents student reactions, conclusions, and future plans for the TV sessions. (GS)

To evaluate predictors of abnormal routine postoperative day 1 (POD1) labs in patients with normal pre-operative renal function following robotic assisted partial nephrectomy (RAPN) and the associated clinical outcomes of these lab results.We analyzed 500 consecutive RAPN from a single surgeon series. Patients with chronic kidney disease (CKD) III or greater were excluded from the study. Three hundred ninty-three RAPN were included in the analysis. Routine POD1 lab tests including hemoglobin (Hgb), creatinine, potassium, and sodium were evaluated to determine rates of abnormal values and rates of clinical intervention. Abnormal Hgb at POD1 was defined as8 g/dL or ≥3 g/dL decrease from the preoperative (baseline) value. Abnormal sodium (Na) preoperatively and postoperatively was defined as135 mEq/L or145 mEq/L. Abnormal potassium (K) was defined preoperatively and POD1 as3.5 mEq/L or5 mEq/L.Of 37.4% (147/393) had one or more abnormal labs at POD1. Of the 101 patients with abnormal Hgb, 15 patients required blood transfusion. Twenty-six patients had abnormal sodium for which two were treated with IV fluids. Twenty-seven patients had potassium abnormalities (12/25 were hypokalemia). Acute kidney injury stage I was seen in 27 patients (6.9%) and stage II in 3 (0.8%). Patients with abnormal labs were more likely to have larger renal mass, higher R.E.N.A.L. scores, intraoperative complications, longer operative times, and higher EBL on multivariate analysis.POD1 serum laboratory tests appear to be necessary following RAPN in patients with normal pre-operative renal function.

Transient Receptor Potential Melastatin 5 (TRPM5) is an intracellular calcium-activated cation-selective ion channel expressed in a variety of cell types. Dysfunction of this channel has recently been implied in a range of disease states including diabetes, enteric infections, inflammatory responses, parasitic infection and other pathologies. However, to date, agonists and positive modulators of this channel with sufficient selectivity to enable target validation studies have not been described, limiting the evaluation of TRPM5 biology and its potential as a drug target. We developed a high-throughput assay using a fluorescent membrane potential dye and a medium- and high-throughput electrophysiology assay using QPatch HTX and SyncroPatch 384PE. By employing these assays, we conducted a primary screening campaign and identified hit compounds as TRPM5 channel positive modulators. An initial selectivity profile confirmed hit selectivity to TRPM5 and is presented here. These small molecule TRPM5 compounds have a high potential both as early tool compounds to enable pharmacological studies of TRPM5 and as starting points for the development of potent, selective TRPM5 openers or positive modulators as novel drugs targeting several pathological states.

Pentosan polysulfate sodium (PPS), a semisynthetic sulfated polysaccharide, is the only FDA-approved oral therapy for interstitial cystitis. Recent studies have described a progressive, vision-threatening macular condition associated with long-term PPS use. We reviewed all publications concerning PPS maculopathy to consolidate known clinical features and to evaluate the strength of this association. Current literature supports a strong dose-dependent association between PPS exposure and a progressive maculopathy impacting the retinal pigment epithelium (RPE) and RPE-photoreceptor interface that may worsen even after drug cessation. Initial symptoms may include prolonged dark adaptation and difficulty reading with relative visual acuity preservation. Fundus examination often shows macular pigment clumps corresponding to lesions of focal RPE thickening. Fundus autofluorescence most clearly depicts the condition, with a distinctive pattern of hypo- and hyperautofluorescent spots in the posterior pole that sometimes extends to the retinal periphery. Many cases also show a characteristic peripapillary hypoautofluorescent halo. Near infrared reflectance may aid in early detection. RPE atrophy, cystoid macular edema, and macular neovascularization may also occur, potentially resulting in loss of central acuity. This newly described association implies significant public health risk. Ophthalmologists should screen PPS users with multimodal retinal imaging, and prescribers should minimize dose and duration of PPS use.

BACKGROUND AND AIMS The hepatic venous pressure gradient (HVPG) is the standard for estimating portal pressure but requires expertise for interpretation. We hypothesized that HVPG could be extrapolated from liver histology using a machine learning (ML) algorithm. APPROACH AND RESULTS Patients with NASH with compensated cirrhosis from a phase 2b trial were included. HVPG and biopsies from baseline and weeks 48 and 96 were reviewed centrally, and biopsies evaluated with a convolutional neural network (PathAI, Boston, MA). Using trichrome-stained biopsies in the training set (n = 130), an ML model was developed to recognize fibrosis patterns associated with HVPG, and the resultant ML HVPG score was validated in a held-out test set (n = 88). Associations between the ML HVPG score with measured HVPG and liver-related events, and performance of the ML HVPG score for clinically significant portal hypertension (CSPH) (HVPG ≥ 10 mm Hg), were determined. The ML-HVPG score was more strongly correlated with HVPG than hepatic collagen by morphometry (ρ = 0.47 vs. ρ = 0.28; P

Histone H3 lysine 4 methylation (H3K4Me) is most often associated with chromatin activation, and removing H3K4 methyl groups has been shown to be coincident with gene repression. H3K4Me demethylase KDM1a/LSD1 is a therapeutic target for multiple diseases, including for the potential treatment of β-globinopathies (sickle cell disease and β-thalassemia), because it is a component of γ-globin repressor complexes, and LSD1 inactivation leads to robust induction of the fetal globin genes. The effects of LSD1 inhibition in definitive erythropoiesis are not well characterized, so we examined the consequences of conditional inactivation of Lsd1 in adult red blood cells using a new Gata1creERT2 bacterial artificial chromosome transgene. Erythroid-specific loss of Lsd1 activity in mice led to a block in erythroid progenitor differentiation and to the expansion of granulocyte-monocyte progenitor–like cells, converting hematopoietic differentiation potential from an erythroid fate to a myeloid fate. The analogous phenotype was also observed in human hematopoietic stem and progenitor cells, coincident with the induction of myeloid transcription factors (eg, PU.1 and CEBPα). Finally, blocking the activity of the transcription factor PU.1 or RUNX1 at the same time as LSD1 inhibition rescued myeloid lineage conversion to an erythroid phenotype. These data show that LSD1 promotes erythropoiesis by repressing myeloid cell fate in adult erythroid progenitors and that inhibition of the myeloid-differentiation pathway reverses the lineage switch induced by LSD1 inactivation.

The cervical remodeling process during pregnancy is characterized by progressive compositional and structural changes in the tissues extra-cellular matrix (ECM). Appropriately timed remodeling is critical for healthy gestation and prevention of premature cervical softening leading to preterm birth (PTB). Modification of the ECM glycosaminoglycans (GAGs) content with advancing pregnancy, especially the non-sulfated GAG hyaluronan (HA), is a fundamental change associated with cervical remodeling. While GAGs have numerous physiological roles, the mechanical consequence of evolving GAG content on cervical structure-function behavior remains an open question. Additionally, an understanding of cervical swelling properties, postulated to be regulated in part by GAGs, is required for the appropriate definition of a reference configuration for mechanical tests and to enhance biological understanding. To investigate cervical swelling, osmotic loading tests are conducted on isolated wild type mouse cervices throughout pregnancy. These tests are performed in various osmolarity solutions to assess the influence of the media on swelling kinetics. A genetically altered strain of mice with depletion of cervical HA is also tested to elucidate the contribution of HA to tissue swelling. Results show ex vivo cervical swelling is significant with volume changes ranging from 20 to 100% after 3h of free swelling. The swelling kinetics depend highly on osmolarity of the media and is altered with advancing pregnancy. The contribution of HA to swelling is only significant in hypo-osmotic solution when HA cervical content is high at the end of pregnancy. In summary, it is critical to account for swelling deformation mechanisms after excision in mechanical experiments. Statement of significance The cervical extracellular matrix (ECM) undergoes drastic changes to fulfill the functional change of the cervix during pregnancy. Inappropriate timing for this transformation can result in preterm birth, a severe clinical challenge. One of the fundamental changes of the cervical ECM is the significant modification of the glycosaminoglycan content, especially hyaluronan (HA), which is thought to contribute significantly to the swelling and mechanical properties of the cervix. This study aims to measure the swelling kinetics of cervical tissue during pregnancy and to investigate the role of HA in these swelling tendencies. Results show the significant swelling of cervical tissue, which evolves as pregnancy progresses, highlighting a key material property feature of the remodeled cervix. Using a mouse strain with a cervical HA depletion, this work shows HA contributes to the swelling trends of late-term cervical tissue, in a hypo-osmotic solution.

The Second State of the Carbon Cycle Report (SOCCR2) culminated in 19 chapters that spanned all North American sectors – from Energy Systems to Agriculture and Land Use – known to be important for understanding carbon (C) cycling and accounting. Wetlands, both inland and coastal, were found to be significant components of C fluxes along the terrestrial to aquatic hydrologic continuum. In this chapter, we synthesize the role of wetlands in the overall C footprint of North America (from Canada to Mexico) as one metric of the societal values placed on these terrestrial-aquatic interfaces. We also summarize the effects of management activities and climate change on the wetland C cycle and give some perspectives on the current and future importance of wetlands to society.

A multifunctional surface, subsurface and systemic therapeutic (MS3T) formulation comprised of two bactericides, both didecyldimethylammonium chloride (DDAC) and a zinc (Zn)-chelate, was developed as an alternative to copper pesticides for crop protection. Agricultural grade chemicals were used to prepare MS3T formulations. Minimal inhibitory concentration (MIC) was determined to be tested in vitro against Xanthomonas alfalfae subsp. citrumelonis (herein called Xa), Escherichia coli (E. coli), and Pseudomonas syringae (Ps). Assessment of the phytotoxic potential was carried out on tomato under greenhouse conditions. Moreover, field trials were conducted during three consecutive years on grapefruit (Chrysopelea paradise) groves to evaluate efficacy against citrus canker (Xanthomonas citri subsp. citri), scab (Elsinoe fawcetti), and melanose (Diaporthe citri). In addition to disease control, improvements to both fruit yield and quality were observed likely due to the nutritional activity of MS3T via the sustained release of plant nutrients (Zn and nitrogen). Zn residues of leaf tissues were analyzed via atomic absorption spectroscopy (AAS) at various time points before and after MS3T foliar applications throughout the duration of the 2018 field trial. Field trial results demonstrated MS3T to be an effective alternative to copper (Cu)-based formulations for the control of citrus canker.

Complexes with ligand-to-metal charge-transfer (LMCT) excited states involving d0 metals represent a new design for photocatalysts. Herein, the photochemistry and photophysics of d0 titanocenes of the type Cp2Ti(C2R)2, where C2R = ethynylphenyl (C2Ph), 4-ethynyldimethylaniline (C2DMA), or 4-ethynyltriphenylamine (C2TPA), have been investigated. Cp2Ti(C2Ph)2 and Cp2Ti(C2DMA)2 have also been characterized by single-crystal X-ray diffraction. The two aryl rings in Cp2Ti(C2DMA)2 are nearly face-to-face in the solid state, whereas they are mutually perpendicular for Cp2Ti(C2Ph)2. All three complexes are brightly emissive at 77 K but photodecompose at room temperature when irradiated into their lowest-energy absorption band. The emission wavelengths and photodecomposition quantum yields are as follows: Cp2Ti(C2Ph)2, 575 nm and 0.65; Cp2Ti(C2TPA)2, 642 nm and 0.42; Cp2Ti(C2DMA)2, 672 nm and 0.25. Extensive benchmarking of the density functional theory (DFT) model against the structural data and of the time-dependent DFT (TDDFT) model against the absorption and emission data was performed using combinations of 13 different functionals and 4 basis sets. The model that predicted the absorption and emission data with the greatest fidelity utilized MN15/LANL2DZ for both the DFT optimization and the TDDFT. Computational analysis shows that absorption involves a transition to a 1LMCT state. Whereas the spectroscopic data for Cp2Ti(C2TPA)2 and Cp2Ti(C2DMA)2 are well modeled using the optimized structure of these complexes, Cp2Ti(C2Ph)2 required averaging of the spectra from multiple rotamers involving rotation of the Ph rings. Consistent with this finding, an energy scan of all rotamers showed a very flat energetic surface, with less than 1.3 kcal/mol separating the minimum and maximum. The computational data suggest that emission occurs from a 3LMCT state. Optimization of the 3LMCT state demonstrates compression of the C-Ti-C bond angle, consistent with the known products of photodecomposition.

We describe a clinical candidate molecule from a new series of glutamate N-methyl-d-aspartate receptor subunit 2B-selective inhibitors that shows enhanced inhibition at extracellular acidic pH values relative to physiologic pH. This property should render these compounds more effective inhibitors of N-methyl-d-aspartate receptors at synapses responding to a high frequency of action potentials, since glutamate-containing vesicles are acidic within their lumen. In addition, acidification of penumbral regions around ischemic tissue should also enhance selective drug action for improved neuroprotection. The aryl piperazine we describe here shows strong neuroprotective actions with minimal side effects in preclinical studies. The clinical candidate molecule NP10679 has high oral bioavailability with good brain penetration and is suitable for both intravenous and oral dosing for therapeutic use in humans. SIGNIFICANCE STATEMENT: This study identifies a new series of glutamate N-methyl-d-aspartate (NMDA) receptor subunit 2B-selective negative allosteric modulators with properties appropriate for clinical advancement. The compounds are more potent at acidic pH, associated with ischemic tissue, and this property should increase the therapeutic safety of this class by improving efficacy in affected tissue while sparing NMDA receptor block in healthy brain.

In rodents and humans, the gut bacteria-derived metabolite trimethylamine N-oxide (TMAO) has been implicated in the progression of cardiovascular disease, chronic kidney disease, fatty liver, and insulin resistance; however, the effects of TMAO on dairy cattle health and milk production have not been defined. We aimed to determine whether intravenous TMAO infusion modifies measures of liver health, glucose tolerance, and milk production in early-lactation cows. Eight early-lactation Holstein cows (30.4 ± 6.41 d in milk; 2.88 ± 0.83 lactations) were enrolled in a study with a replicated 4 × 4 Latin square design. Cows were intravenously infused TMAO at 0 (control), 20, 40, or 60 g/d for 6 d. Washout periods lasted 9 d. Intravenous glucose tolerance tests (GTT) occurred on d 5. Blood was collected daily. Milk was collected on d -1, 0, 5, and 6. Urine was collected on d -1 and 6. Circulating metabolites, milk components, and TMAO concentrations in milk, urine, and plasma were quantified. Data were analyzed using a mixed model that included the fixed effects of treatment. Concentrations of TMAO in plasma, milk, and urine increased linearly with increasing dose. Dry matter intake and milk production were not modified by treatment. Daily plasma triacylglycerol, fatty acid (FA), and glucose concentrations were not modified. Serum albumin, total protein, globulin, total bilirubin, direct bilirubin, aspartate aminotransferase, γ-glutamyl transferase, and glutamate dehydrogenase concentrations were also not modified by treatment. Serum GTT glucose, FA, and insulin concentrations were not modified by treatment. Plasma total, reduced, and oxidized glutathione concentrations were also not modified by treatment. We conclude that a 6-d intravenous infusion of TMAO does not influence measures of liver health, glucose tolerance, or milk production in early-lactation dairy cows.

Photosynthesis and respiration rely upon a proton gradient to produce ATP. In photosynthesis, the Respiratory Complex I homologue, Photosynthetic Complex I (PS-CI) is proposed to couple ferredoxin oxidation and plastoquinone reduction to proton pumping across thylakoid membranes. However, little is known about the PS-CI molecular mechanism and attempts to understand its function have previously been frustrated by its large size and high lability. Here, we overcome these challenges by pushing the limits in sample size and spectroscopic sensitivity, to determine arguably the most important property of any electron transport enzyme – the reduction potentials of its cofactors, in this case the iron-sulphur clusters of PS-CI (N0, N1 and N2), and unambiguously assign them to the structure using double electron-electron resonance. We have thus determined the bioenergetics of the electron transfer relay and provide insight into the mechanism of PS-CI, laying the foundations for understanding of how this important bioenergetic complex functions. Photosynthetic Complex I (PS-CI) is proposed to couple ferredoxin oxidation and plastoquinone reduction to proton pumping across thylakoid membranes. Here the authors determine the reduction potentials of the iron-sulphur clusters of PS-CI and thus the bioenergetics of the electron transfer relay.

Preventing eutrophication of inland freshwater ecosystems requires quantifying the phosphorus (P) content of the streams and rivers that feed them. Typical methods for measuring P assess soluble reactive P (SRP) or total P (TP) and require expensive analytical techniques that produce hazardous waste. Here we present a novel method for measuring the more relevant bioavailable P (BAP); this assay utilizes the growth of familiar baker’s yeast, avoids production of hazardous waste, and reduces cost relative to measurements of SRP and TP. The yeast BAP (yBAP) assay takes advantage of the observation that yeast density at saturating growth increases linearly with provided P. We show that this relationship can be used to measure P in freshwater in concentration ranges relevant to eutrophication. In addition, we measured yBAP in water containing known amounts of fertilizer and in samples from agricultural waterways. We observed that the majority of yBAP values were between those obtained from standard SRP and TP measurements, demonstrating that the assay is compatible with real-world settings. The cost-effective and nonhazardous nature of the yeast-based assay suggests that it could have utility in a range of settings, offering added insight to identify water systems at risk of eutrophication from excess phosphorus.

Phenotypic whole cell high-throughput screening of a ∼150,000 diverse set of compounds against Mycobacterium tuberculosis (Mtb) in cholesterol-containing media identified 1,3-diarylpyrazolyl-acylsulfonamide 1 as a moderately active hit. Structure-activity relationship (SAR) studies demonstrated a clear scope to improve whole cell potency to MIC values of

Long-term storage of oogonia and germ-line stem cells provides an alternative to the limitations associated with cryopreserving eggs of important fish species. These cell types are less vulnerable to the stresses of freezing. Cryopreservation has enormous potential for aquaculture advancement, but protocols must be developed for each species and cell type since its success hinges on various input factors. Blue Catfish Ictalurus furcatus were selected as the test species in this study because of the need to improve fry production of Blue Catfish ♂ × Channel Catfish I. punctatus ♀ hybrids, which can be facilitated by storing oogonia in gene banks. Our objective was to develop a freezing protocol for oogonia of this species. We tested different permeating and nonpermeating cryoprotectants, concentrations of these agents, and freezing rates. We proved that all three factors influenced postthaw recovery of oogonia. Of the permeating cryoprotectants, 1.0 M dimethyl sulfoxide resulted in the most live cells with the highest viability percentages, and adding 0.2 M lactose with 10% egg yolk further improved the results. There were also specific interactions in which the effects of concentration and freezing rate varied among the cryoprotectant treatments. The most effective freezing rate was −1.0°C/min, and cell viability was reduced at −2.5°C/min and −5.0°C/min. From these results, we propose adding 1.0 M dimethyl sulfoxide with 0.2 M lactose and 10% egg yolk to cryomedia and freezing it at a rate of −1.0°C/min. By developing a cryopreservation protocol for a commonly cultured catfish, this work may guide the development of protocols for other species of interest.

BACKGROUND: Blood clot contraction, volume shrinkage of the clot, is driven by platelet contraction and accompanied by compaction of the erythrocytes and their gradual shape change from biconcave to polyhedral, with the resulting cells named polyhedrocytes. OBJECTIVES: Here, we examined the role of erythrocyte rigidity on clot contraction and erythrocyte shape transformation. METHODS: We used an optical tracking methodology that allowed us to quantify changes in contracting clot size over time. RESULTS AND CONCLUSIONS: Erythrocyte rigidity has been shown to be increased in sickle cell disease (SCD), and in our experiments erythrocytes from SCD patients were 4-fold stiffer than those from healthy subjects. On average, the final extent of clot contraction was reduced by 53% in the clots from the blood of patients with SCD compared to healthy individuals, and there was significantly less polyhedrocyte formation. To test if this reduction in clot contraction was due to the increase in erythrocyte rigidity, we used stiffening of erythrocytes via chemical cross-linking (glutaraldehyde), rigidifying Wright(b) antibodies (Wr(b)), and naturally more rigid llama ovalocytes. Results revealed that stiffening erythrocytes result in impaired clot contraction and fewer polyhedrocytes. These results demonstrate the role of erythrocyte rigidity in the contraction of blood clots and suggest that the impaired clot contraction/shrinkage in SCD is due to the reduced erythrocyte deformability, which may be an underappreciated mechanism that aggravates obstructiveness of erythrocyte- rich (micro)thrombi in SCD.

Vibrational Stark shifts were explored in aqueous solutions of organic molecules with carbonyl- and nitrile-containing constituents. In many cases, the vibrational resonances from these moieties shifted toward lower frequency as salt was introduced into solution. This is in contrast to the blue-shift that would be expected based upon Onsager’s reaction field theory. Salts containing well-hydrated cations like Mg2+ or Li+ led to the most pronounced Stark shift for the carbonyl group, while poorly hydrated cations like Cs+ had the greatest impact on nitriles. Moreover, salts containing I– gave rise to larger Stark shifts than those containing Cl–. Molecular dynamics simulations indicated that cations and anions both accumulate around the probe in an ion- and probe-dependent manner. An electric field was generated by the ion pair, which pointed from the cation to the anion through the vibrational chromophore. This resulted from solvent-shared binding of the ions to the probes, consistent with their positions in the Hofmeister series. The “anti-Onsager” Stark shifts occur in both vibrational spectroscopy and fluorescence measurements.

A gram-scale synthesis of iboxamycin, an antibiotic candidate bearing a fused bicyclic amino acid residue, is presented. A pivotal transformation in the route involves an intramolecular hydrosilylation-oxidation sequence to set the ring-fusion stereocenters of the bicyclic scaffold. Other notable features of the synthesis include a high-yielding, highly diastereoselective alkylation of a pseudoephenamine amide, a convergent sp3-sp2 Negishi coupling, and a one-pot transacetalization-reduction reaction to form the target compound's oxepane ring. Implementation of this synthetic strategy has provided ample quantities of iboxamycin to allow for its in vivo profiling in murine models of infection.

Centrifugally spun polyacrylonitrile (PAN) microfibers surface-coated with Co3O4 nanoparticles were prepared as precursors to produce coated Co3O4 carbon-fiber (CCF) composites for lithium-ion battery anodes. The Co3O4/C composite-fiber anodes were obtained after the stabilization of surface-coated Co3O4/PAN fibers at 200 °C for four hours, and subsequent carbonization at 600 °C for 6 hours. The electrochemical performance of the Co3O4/C composite-fiber anode with different active material loading was evaluated by using galvanostatic charge/discharge, rate performance, cyclic voltammetry, and electrochemical impedance spectroscopy experiments. The CCF anode delivered a specific charge capacity of 632 and 420 mAh g−1 after 100 cycles at 100 and 200 mA g−1, respectively, and exhibited good rate capability. An improved electrochemical performance of the CCF was observed compared to the carbon-fiber (CF) anode (300 mAh g−1), which was attributed to the interaction between CFs and Co3O4 nanoparticles. The synthesis method presented in this work can provide an effective avenue for the fabrication of surface coated-fiber materials, including free-standing anode materials for lithium-ion batteries with increased specific capacity and improved electrochemical performance compared to carbon-fiber electrodes.

The extension of plasmonics to materials beyond the conventional noble metals opens up a novel and exciting regime after the inspiring discovery of characteristic localized surface plasmon resonances (LSPRs) in doped semiconductor nanocrystals originating from the collective oscillations of free holes in the valence band. We herein prepare colloidal monodisperse eccentric dual plasmonic noble metal-nonstoichiometric copper chalcogenide (Au@Cu2−xSe) hybrid hetero-nanostructures with precisely controlled semiconductor shell size and two tunable LSPRs in both visible (VIS) and near-infrared (NIR) regions associated with Au and Cu2−xSe, respectively. Through systematic evaluations of the photocatalytic performance of Au@Cu2−xSe upon sole NIR and dual VIS + NIR simultaneous excitations, we are capable of unambiguously elucidating the role of plasmonic coupling between two dissimilar building blocks on the accelerated photocatalytic reactions with greater rate constants from both experimental and computational perspectives. The significantly enhanced strength of the electromagnetic field arising from efficient plasmonic coupling under the excitation of two LSPRs results in the superior activities of dual plasmonic Au@Cu2−xSe in photocatalysis. The new physical and chemical insights gained from this work provide the keystone for the rational design and construction of high-quality dual- or even multi-plasmonic nano-systems with optimized properties for widespread applications ranging from photocatalysis to molecular spectroscopies.

The kidney proximal tubule is the primary site for solute reabsorption, secretion and where kidney diseases can originate, including drug-induced toxicity. Two-dimensional cell culture systems of the human proximal tubule cells (hPTCs) are often used to study these processes. However, these systems fail to model the interplay between filtrate flow, fluid shear stress (FSS), and functionality essential for understanding renal diseases and drug toxicity. The impact of FSS exposure on gene expression and effects of FSS at differing rates on gene expression in hPTCs has not been thoroughly investigated. Here, we performed RNA-sequencing of human RPTEC/TERT1 cells in a microfluidic chip-based 3D model to determine transcriptomic changes. We measured transcriptional changes following treatment of cells in this device at three different fluidic shear stress. We observed that FSS changes the expression of PTC-specific genes and impacted genes previously associated with renal diseases in genome-wide association studies (GWAS). At a physiological FSS level, we observed cell morphology, enhanced polarization, presence of cilia, and transport functions using albumin reabsorption via endocytosis and efflux transport. Here, we present a dynamic view of hPTCs response to FSS with increasing fluidic shear stress conditions and provide insight into hPTCs cellular function under biologically relevant conditions.

The khapra beetle, Trogoderma granarium, is an important quarantine pest of stored-products. While it is not established in the North America, frequent interceptions highlight the need for treatments to eradicate isolated populations if they occur. Methyl bromide has long been the standard fumigant used for this purpose; however, increasing restrictions on its use necessitate the development of new treatment options. Here we evaluate a treatment for khapra beetle using a combination of sulfuryl fluoride (SF) and propylene oxide (PPO). Experiments were conducted to determine the most tolerant stages and the effective rates for each compound. Combination treatments using both products were then evaluated at several temperatures to determine effective doses for quarantine level control. The egg stage was by far the most tolerant to SF, requiring concentration × time (CT) products roughly 10-fold greater than the next most tolerant stage, diapausing larvae. Diapausing larvae were significantly more tolerant to SF than non-diapausing larvae in a recently collected ‘field’ strain, but not in a more than 30-yr-old ‘laboratory’ culture. PPO treatments were shown to completely control the egg stage at CTs greater than 155 hr-mgL-1 at both 10 and 20°C. Resulting combination treatments with initial dose rates of 96 and 40 mgL-1 at 10°C and 80 and 40 mgL-1 at 20°C are proposed for SF and PPO, respectively. These combination treatments utilize SF’s efficacy against the larval stage along with PPO’s superior ovicidal properties to provide enhanced treatment efficacy over each product alone against all life stages of khapra beetle.

We report the fabrication of 6-phenylhexylsilane derivatized, sputtered silicon, solid phase microextraction fibers that show parts per trillion detection limits for polyaromatic hydrocarbons, and negligible carry over and phase bleed. Their fabrication involves sputtering silicon on silica fibers under various conditions. Six different fibers were evaluated by generating three different thicknesses of sputtered silicon at two different throw distances, which altered the morphologies of the silicon surfaces. All of the fibers were coated with similar thicknesses of 6-phenylhexylsilane (ca. 2 nm). These fibers were characterized with multiple analytical techniques. The optimum fiber configuration was then used to analyze polyaromatic hydrocarbons via direct immersion, gas chromatography mass spectrometry. Our best fiber for the extraction of low molecular weight polyaromatic hydrocarbons in water had similar performance to that of a commercial fiber. However, our fiber demonstrated ca. 3 times the extraction efficiency for higher molecular weight polyaromatic hydrocarbons. In addition, it outperformed the commercial fiber by showing better linearity, repeatability, and detection limits. A method for analyzing polyaromatic hydrocarbons in baby formula was developed, which showed very good linearity (0.5-125 ppb), repeatability (2-26%), detection limits (0.12-0.81 ppb), and recoveries (103-135%). In addition, our fiber showed much less (negligible) carry over and phase bleed than the commercially available fibers.