Some considerations and thoughts on the pragmatic classification of apomictic Rubus taxa : dedicated to Professor Dr. Dr. H. E. Weber on the occasion of his 65th birthday

Ausgehend von seinem Studium der Gattung Rubus in der Tschechischen Republik beschreibt der Autor die Klassifikation von Brombeeren (Subgenus Rubus) in Europa, ihre Geschichte, den gegenwärtigen Kenntnisstand sowie aktuelle Probleme. Der Autor zählt sich zu den Anhängern der "Weberschen Batologie", welcher die Fortschritte der vergangenen 25 Jahre in der Rubus-Taxonomie in Europa zu verdanken sind. Es wird akzeptiert, daß nicht jede Brombeerpflanze dem System eingeordnet werden kann. Die Gründe für die taxonomischen Probleme liegen in der Natur der Evolutionsprozesse dieser Gruppe: unvollständige Apomixis, häufige Hybridisierung, Aufspaltung der Nachkommenschaft in unterschiedliche Morphotypen, Wiedererlangen der Sexualität, vorübergehende Existenz von Spaltungsprodukten. Die potentielle Arealentwicklung eines neuen Biotyps innerhalb der Gruppe kann folgendermaßen skizziert werden: Einzelpflanze - LOkalsippe - regionale Art - weitverbreitete Art. Zur taxonomischen Bewertung einer Sippe sollte deshalb neben ausreichender morphologischer Charakterisierung vor allem die Arealgröße berücksichtigt werden. Sie ermöglicht die Zuordnung des fraglichen Taxons zu einer der genannten Rangstufen. Aufgrund seiner Erfahrungen aus der Tschechischen Republik schlägt der Autor einige Änderungen der Einstufungskriterien vor. Der Hauptunterschied besteht darin, die Untergrenze für die Einstufung als Regionalart auf 20 km Arealdurchmesser zu senken. Im Unterschied zu anderen Pflanzengruppen gilt bei den apomiktischen Brombeeren, daß weiter verbreitete Sippen größere pflanzengeographische Bedeutung haben als solche mit kleinen Arealen. Auch wenn bei der Neubeschreibung von Rubus-Arten strengere Anforderungen gestellt werden, zeigt sich, daß in der Vergangenheit mehrere gut unterscheidbare Arten vernachlässigt wurden und daß die Artenzahl innerhalb des Subgenus Rubus weiter ansteigt. Der Autor betont die Notwendigkeit des Studiums der Gruppe Glandulosi in Mitteleuropa und weist darauf hin, daß die Kooperation mit Populationsökologen nützlich sei, um die Mengeanteile der taxonomisch nicht klassifizierten Brombeeren im Gelände zu beschreiben.Based on his studies of the genus Rubus in the Czech Republic, the author describes classification of brambles from Rubus subgen. Rubus in Europe, its recent history, present state, and current problems. In general, the author follows the adherents of "Weberian batology" which in the last 25 years has assumed European responsibility for attempting to ciassify that particular genus. The thesis that not every bramble plant can be inciuded in the ciassification is accepted. The objective reasons for taxonomic difficulties within Rubus subgen. Rubus are connected with special features of taxogenesis of its members, especially with incomplete apomixis, frequent hybridization, splitting of the progeny into different morphotypes, resexualization, transitory existence of segregants, etc. The progress of the evolution of a new taxon in the given taxonomic group can be ranked: individual bush - local type - regional species - species with an extensive distribution area. When classifying a taxon, alongside sufficient morphological characteristics, great emphasis should be put on the distribution area; its extent can render possible the taxon to be accepted into the classification scheme. On the basis of experience gained from the Czech Republic, the author has accepted some modifications of the scale for acceptance of plants as species. The basic difference is in lowering the low limit of the extent of the distribution area for regional species, to be acceptable for their lnclusion to the classification, i.e. to 20 km in diameter. In contrast to taxa of other plant groups, species of apomictic brambles with more extensive distribution areas are phytogeographically more important than those with small distribution areas. In spite of the use of stricter requirements for the description of new species in Rubus, it appears that many (distinct) species have been neglected until now, and that the number of species in Rubus subgen. Rubus is continuously increasing. The author stresses the necessity of studying the group ser. Glandulosi in Central Europe and points out the usefulness of cooperation with population ecologists to describe the quantitative representation of taxonomically unclassified bramble plants in the field

Face-Fusion of Icosahedral Boron Hydride Increases Affinity to γ‐Cyclodextrin: closo,closo‐[B₂₁H₁₈]⁻ as an Anion with Very Low Free Energy of Dehydration

[Abstract] The supramolecular recognition of closo,closo‐[B₂₁H₁₈]⁻ by cyclodextrins (CDs) has been studied in aqueous solution by isothermal titration calorimetry and nuclear magnetic resonance spectroscopy. These solution studies follow up on previous mass‐spectrometric measurements and computations, which indicated the formation and stability of CD ⋅ B₂₁H₁₈⁻ complexes in the gas phase. The thermodynamic signature of solution‐phase binding is exceptional, the association constant for the γ‐CD complex with B₂₁H₁₈⁻ reaches 1.8×10⁶ M⁻¹, which is on the same order of magnitude as the so far highest observed value for the complex between γ‐CD and a metallacarborane. The nature of the intermolecular interaction is also examined by quantum‐mechanical computational protocols. These suggest that the desolvation penalty, which is particularly low for the B₂₁H₁₈⁻ anion, is the decisive factor for its high binding strength. The results further suggest that the elliptical macropolyhedral boron hydride is another example of a CD binder, whose extraordinary binding affinity is driven by the chaotropic effect, which describes the intrinsic affinity of large polarizable and weakly solvated chaotropic anions to hydrophobic cavities and surfaces in aqueous solution.K.I.A. and W.M.N. are grateful to the DFG for grant NA-686/8 within the priority program SPP 1807 “Control of London Dispersion Interactions in Molecular Chemistry”. J.H., J.F., and D.H. thank the Czech Science Foundation (grant number 17-08045S) and M.I.F.P., M.C.L, and J.A.S.L. thank the regional government Xunta de Galicia for financial support (Project Grupo Potencial Crecemento -GPC- ED431B 2017/59). J.M.O.-E. acknowledges financial support from the Spanish MICINN through project CTQ2018-094644-B-C22German Research Foundation; NA‐686/8Czech Science Foundation; 17‐08045SXunta de Galicia; ED431B 2017/5

Unusual cage rearrangements in 10-vertex nido-5,6-dicarbaborane derivatives : An interplay between theory and experiment

The reaction between selected X-nido-5,6-C2B8H11 compounds (where X = Cl, Br, I) and "Proton Sponge" [PS; 1,8-bis(dimethylamino)naphthalene], followed by acidification, results in extensive rearrangement of all cage vertices. Specifically, deprotonation of 7-X-5,6-C2B8H11 compounds with one equivalent of PS in hexane or CH2Cl2 at ambient temperature led to a 7 → 10 halogen rearrangement, forming a series of PSH+[10-X-5,6-C2B8H10]- salts. Reprotonation using concentrated H2SO4 in CH2Cl2 generates a series of neutral carbaboranes 10-X-5,6-C2B8H11, with the overall 7 → 10 conversion being 75%, 95%, and 100% for X = Cl, Br, and I, respectively. Under similar conditions, 4-Cl-5,6-C2B8H11 gave ∼66% conversion to 3- Cl-5,6-C2B8H11. Since these rearrangements could not be rationalized using the Bvertex swing mechanism, new cage rearrangement mechanisms, which are substantiated using DFT calculations, have been proposed. Experimental 11B NMR chemical shifts are well reproduced by the computations; as expected δ(11B) for B(10) atoms in derivatives with X = Br and I are heavily affected by spin-orbit coupling

Henkilötietojärjestelmän kehitys Liferay-alustalle

Opinnäytetyön tarkoitus on luoda asiakkaan vanhentuneen ja ulkoisella sivustolla sijaitsevan puhelinluettelojärjestelmän tilalle uusi henkilötietojärjestelmä asiakkaan omalle verkkosivulle. Uuteen henkilötietojärjestelmään kuuluu yhteystietojen tallennus, tuonti ulkoisesta järjestelmästä asiakkaan omaan Liferay-ympäristöön sekä henkilötietojen näyttäminen kahdella erilaisella toteutuksella. Henkilötietojen näyttöön luotiin kaksi erilaista komponenttia: puhelinluettelo sekä räätälöityjen listojen luontiin ja näyttämiseen tarkoitettu komponentti. Molemmat komponentit luotiin Liferayn portlet-liitännäisinä. Opinnäytetyön tarkoituksena ei ole kuitenkaan toimia ohjeena sille, miten Liferaylle luodaan portlet-liitännäisiä, vaan se on kuvaus asiakkaalle tehdystä työstä. Työn toimeksiantaja on Visma Consulting Oy, jonka välityksellä työ tehtiin kolmannen osapuolen asiakkaalle. Asiakas pidetään anonyyminä opinnäytetyössä. Yhteistyötä asiakkaan ja Visma Consultingin välillä on ollut jo ennen opinnäytetyötä ja muun muassa Liferay-ympäristö, jolle portletit asennetaan, on Visma Consultingin toteuttama.The purpose of this thesis is to create a new personnel information system into the client’s existing website to replace their old telephone directory located on an external site. The new personnel information system consists of components that handle saving the contact information of the personnel, importing them from the client’s external system to their own Liferay-environment and presenting that information using two different implementations. The information is presented as a new telephone directory as well as a component that allows the creation and presentation of custom lists of contacts. Both components were implemented as Liferay portlet-plugins. The purpose of this thesis is not to act as a guideline on how to create portlet-plugins for Liferay, but to simply showcase and go into detail on what was created for the client. The components were created for Visma Consulting Oy, who is not the end client, but a consulting company from which the components were ordered from by a third-party client. The client will be kept anonymous in the thesis. Co-operation between the client and Visma Consulting has been happening even before this thesis and the Liferay-environment, among other things, was created for the client by Visma Consulting

Influence of Antipodally Coupled Iodine and Carbon Atoms on the Cage Structure of 9,12-I2-closo-1,2-C2B10H10 : An Electron Diffraction and Computational Study

Because of the comparable electron scattering abilities of carbon and boron, the electron diffraction structure of the C2v-symmetric molecule closo-1,2-C2B10H12 (1), one of the building blocks of boron cluster chemistry, is not as accurate as it could be. On that basis, we have prepared the known diiodo derivative of 1, 9,12-I2-closo-1,2-C2B10H10 (2), which has the same point-group symmetry as 1 but in which the presence of iodine atoms, with their much stronger ability to scatter electrons, ensures much better structural characterization of the C2B10 icosahedral core. Furthermore, the influence on the C2B10 geometry in 2 of the antipodally positioned iodine substituents with respect to both carbon atoms has been examined using the concerted application of gas electron diffraction and quantum chemical calculations at the MP2 and density functional theory (DFT) levels. The experimental and computed molecular geometries are in good overall agreement. Molecular dynamics simulations used to obtain vibrational parameters, which are needed for analyzing the electron diffraction data, have been performed for the first time for this class of compound. According to DFT calculations at the ZORA-SO/BP86 level, the 11B chemical shifts of the boron atoms to which the iodine substituents are bonded are dominated by spin-orbit coupling. Magnetically induced currents within 2 have been calculated and compared to those for [B12H12]2-, the latter adopting a regular icosahedral structure with Ih point-group symmetry. Similar total current strengths are found but with a certain anisotropy, suggesting that spherical aromaticity is present; electron delocalization in the plane of the hetero atoms in 2 is slightly hindered compared to that for [B12H12]2-, presumably because of the departure from ideal icosahedral symmetry

Two Shared Icosahedral Metallacarboranes through Iron: A Joint Experimental and Theoretical Refinement of Mössbauer Spectrum in [Fe(1,2-C2B9H11)2]Cs

SUBJECTS:Anions,Conformation,Energy,Molecular structure,Quantum mechanicsMössbauer and X-ray photoelectron spectroscopies (XPS) are complemented with high-level quantum-chemical computations in the study of the geometric and electronic structure of the paramagnetic salt of the metallacarborane sandwich complex [Fe(1,2-CBH)]Cs = FeSanCs. Experimental Fe isomer shifts and quadrupole splitting parameters are compared with the theoretical prediction, with good agreement. The appearance of two sets of Cs(3d) doublets in the XPS spectrum, separated by 2 eV, indicates that Cs has two different chemical environments due to ease of the Cs cation moving around the sandwich complex with low-energy barriers, as confirmed by quantum-chemical computations. Several minimum-energy geometries of the FeSanCs structure with the corresponding energies and Mössbauer parameters are discussed, in particular the atomic charges and spin population and the surroundings of the Fe atom in the complex. The Mössbauer spectra were taken at different temperatures showing the presence of a low-spin Fe atom with S = 1/2 and thus confirming a paramagnetic Fe species.We are grateful to Prof. Ibon Alkorta (IQM-CSIC) for providing the MEP of trans-FeSan anion conformer. J.F.M. and J.Z.D.-P. acknowledge financial support from grant RTI2018-095303-B-C51 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” and from grant S2018-NMT-4321 funded by the Comunidad de Madrid and by “ERDF A way of making Europe”. M.F., J.E., and J.M.O.-E. are grateful to Ministerio de Ciencia, Innovacióny Universidades, for financial support with grant number PID2021-125207NB-C32. O.B.O. and D.R.A. acknowledge the financial support from the Universidad de Buenos Aires (grant no. 20020190100214BA), the Consejo Nacional de Investigaciones Científicas y Técnicas (grant nos PIP11220200100467CO, PIP 11220130100377CO, and PIP11220130100311CO), and the Agencia Nacional de Promoción Científica y Tecnológica, Argentina (grant no. PICT-201-0381).Peer reviewe

A novel stibacarbaborane cluster with adjacent antimony atoms exhibiting unique pnictogen bond formation that dominates its crystal packing

We have prepared nido-7,8,9,11-Sb2C2B7H9, the first cluster with simultaneous Sb-B, Sb-C and Sb-Sb atom pairs with interatomic separations with magnitudes that approach the respective sums of covalent radii. However, the length of the Sb-Sb separation in this cluster is slightly less than the sum of the covalent radii. Quantum chemical analysis has revealed that the crystal packing of nido-7,8,9,11-Sb2C2B7H9 is predominantly dictated by pnictogen (Pn) bonding, an unconventional σ-hole interaction. Indeed, the interaction energy of a very strong Sb2⋯H-B Pn-bond in the nido-7,8,9,11-Sb2C2B7H9 dimer exceeds -6.0 kcal mol-1. This is a very large value and is comparable to the strengths of known Pn-bonds in Cl3Pn⋯π complexes (Pn = As, Sb)