Big,Strong, Neutral,Twisted, and Chiral π Acids

General synthetic access to expanded π‐acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion–π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron‐withdrawing substituents decreases and the high π acidity needed for strong anion–π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion–π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from ?3.96 to ?4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X‐ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation–π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches ?4.45 eV, whereas two sulfone moieties give a value of ?4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion–π interactions, these conceptually innovative π‐acidic surfaces are also of interest as electron transporters in conductive materials.     

Comparative metabolite profiling of carboxylic acids in rat urine by CE‐ESI MS/MS through positively pre‐charged and 2H‐coded derivatization

A new approach to the selective comparative metabolite profiling of carboxylic acids in rat urine was established using CE‐MS and a method for positively pre‐charged and ²H‐coded derivatization. Novel derivatizing reagents, N‐alkyl‐4‐aminomethyl‐pyridinum iodide (alkyl=butyl, butyl‐d9 or hexyl), containing quaternary amine and stable‐isotope atoms (deuterium), were introduced for the derivatization of carboxylic acids. CE separation in positive polarity showed high reproducibility (0.99–1.32% RSD of migration time) and eliminated problems with capillary coating known in CE‐MS anion analyses. Essentially complete ionization and increased hydrophobicity after the derivatization also enhanced MS detection sensitivity (e.g. formic acid was detected at 0.5 pg). Simultaneous derivatization of one sample using two structurally similar reagents, N‐butyl‐4‐aminomethyl‐pyridinum iodide (BAMP) and N‐hexyl‐4‐aminomethyl‐pyridinum iodide, provided additional information for recognizing a carboxylic acid in an unknown sample. Moreover, characteristic fragmentation acquired by online CE‐MS/MS allowed for identification and categorization of carboxylic acids. Applying this method on rat urine, we found 59 ions matching the characteristic patterns of carboxylic acids. From these 59, 32 ions were positively identified and confirmed with standards. For comparative analysis, 24 standard carboxylic acids were derivatized by chemically identical but isotopically distinct BAMP and N‐butyl‐d9‐4‐aminomethyl‐pyridinium iodide, and their derivatization limits and linearity ranges were determined. Comparative analysis was also performed on two individual urine samples derivatized with BAMP and N‐butyl‐d9‐4‐aminomethyl‐pyridinium iodide. The metabolite profiling variation between these two samples was clearly visualized.     

Two-dimensional lanthanide coordination polymers with bis(diphenylphosphino)hexane dioxide. The determination of the polymeric structure from twinned crystals

Lanthanide nitrates and bis(diphenylphosphino)hexane dioxide (dpphO₂) formed under solvothermal conditions a series of coordination polymers [Ln(dpphO₂)₂(NO₃)₂](NO₃) (Ln = Pr (1), Nd (2), Sm (3), Dy (4), Lu (5)), featuring two-dimensional network structure of the (4, 4) topology. The compounds [Ln(dpphO₂)₂Cl₂]Cl (Ln = Pr (6), Nd (7), Gd (8)) were obtained from corresponding chlorides. Coordination polymer 7 formed regular single crystals of the orthorhombic Pna₂₁$\mathit{Pna}{2}_1$ space group. The nitrate complexes crystallized in the orthorhombic Aea2 space group, however, the crystals were pseudo-merohedral twins simulating a tetragonal diffraction pattern. Unlike our previously characterized neutral polymers with bis(diphenylphosphino)ethane dioxide, all present coordination networks are cationic, with anions located between or within the two-dimensional layers.     

Ultrafast excited state dynamics controlling photochemical isomerization of N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium coordinated to a {Re I(CO)3(2,2'-bipyridine)} chromophore

Two multifunctional photoactive complexes [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) and [Re(MeDpe(+))(CO)(3)(bpy)](2+) (MeDpe(+)=N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium, bpy=2,2'-bipyridine) were synthesized, characterized, and their redox and photonic properties were investigated by cyclic voltammetry; ultraviolet-visible-infrared (UV/Vis/IR) spectroelectrochemistry, stationary UV/Vis and resonance Raman spectroscopy; photolysis; picosecond time-resolved absorption spectroscopy in the visible and infrared regions; and time-resolved resonance Raman spectroscopy. The first reduction step of either complex occurs at about -1.1 V versus Fc/Fc(+) and is localized at MeDpe(+). Reduction alone does not induce a trans-->cis isomerization of MeDpe(+). [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) is photostable, while [Re(MeDpe(+))(CO)(3)(bpy)](2+) and free MeDpe(+) isomerize under near-UV irradiation. The lowest excited state of [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) has been identified as the Re(Cl)(CO)(3)-->MeDpe(+ 3)MLCT (MLCT=metal-to-ligand charge transfer), decaying directly to the ground state with lifetimes of approximately 42 (73 %) and approximately 430 ps (27 %). Optical excitation of [Re(MeDpe(+))(CO)(3)(bpy)](2+) leads to population of Re(CO)(3)-->MeDpe(+) and Re(CO)(3)-->bpy (3)MLCT states, from which a MeDpe(+) localized intraligand (3)pipi* excited state ((3)IL) is populated with lifetimes of approximately 0.6 and approximately 10 ps, respectively. The (3)IL state undergoes a approximately 21 ps internal rotation, which eventually produces the cis isomer on a much longer timescale. The different excited-state behavior of the two complexes and the absence of thermodynamically favorable interligand electron transfer in excited [Re(MeDpe(+))(CO)(3)(bpy)](2+) reflect the fine energetic balance between excited states of different orbital origin, which can be tuned by subtle structural variations. The complex [Re(MeDpe(+))(CO)(3)(bpy)](2+) emerges as a prototypical, multifunctional species with complementary redox and photonic behavior.     

Screening of pi-basic naphthalene and anthracene amplifiers for pi-acidic synthetic pore sensors

Synthetic ion channels and pores attract current attention as multicomponent sensors in complex matrixes. This application requires the availability of reactive signal amplifiers that covalently capture analytes and drag them into the pore. pi-Basic 1,5-dialkoxynaphthalenes (1,5-DAN) are attractive amplifiers because aromatic electron donor-acceptor (AEDA) interactions account for their recognition within pi-acidic naphthalenediimide (NDI) rich synthetic pores. Focusing on amplifier design, we report here the synthesis of a complete collection of DAN and dialkoxyanthracene amplifiers, determine their oxidation potentials by cyclic voltammetry, and calculate their quadrupole moments. Blockage experiments reveal that subtle structural changes in regioisomeric DAN amplifiers can be registered within NDI pores. Frontier orbital overlap in AEDA complexes, oxidation potentials, and, to a lesser extent, quadrupole moments are shown to contribute to isomer recognition by synthetic pores. Particularly important with regard to practical applications of synthetic pores as multianalyte sensors, we further demonstrate that application of the lessons learned with DAN regioisomers to the expansion to dialkoxyanthracenes provides access to privileged amplifiers with submicromolar activity.     

Rheological properties of asphalt/SBS/clay blends

The effect of the addition of clay as a third component in polymer modified asphalts has been investigated. After a preliminary investigation on the binary asphalt/clay and polymer/clay blends, the tertiary blends were prepared by adding the clay and polymer to the asphalt, either separately or in the form of a premixed master batch. Intercalated nanocomposites with comparable interlayer distances and glass transition temperatures were obtained in both cases. However, the results show that the mixing procedure significantly affected the final rheological properties. The master curves built in the linear viscoelastic range and represented in both the frequency and the temperature domains help to visualize and evaluate such differences.     

Enolate Stabilization by Anion–π Interactions: Deuterium Exchange in Malonate Dilactones on π‐Acidic Surfaces

Of central importance in chemistry and biology, enolate chemistry is an attractive topic to elaborate on possible contributions of anion–π interactions to catalysis. To demonstrate the existence of such contributions, experimental evidence for the stabilization of not only anions but also anionic intermediates and transition states on π‐acidic aromatic surfaces is decisive. To tackle this challenge for enolate chemistry with maximal precision and minimal uncertainty, malonate dilactones are covalently positioned on the π‐acidic surface of naphthalenediimides (NDIs). Their presence is directly visible in the upfield shifts of the α‐protons in the ¹H NMR spectra. The reactivity of these protons on π‐acidic surfaces is measured by hydrogen–deuterium (H–D) exchange for 11 different examples, excluding controls. The velocity of H–D exchange increases with π acidity (NDI core substituents: SO₂R>SOR>H>OR>OR/NR₂>SR>NR₂). The H–D exchange kinetics vary with the structure of the enolate (malonates>methylmalonates, dilactones>dithiolactones). Moreover, they depend on the distance to the π surface (bridge length: 11–13 atoms). Most importantly, H–D exchange depends strongly on the chirality of the π surface (chiral sulfoxides as core substituents; the crystal structure of the enantiopure (R,R,P)‐macrocycle is reported). For maximal π acidity, transition‐state stabilizations up to ?18.8 kJ mol^?1 are obtained for H–D exchange. The Brønsted acidity of the enols increases strongly with π acidity of the aromatic surface, the lowest measured pK_a=10.9 calculates to a ΔpK_a=?5.5. Corresponding to the deprotonation of arginine residues in neutral water, considered as “impossible” in biology, the found enolate–π interactions are very important. The strong dependence of enolate stabilization on the unprecedented seven‐component π‐acidity gradient over almost 1 eV demonstrates quantitatively that such important anion–π activities can be expected only from strong enough π acids.     

Dynamic programming based metaheuristics for the dial-a-ride problem

The organization of a specialized transportation system to perform transports for elderly and handicapped people is usually modeled as dial-a-ride problem. Users place transportation requests with specified pickup and delivery locations and times. The requests have to be completed under user inconvenience considerations by a specified fleet of vehicles. In the dial-a-ride problem, the aim is to minimize the total travel times respecting the given time windows, the maximum user ride times, and the vehicle restrictions. This paper introduces a dynamic programming algorithm for the dial-a-ride problem and demonstrates its effective application in (hybrid) metaheuristic approaches. Compared to most of the works presented in literature, this approach does not make use of any (commercial) solver. We present an exact dynamic programming algorithm and a dynamic programming based metaheuristic, which restricts the considered solution space. Then, we propose a hybrid metaheuristic algorithm which integrates the dynamic programming based algorithms into a large neighborhood framework. The algorithms are tested on a given set of benchmark instances from the literature and compared to a state-of-the-art hybrid large neighborhood search approach.     

Voltametric,Amperometric, and Chronopotentiometric Determination of Submicromolar Concentrations of Carboxin

New procedures for the determination of pesticide carboxin were developed using differential pulse voltammetry, HPLC with amperometric detection and chronopotentiometry at carbon paste electrode and reticulated vitreous carbon electrode, respectively. Developed procedures based on electrochemical oxidation of carboxin were successfully applied on the determination of carboxin in the model samples of drinking and river water. Limits of detection in samples of river water were in 10^?7 mol L^?1 concentration range for all procedures and electrodes used. All developed procedures proved to be sensitive, accurate and, due to the resistance of the electrode to the passivation, also simple to handle.     

Synthetic pores with sticky pi-clamps

In this report, we describe design, synthesis, evaluation and molecular dynamics simulations of synthetic multifunctional pores with pi-acidic naphthalenediimide clamps. Experimental evidence is provided for the formation of unstable but inert, heterogeneous and acid-insensitive dynamic tetrameric pores that are sensitive to base and ionic strength. Blockage experiments reveal that the introduction of aromatic electron donor-acceptor interactions provides access to the selective recognition of pi-basic intercalators within the pore. This breakthrough is important for the application of synthetic pores as multianalyte sensors.