Phenology of brown bear breeding season and related geographical cues

© 2020 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited[EN] Knowledge about breeding biology is often incomplete in species with complex reproductive strategies. The brown bear Ursus arctos is a polygamous seasonal breeder inhabiting a wide variety of habitats and environmental conditions. We compiled information about brown bear breeding season dates from 36 study areas across their distribution range in the Palearctic and Nearctic regions and investigated how their breeding phenology relates to geographical factors (latitude, photoperiod, altitude and region). Brown bear matings were observed for 8 months, from April to November, with a peak in May–July. We found a 59-day difference in the onset of bear breeding season among study areas, with an average 2.3 days delay for each degree of latitude northwards. The onset of the breeding season showed a strong relationship with photoperiod and latitude, but not with region (i.e. Palearctic vs Nearctic) and altitude. First observations of bear mating occurred earlier in areas at lower latitudes. Photoperiod ranged between 14 and 18 hours at the beginning of the season for most of the study areas. The duration of the breeding season ranged from 25 to 138 days among study areas. None of the investigated factors was related to the length of the breeding season. Our results support the relevance of photoperiod to the onset of breeding, as found in other ursids, but not a shorter breeding season at higher latitudes, a pattern reported in other mammals. Our findings suggest a marked seasonality of bear reproductive behaviour, but also certain level of plasticity. Systematic field observations of breeding behaviour are needed to increase our knowledge on the factors determining mating behaviour in species with complex systems and how these species may adapt to climate change.SIWe thank Marjan Artnak, Peter Bajc, Matic Brenk, Tomáš Flajs, Uroš Grželj, Robert Hlavica, Aleš Jagodnik, Peter Klančar, Anton Marinčič, Mariusz Nędzyński, Borut Semenič and Vladimir Vician for providing information about their observations of bear mating. Robert Gatzka assisted with data collection in the Biezszcady Mountains. We thank Jon Swenson and Jumpei Tomiyasu for their help in the literature search. AGR and NS were supported by the BearConnect project funded by the National Science Centre in Poland (2016/22/Z/NZ8/00121) through the 2015-2016 BiodivERsA COFUND call for research proposals, with the national funders ANR/DLR-PT/UEFISCDI/NCN/RCN. Additional funding from the Polish Ministry of Science and Higher Education (project NN304- 294037, NS, IEC, KB), the National Science Centre in Poland (project DEC-2013/08/M/NZ9/ 00469, NS), the National Centre for Research and Development (GLOBE, POL-NOR/198352/85/ 2013, NS, TZK, FZ) and Slovenian Research Agency (P4-0059, MK) is acknowledged. AGR and NS conceived the study and wrote a first draft of the paper; AGR and NS compiled the data, AGR analyzed the data; all authors provided data and comments that improved the manuscript. We thank two anonymous reviewers for useful comments on the previous versions of the manuscript

Curcumin derivedpyrazoles and related compounds

In this comprehensive review we discuss the publications reporting pyrazoles derived from curcumin, curcuminoids and hemi-curcuminoids (149 examples) together with some biological and pharmacological properties.(Thanks are given to the Ministerio de Economía y Competitividad of Spain for financial support (Project numbers CTQ2012-13129-C02-02 and CTQ2014-56833-R) and Comunidad Autónoma de Madrid (S2013/MIT-2841, Fotocarbon). Computer, storage and other resources from the CTI (CSIC) are gratefully acknowledged. One of us (C. I. Nieto) is indebted to UNED for a predoctoral fellowship (FPI “Grupos de Investigación” UNED).Peer Reviewe

Crystal structure of (1Z,4Z)-2,4-dimethyl-3H-benzo[b][1,4]diazepine

The title compound, C11H12N2, is not planar due to the folding of the seven-membered ring. In the crystal, molecules are packed opposite each other to minimize the electronic repulsion but the long intermolecular distances indicate that no directional contacts are found.Funding for this research was provided by: Ministerio de Economía y Competitividad, Secretaría de Estado de Investigación , Desarrollo e Innovación (award No. CTQ2014- 56933-R); Ministerio de Economı´a y Competitividad, Consejo Superior de Investigaciones Cientı´ficas (award No. CTQ2015- 63997-C2-2-P); Comunidad Autónoma de Madrid (award No. S2009/PPQ-1533); Universidad Nacional de Educación a Distancia (award No. GI_SUPRABIO_01).Peer Reviewe

Pyrazaboles and pyrazolylboranes

The synthesis, reactivity, and properties of pyrazaboles and pyrazolylboranes have been reviewed with special attention to the NMR properties and X-ray structures. 104 X-ray structures are presented and 150 references are cited, which is a significant expansion of previous reviews. It appears that several items are incomplete and others deserve further development indicating than the field of pyrazaboles and of pyrazolylboranes needs new research contributions in particular in the field of coordination chemistry, a field that is clearly underdeveloped.Peer reviewe

C and 15 N NMR shieldings of 1,2,4-diazaphospholes in the solid state and in solution

Abstract. The solid state 13 C and 15 N CPMAS NMR spectra of 3,5-di-tert-butyl-1,2,4-diazaphosphole 4 and 3,5-diphenyl-1,2,4-diazaphosphole 5 have been recorded. The X-ray structure of the first compound was already known (it is a cyclic dimer with localized N-H protons) while the structure of the second cannot be determined due to the difficulty to grow suitable single crystals. NMR results pointed out that 4 is a "classical" compound while 5 is probably a tetramer showing Intermolecular Solid-State Proton Transfer (ISSPT). GIAO/ab initio calculations have been carried out to estimate the absolute 1 H, 13 C and 15 N shieldings. The agreement with the experimental chemical shifts is good enough to assign the signals of carbons C-3 and C-5

X‑ray Molecular Structures of 23 N1-4-Nitrophenyl, 2,4-Dinitrophenyl, and 2,4,6-Trinitrophenyl-2-pyrazolines

Herein, we present a complete crystallographic study of three series of N1-aryl substituted-2-pyrazolines, the aryl group being 4-nitrophenyl (series1), 2,4-dinitrophenyl (series2), and 2,4,6-trinitrophenyl (series3). The structural features, bond distances and angles as well as torsions for each single compound will be described and comparatively discussed with data for related heterocycles found in the Cambridge Structural Database (2020.2.0). A deeper look at the data has been achieved to know the influence of the substituents on the molecular structures. In the crystals of compounds with stereogenic centers at positions 4 and 5, the presence of both enantiomers has been encountered in 12 cases out of 14 that include a literature result. Finally, molecular packings in all series have been analyzed reaching the conclusion that they follow several patterns depending on the existence or not, and the type of intermolecular interactions. A general pattern has been observed which implies a certain tendency of the molecules to arrange into chains, whose additional contacts could extend the dimensionality of the network

Libration of phenyl groups detected by VT-SSNMR: Comparison with X-ray crystallography

The X-ray crystal structure of 2-benzyl-1H-benzimidazole, 2BnBzIm, was determined at 293 K showing no dynamic phenomena (disorder) of any class. On the other hand, some C NMR signals were absent in the CPMAS spectrum (100 MHz, 300 K). We decided to carry out variable-temperature SSNMR and discovered that the missing signals are ortho and meta carbons of the phenyl ring of the benzyl group. Line-shape analysis and the Eyring equation were used to determine the barrier, which was compared with the calculated DFT for the gas phase that it is much lower.This work was supported by Ministerio de Economía, Industria y Competitividad of Spain (CTQ2014‐56833‐R and CTQ2015‐63997‐C2‐2‐P) and Comunidad Autónoma de Madrid (Project FOTOCARBON, ref. S2013/ MIT2841). Carla I. Nieto is indebted to UNED for a predoctoral contract “FPI Grupos de Investigación.”Peer Reviewe

Structure of N,N′-bis(amino acids) in the solid state and in solution. A 13C and 15N CPMAS NMR study

(Chemical Equation Presented) Three bis(amino acids) linked by the amino groups have been prepared and structurally characterized. We have named them Gly-Gly, Ala-Ala and Gly-Ala (or Ala-Gly). These compounds have been characterized by NMR both in solution and in the solid state. They exist as zwitterions with the ammonium group proximal to the carboxylate anion. In the case of Gly-Ala, a dynamic situation is observed by CPMAS NMR (13C and 15N) corresponding to a double proton migration between two proximal tautomers. © 2008 American Chemical Society.Peer Reviewe

Phenology of brown bear breeding season and related geographical cues

Knowledge about breeding biology is often incomplete in species with complex reproductive strategies. The brown bear Ursus arctos is a polygamous seasonal breeder inhabiting a wide variety of habitats and environmental conditions. We compiled information about brown bear breeding season dates from 36 study areas across their distribution range in the Palearctic and Nearctic regions and investigated how their breeding phenology relates to geographical factors (latitude, photoperiod, altitude and region). Brown bear matings were observed for 8 months, from April to November, with a peak in May%July. We found a 59-day difference in the onset of bear breeding season among study areas, with an average 2.3 days delay for each degree of latitude northwards. The onset of the breeding season showed a strong relationship with photoperiod and latitude, but not with region (i.e. Palearctic vs Nearctic) and altitude. First observa- tions of bear mating occurred earlier in areas at lower latitudes. Photoperiod ranged between 14 and 18 hours at the beginning of the season for most of the study areas. The duration of the breeding season ranged from 25 to 138 days among study areas. None of the investigated factors was related to the length of the breeding season. Our results support the relevance of photoperiod to the onset of breeding, as found in other ursids, but not a shorter breeding season at higher latitudes, a pattern reported in other mammals. Our findings suggest a marked seasonality of bear reproductive behaviour, but also certain level of plasticity. Systematic field observations of breeding behaviour are needed to increase our knowledge on the factors determining mating behaviour in species with complex systems and how these species may adapt to climate change

Molecular structure in the solid state by X-ray crystallography and SSNMR and in solution by NMR of two 1,4-diazepines

The crystals of two 1,4-diazepines prepared from curcuminoid β-diketones and ethylenediamine were studied by X-ray crystallography and NMR. Their tautomerism, intramolecular hydrogen bonds and conformation were determined.This work was supported by Ministerio de Economía y Competitividad of Spain (CTQ2014-56833-R and CTQ2015-63997-C2-2- P) and Comunidad Autónoma de Madrid (Project MADRISOLAR2, ref. S2009/PPQ-1533). Carla I. Nieto is indebted to UNED for a predoctoral contract >FPI Grupos de Investigación>.Peer Reviewe