Asymmetric indolylmaleimide derivatives and their complexation with zinc(II)-cyclen

The spectroscopic properties of two asymmetric indolylmaleimide derivatives, 4-bromo-3-(1'H-indol-3'-yl)maleimide and 4-methyl-3-(1'H-indol-3'-yl)maleimide, are investigated. The bromo derivative was crystallized and its X-ray structure was determined. Both compounds are strongly colored while their separate components (indole and maleimide) absorb in the UV region only. To understand the ground- and excited-state behavior, the photophysical properties of the two compounds were studied in detail by steady state and time-resolved absorption and emission spectroscopy. Their solvatochromic behavior was investigated by using the Kamlet-Taft approach, which indicates some charge transfer (CT) character in the excited state. Nano- and femtosecond transient absorption spectroscopy was used for the identification and investigation of the CT state. Furthermore, the effect of the complexation with zinc(II) 1,4,7,11-tetraazacyclododecane (Zn-cyclen) on the photophysical properties of these two compounds was studied. An enhancement of the fluorescence intensity upon self-assembly (up to 90 times) and high association constants were observed, which illustrate the potential use of these compounds as luminescent sensors. DFT calculations indicate that HOMO-1 to LUMO excitation is mainly responsible for the charge transfer character and that this transition changes its character drastically when Zn-cyclen complexation occurs, thus giving it sensor properties.     

The chemo- enzymatic synthesis of labeled <Emphasis Type="SmallCaps">l</Emphasis>-amino acids and some of their derivatives

This review compiles the combined chemical and enzymatic synthesis of aromatic l-amino acids (l-phenylalanine, l-tyrosine, l-DOPA, l-tryptophan, and their derivatives and precursors) specifically labeled with carbon and hydrogen isotopes, which were elaborated in our research group by the past 20 years. These compounds could be then employed to characterize the mechanisms of enzymatic reactions via kinetic and solvent isotope effects methods.     

Harnessing Effective Molarity to Design an Electrochemical DNA‐based Platform for Clinically Relevant Antibody Detection

Easy‐to‐use platforms for rapid antibody detection are likely to improve molecular diagnostics and immunotherapy monitoring. However, current technologies require multi‐step, time‐consuming procedures that limit their applicability in these fields. Herein, we demonstrate effective molarity‐driven electrochemical DNA‐based detection of target antibodies. We show a highly selective, signal‐on DNA‐based sensor that takes advantage of antibody‐binding‐induced increase of local concentration to detect clinically relevant antibodies in blood serum. The sensing platform is modular, rapid, and versatile and allows the detection of both IgG and IgE antibodies. We also demonstrate the possible use of this strategy for the monitoring of therapeutic monoclonal antibodies in body fluids. Our approach highlights the potential of harnessing effective molarity for the design of electrochemical sensing strategies.     

Zn(II) Heteroleptic Halide Complexes with 2-Halopyridines: Features of Halogen Bonding in Solid State

Reactions between Zn(II) dihalides and 2-halogen-substituted pyridines 2-XPy result in a series of heteroleptic molecular complexes [(2-XPy)₂ZnY₂] (Y = Cl, X = Cl (1), Br (2), I (3); Y = Br, X = Cl (4), Br (5), I (6), Y = I, X = Cl (7), Br (8), and I (9)). Moreover, 1–7 are isostructural (triclinic), while 8 and 9 are monoclinic. In all cases, halogen bonding plays an important role in formation of crystal packing. Moreover, 1–9 demonstrate luminescence in asolid state; for the best emitting complexes, quantum yield (QY) exceeds 21%.     

A Two-Stage Active-Set Algorithm for Bound-Constrained Optimization

In this paper, we describe a two-stage method for solving optimization problems with bound constraints. It combines the active-set estimate described in Facchinei and Lucidi (J Optim Theory Appl 85(2):265–289, 1995) with a modification of the non-monotone line search framework recently proposed in De Santis et al. (Comput Optim Appl 53(2):395–423, 2012). In the first stage, the algorithm exploits a property of the active-set estimate that ensures a significant reduction in the objective function when setting to the bounds all those variables estimated active. In the second stage, a truncated-Newton strategy is used in the subspace of the variables estimated non-active. In order to properly combine the two phases, a proximity check is included in the scheme. This new tool, together with the other theoretical features of the two stages, enables us to prove global convergence. Furthermore, under additional standard assumptions, we can show that the algorithm converges at a superlinear rate. Promising experimental results demonstrate the effectiveness of the proposed method.     

Effect of maleic anhydride content on the rheology and phase behavior of poly(styrene-co -maleic anhydride)/ poly(methyl methacrylate) blends

 We investigated the thermo- rheological behavior of high glass transition, high molecular weight and small dynamic asymmetry blends of poly(styrene-co-maleic anhydride) (SMA) and poly (methyl methacrylate) (PMMA) with varying amounts of maleic anhydride (MA) content, namely 8 wt%, 14 wt% and 32 wt%, in the SMA component. The phase separation (binodal) temperature of each blend was determined rheologically using a combination of dynamic frequency and temperature sweeps in parallel plate geometry; it was marked by a change in slope of the elastic modulus and the occurrence of a peak in tan δ in temperature sweeps. Failure of the time-temperature superposition principle and observation of two peaks in the Cole-Cole plots corroborated these findings. The blends displayed lower critical solution temperature (LCST) behavior with the critical temperatures exhibiting a non-monotonic dependence on the MA content. From rheological and thermal measurements it was concluded that SMA/PMMA blends containing 14% MA were more miscible than those containing 8% or 32% MA, a finding attributed to the compositional dependence of the interplay between SMA-SMA and SMA-PMMA interactions in the different samples. MA also influenced the dynamic asymmetry and pretransitional concentration fluctuations. The phase diagrams corresponding to each blend were modeled using a two-parameter temperature dependent interaction parameter, based on the concept of generalized Gibbs free energy of mixing. The fitted values of interaction parameter were in good agreement with values calculated explicitly using the Flory-Huggins theory. Received: 16 February 2001 Accepted: 11 July 2001     

Geometric properties of root vectors for equation of nonhomogeneous damped string: transformation operators method

The spectral decomposition theorem for a class of nonselfadjoint operators in a Hilbert space is obtained in the paper. These operators are the dynamics generators for the systems governed by 1–dim hyperbolic equations with spatially nonhomogeneous coefficients containing first order damping terms and subject to linear nonselfadjoint boundary conditions. These equations and boundary conditions describe, in particular, a spatially nonhomogeneous string subject to a distributed viscous damping and also damped at the boundary points. The main result leading to the spectral decomposition is the fact that the generalized eigenvectors (root vectors) of the above operators form Riesz bases in the corresponding energy spaces. The proofs are based on the transformation operators method. The classical concept of transformation operators is extended to the equation of damped string. Originally, this concept was developed by I. M. Gelfand, B. M. Levitan and V. A. Marchenko for 1–dim Schrödinger equation in connection with the inverse scattering problem. In the classical case, the transformation operator maps the exponential function (stationary wave function of the free particle) into the Jost solution of the perturbed Schrödinger equation. For the equation of a nonhomogeneous damped string, it is natural to introduce two transformation operators (outgoing and incoming transformation operators). The terminology is motivated by an analog with the Lax—Phillips scattering theory. The transformation operators method is used to reduce the Riesz bases property problem for the generalized eigenvectors to the similar problem for a system of nonharmonic exponentials whose complex frequencies are precisely the eigenvalues of our operators. The latter problem is solved based on the spectral asymptotics and known facts about exponential families. The main result presented in the paper means that the generator of a finite string with damping both in the equation and in the boundary conditions is a Riesz spectral operator. The latter result provides a class of nontrivial examples of non—selfadjoint operators which admit an analog of the spectral decomposition. The result also has significant applications in the control theory of distributed parameter systems.     

Synthesis and characterisation of the 3-amino-derivative of γ-cyclodextrin, showing receptor ability and metal ion coordination properties

The 3-hydroxy group of one glucopyranosinic ring of γ-cyclodextrin was selectively substituted with an amino moiety to obtain a new compound able to complex copper(II). Indeed, the new ligand, an altro-γ-CD, forms stable complexes with Cu(II), as the analogous 3-amino derivative β-CD previously exploited for the chiral separation of some amino acids by ligand exchange mechanism in capillary electrophoresis. Furthermore, the ligand forms a stable inclusion complex with anthraquinone-2-sulfonate.