Die Wasserstoffbrücke – eine aktualisierte Definition

Die Wasserstoffbrücke ist eine Wechselwirkung, bei der ein Wasserstoffatom von zwei Atomen statt nur einem angezogen wird und als Brücke zwischen den beiden wirkt. Die Anziehung wird mit zunehmender Elektronegativität jedes der beiden Atome stärker. In klassischer Betrachtungsweise sind Wasserstoffbrücken weitgehend elektrostatisch, in manchen Fällen sogar teilkovalent. Das Konzept der Wasserstoffbrücke wurde im Laufe der Zeit immer wieder erweitert, um auch schwächere und dispersivere Wechselwirkungen einzubeziehen, sofern eine gewisse elektrostatische Beschaffenheit der Wechselwirkung gegeben ist. In der Praxis wird eine enorme Vielfalt an sehr starken, starken, mäßig starken, schwachen und sehr schwachen Wasserstoffbrücken beobachtet. Aktuell werden schwache Wasserstoffbrücken mit vielen Fragen der Strukturchemie und der Biologie in Verbindung gebracht. Während starke Wasserstoffbrücken von allen bestehenden Definitionen der Erscheinung erfasst werden, können schwächere zu Problemen bei der Benennung und zu Konflikten mit bestehenden Definitionen führen. Kürzlich wurde der International Union of Pure and Applied Chemistry (IUPAC) eine Empfehlung für eine aktualisierte Definition des Begriffs “Wasserstoffbrücke” vorgelegt. In diesem Essay soll die vorgeschlagene Definition ausführlich erläutert werden.     

Effect of normal variations on disease classification of Raman spectra from cervical tissue

In this paper, we examine how variations in normal tissue can influence disease classification of Raman spectra. Raman spectra from normal areas may be affected by previous disease or proximity to areas of dysplasia. Spectra were acquired in vivo from 172 patients and classified into five tissue categories: true normal (no history of disease), previous disease normal (history of disease, current normal diagnosis), adjacent normal (disease on cervix, spectra acquired from visually normal area), low grade, and high grade. Taking into account the various "normal" states of the tissue before statistical analysis led to a disease classification accuracy of 97%. These results indicate that abnormal changes significantly affect Raman spectra, even when areas are histopathologically normal. The sensitivity of Raman spectroscopy to subtle biochemical differences must be considered in order to successfully implement it in a clinical setting for diagnosing cervical dysplasia and cancer.     

Nature and strength of C-H···O interactions involving formyl hydrogen atoms: computational and experimental studies of small aldehydes

Structural and electronic properties of C-H···O contacts in compounds containing a formyl group are investigated from the perspective of both hydrogen bonding and dipole-dipole interactions, in a systematic and graded approach. The effects of α-substitution and self-association on the nature of the formyl H-atom are studied with the NBO and AIM methodologies. The relative dipole-dipole contributions in formyl C-H···O interactions are obtained for aldehyde dimers. The stabilities and energies of aldehyde clusters (dimer through octamer) have been examined computationally. Such studies have an implication in crystallization mechanisms. Experimental X-ray crystal structures of formaldehyde, acrolein and N-methylformamide have been determined in order to ascertain the role of C-H···O interactions in the crystal packing of formyl compounds.     

Forward–Backward–Half Forward Dynamical Systems for Monotone Inclusion Problems with Application to v-GNE

Journal of Optimization Theory and Applications - In this paper, the first-order forward–backward–half forward dynamical systems associated with the inclusion problem consisting of...     

Ultrafast dynamics and excited state deactivation of [Ru(bpy)2Sq]+ and its derivatives

Femtosecond transient absorption spectroscopy has been employed to understand the excited state dynamics of [Ru(bpy)(2)Sq](+) (I; bpy is 2,2'-bipyridyl, and Sq is the deprotonated species of the semiquinone form of 1,2-dihydroxy benzene) and its derivatives, a widely studied near-infrared (NIR) active electrochromic dye. Apart from the well-defined dpi(Ru) --> pi(bpy)-based metal-to-ligand charge transfer (MLCT) transition bands at approximately 480 nm, this class of molecules generally shows another dpi(Ru) --> pi(Sq)(SOMO)-based intense MLCT band at around 900 nm, which is known to be redox active and bleaches reversibly upon a change in the oxidation state of the coordinated dioxolene moiety. To have better insight into the photoinduced electron transfer dynamics associated with this MLCT transition, detailed investigations have been carried out on exciting this MLCT band at 800 nm. Immediately after photoexcitation, bleach at 900 nm has been observed, whose recovery is found to follow a triexponential function with major contribution from the ultrafast component. This ultrafast component of approximately 220 fs has been ascribed to the S(1) to S(0) internal conversion process. In addition to the bleach, we have detected two transient species absorbing at 730 and 1000 nm with a formation time approximately 220 fs for both species. The excited state lifetimes for these two transient species have been measured to be 1.5 and 11 ps and have been attributed to excited singlet ((1)MLCT) and triplet ((3)MLCT) states, respectively. Transient measurements carried out on the different but analogous derivatives (II and III) have also shown similar recovery dynamics except that the rate for the internal conversion process has increased with the decrease in the S(1) to S(0) energy gap. The observed results are consistent with the energy gap law for nonradiative decay from S(1) to S(0).     

Weyl group multiple Dirichlet series constructed from quadratic characters

We construct multiple Dirichlet series in several complex variables whose coefficients involve quadratic residue symbols. The series are shown to have an analytic continuation and satisfy a certain group of functional equations. These are the first examples of an infinite collection of unstable Weyl group multiple Dirichlet series in greater than two variables having the properties predicted in [2].     

Treasury Management Model with Foreign Exchange Exposure

In this paper we formulate a model for foreign exchange exposure management and (international) cash management taking into consideration random fluctuations of exchange rates. A vector error correction model (VECM) is used to predict the random behaviour of the forward as well as spot rates connecting dollar and sterling. A two-stage stochastic programming (TWOSP) decision model is formulated using these random parameter values. This model computes currency hedging strategies, which provide rolling decisions of how much forward contracts should be bought and how much should be liquidated.The model decisions are investigated through ex post simulation and backtesting in which value at risk (VaR) for alternative decisions are computed. The investigation (a) shows that there is a considerable improvement to “spot only” strategy, (b) provides insight into how these decisions are made and (c) also validates the performance of this model.