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

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

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)

Borane Polyhedra as Building Blocks for Unknown but Potentially Isolatable New Molecules – Extensions based on Computations of the Known B18H22 Isomers

Known borane polyhedral cluster characteristics can be used for predicting new architectural constructs. We propose additional structures derived from B18H22 : three positional isomers different from the well-known anti-B18H22 and syn-B18H22 boranes. We have also derived two new cyclic structures based on the condensation of borane pentagonal pyramids and bipyramids. The concatenation of polyhedral borane molecules is also considered from a mathematical point of view. (doi: 10.5562/cca2304

A computational analysis of the apparent nido vs. hypho conflict : are we dealing with six- or eight-vertex open-face diheteroboranes?

A series of computational studies have been undertaken to investigate the electronic structures and bonding schemes for six hetero-substituted borane cages, all of which have been presented in the literature as potential hypho structures. The six species are hypho-7,8-[C2B6H13]- ( 1a ), hypho-7,8-[CSB6H11]- ( 1b ), hypho-7,8-[S2B6H9]- ( 1c ), hypho-7,8-[NSB6H11] ( 1d ), exo-7-Me-hypho-7,8-[NCB6H12] ( 1e ), and endo-7-Me-hypho-7,8-[NCB6H12] ( 1f ) and the so-called mno rule has been applied to each of them. As no structural data are known for the carbathia-, azathia-, and dithiahexaboranes, we have also applied the ab initio/GIAO/NMR structural tool for 1b-1d , with 1c having been prepared for this purpose. We conclude that an mno count of 10 means that 1a , 1b , 1d , 1e , and 1f should be termed pseudo-nido or pseudo-hypho. Only can be considered to be correctly termed hypho-7,8-[S2B6H9]-

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

Nuclear magnetic shielding of monoboranes : calculation and assessment of 11B NMR chemical shifts in planar BX3 and in tetrahedral [BX4]- systems

The financial support of the Czech Science Foundation (project No. 17-08045S) is gratefully acknowledged.11B NMR chemical shifts of tricoordinated BX3 and tetracoordinated BX4- compounds (X = H, CH3, F, Cl, Br, I, OH, SH, NH2, and CH=CH2) were computed and the shielding tensors were explored not only within the nonrelativistic GIAO approach but also by applying both relativistic ZORA computations including spin-orbit coupling as well as by employing scalar nonrelativistic ZORA computations (BP86 level of density functional theory). The contributions of the spin-orbit coupling to the overall shieldings are decisive for X = Br and I in both series. No relationship was found between the 2p orbital occupancies or 1/∆E (difference between LUMO and suitably occupied MO that can be coupled with LUMO) with the shielding tensors (or their principal values) in the BX3 series. However, a multidimensional statistical approach known as factor analysis (frequently used in chemometrics) revealed that three factors account for 92 % of the cumulative proportion of total variance. The main components of the first factor are occupancies in the 2px and 2py orbitals and 1/∆E, the second factor is mainly the occupancy in the 2pz orbital and the inductive substituent parameters by Taft and, finally, the third factor consists exclusively (99.3 %) of the electrostatic potentials (Vmax), which is directly related to the so-called π-hole magnitudes.PostprintPeer reviewe

Stereochemie karboranů vznikajících sedmistupňovou degradací dekaboranu

The final level of geometry optimizations of these clusters of various molecular shapes included the effect of electron correlation, which considerably improved the fit between the calculated (GIAO-SCF or GIAO-MP2) and experimental 11B chemical shifts

Dihalogen and Pnictogen Bonding in Crystalline Icosahedral Phosphaboranes

Noncovalent interactions in the single crystal of 3,6-Cl2-closo-1,2-P2B10H8 and in the crystal of closo-1,7-P2B10Cl10•toluene were analyzed by means of quantum chemical computations. The crystal packing in the second crystal was dominated by numerous B-Cl···Cl-B dihalogen and strong B-P···π pnictogen bonds, the latter of which were characterized by a small length of 3.08 Å and a large interaction energy value, exceeding −10 kcal mol−1