Speciation of the Vanadium(III) Complexes with 1,10-Phenanthroline, 2,2′-Bipyridine,and 8-Hydroxyquinoline

The complex species formed between vanadium(III) and 1,10-phenanthroline (phen), 2,2′-bipyridine (bipy), and 8-hydroxyquinoline (8hq) were studied in aqueous solution by means of electromotive forces measurements, emf(H), at 25 °C with 3.0 mol⋅dm⁻³ KCl as the ionic medium. The potentiometric data were analyzed using the least-squares computational program LETAGROP, taking into account the hydrolytic vanadium(III) species formed in solution. Analysis of the vanadium(III)–phen system data shows the formation of [VHL]⁴⁺, [V(OH)L]²⁺, [V₂OL₂]⁴⁺ and [V₂OL₄]⁴⁺ complexes. In the vanadium(III)–bipy system the [VHL]⁴⁺, [V(OH)L]²⁺, [V₂OL₂]⁴⁺ and [V₂OL₄]⁴⁺ complexes were observed, and in the vanadium(III)–8hq system the complexes [V(OH)L]⁺, [V(OH)₂L], [VL₂]⁺ and [VL₃] were detected.     

Prins-type macrocyclizations as an efficient ring-closing strategy in natural product synthesis

Prins-type macrocyclizations have recently emerged as a successful strategy in the synthesis of polyketide-derived natural products. This reaction provides a concise and selective means to form tetrahydropyran-containing macrocyclic rings of varying size. A high degree of functionality within the macrocycle is tolerated and the yields for these transformations are typically good to excellent. Since the initial report of a Prins macrocyclization reaction in 1979, examples of this approach did not re-emerge until 2008. However, the use of this method in natural product synthesis has rapidly gained momentum in the synthetic community, with multiple examples of this macrocyclization tactic reported in the recent literature.     

Nonlinear robust optimization via sequential convex bilevel programming

In this paper, we present a novel sequential convex bilevel programming algorithm for the numerical solution of structured nonlinear min–max problems which arise in the context of semi-infinite programming. Here, our main motivation are nonlinear inequality constrained robust optimization problems. In the first part of the paper, we propose a conservative approximation strategy for such nonlinear and non-convex robust optimization problems: under the assumption that an upper bound for the curvature of the inequality constraints with respect to the uncertainty is given, we show how to formulate a lower-level concave min–max problem which approximates the robust counterpart in a conservative way. This approximation turns out to be exact in some relevant special cases and can be proven to be less conservative than existing approximation techniques that are based on linearization with respect to the uncertainties. In the second part of the paper, we review existing theory on optimality conditions for nonlinear lower-level concave min–max problems which arise in the context of semi-infinite programming. Regarding the optimality conditions for the concave lower level maximization problems as a constraint of the upper level minimization problem, we end up with a structured mathematical program with complementarity constraints (MPCC). The special hierarchical structure of this MPCC can be exploited in a novel sequential convex bilevel programming algorithm. We discuss the surprisingly strong global and locally quadratic convergence properties of this method, which can in this form neither be obtained with existing SQP methods nor with interior point relaxation techniques for general MPCCs. Finally, we discuss the application fields and implementation details of the new method and demonstrate the performance with a numerical example.     

Maximal Inequalities of the Itô Integral with Respect to Poisson Random Measures or Lévy Processes on Banach Spaces

We are interested in maximal inequalities satisfied by a stochastic integral driven by a Poisson random measure in a general Banach space.     

Magnetically responsive carboxylated magnetite-polydipyrrole/polydicarbazole nanocomposites of core-shell morphology. Preparation, characterization, and use in DNA hybridization

Novel bis-heterocyclic mono- and dicarboxylated dipyrrole and dicarbazole monomers have been synthesized in a modular manner. Their oxidative polymerization around magnetite nanosized particles has been investigated and optimized toward new magnetic magnetite-polydipyrrole/polydicarbazole nanocomposites (NCs) of a core-shell morphology. These NCs were thoroughly characterized by FT-IR, TGA (Thermal Gravimetric Analysis), low- and high-resolution TEM/HR-TEM microscopies, and M?ssbauer spectroscopy along with magnetization studies. Exploiting the versatile COOH chemistry (activation by water-soluble diimides) introduced by the polymeric shell, DNA hybridization experiments have been conducted onto NC surfaces using an efficient blue-colored HRP-based enzymatic screening biological system. Highly parallel NC-supported DNA hybridization experimentations revealed that these NCs presented an interesting potential for DNA-based diagnostic applications.     

High-Quality Protein Crystal Growth of Mouse Lipocalin-Type Prostaglandin D Synthase in Microgravity

Lipocalin-type prostaglandin (PG) D synthase (L-PGDS) catalyzes the isomerization of PGH(2) to PGD(2) and is involved in the regulation of pain and of nonrapid eye movement sleep and the differentiation of male genital organs and adipocytes, etc. L-PGDS is secreted into various body fluids and binds various lipophilic compounds with high affinities, acting also as an extracellular transporter. Mouse L-PGDS with a C65A mutation was previously crystallized with citrate or malonate as a precipitant, and the X-ray crystallographic structure was determined at 2.0 ? resolution. To obtain high-quality crystals, we tried, unsuccessfully, to crystallize the C65A mutant in microgravity under the same conditions used in the previous study. After further purifying the protein and changing the precipitant to polyethylene glycol (PEG) 8000, high-quality crystals were grown in microgravity. The precipitant solution was 40% (w/v) PEG 8000, 100 mM sodium chloride, and 100 mM HEPES-NaOH (pH 7.0). Crystals grew on board the International Space Station for 11 weeks in 2007, yielding single crystals of the wild-type L-PGDS and the C65A mutant, both of which diffracted at around 1.0 ? resolution. The crystal quality was markedly improved through the use of a high-viscosity precipitant solution in microgravity, in combination with the use of a highly purified protein.     

A Hot‐Segment‐Based Approach for the Design of Cross‐Amyloid Interaction Surface Mimics as Inhibitors of Amyloid Self‐Assembly

The design of inhibitors of protein–protein interactions mediating amyloid self‐assembly is a major challenge mainly due to the dynamic nature of the involved structures and interfaces. Interactions of amyloidogenic polypeptides with other proteins are important modulators of self‐assembly. Here we present a hot‐segment‐linking approach to design a series of mimics of the IAPP cross‐amyloid interaction surface with Aβ (ISMs) as nanomolar inhibitors of amyloidogenesis and cytotoxicity of Aβ, IAPP, or both polypeptides. The nature of the linker determines ISM structure and inhibitory function including both potency and target selectivity. Importantly, ISMs effectively suppress both self‐ and cross‐seeded IAPP self‐assembly. Our results provide a novel class of highly potent peptide leads for targeting protein aggregation in Alzheimer’s disease, type 2 diabetes, or both diseases and a chemical approach to inhibit amyloid self‐assembly and pathogenic interactions of other proteins as well.     

Biomimetic Peptide Catalytic Bond-Forming Utilizing a Mild Brønsted Acid

Since the global peptide drug market demand has been predicted to increase, highly efficient and inexpensive mass scale peptides are required. However, the production process raises questions about the cost of energy input, scale-up production, raw materials, and solvents treatment. This paper introduces 2 methods for the 2–4 mer oligopeptides bond formation for batch reaction utilizing 50–100 mol% of a mild Brønsted acid under the mild condition. One of the methods has been capably adapted to flow synthesis at room temperature using organic solvents with boiling points below 100 °C. The method applies the tert-butoxycarbonyl amino methoxy group, forming the desired dipeptide without solvent at mild temperatures. Furthermore, the conversion of the carboxylic acid leaving the group to phenyl ester promotes peptide bond formation, and the reaction were applied to di, tri, and tetrapeptide bond formation in excellent yield without notable racemization at ambient temperature (up to >99 % yield and 99 : 1 dr). Finally, this study proposes this new production method to overcome the limited scale-up production by reaction device scale: liquid phase biomimetic catalytic peptide flow synthesis utilizing a mild Brønsted acid.     

The Susceptibility of Non-UV Fluorescent Membrane Dyes to Dynamical Properties of Lipid Membranes

Fluorescence spectroscopy and microscopy are powerful techniques to detect dynamic properties in artificial and natural lipid membrane systems. Unfortunately, most fluorescent dyes that sense dynamically relevant membrane parameters are UV sensitive. Their major disadvantage is a high susceptibility to fluorescence bleaching. Additionally, the risk for hazardous damages in biological components generally increases with decreasing excitation wavelength. Therefore the use of non-UV–sensitive membrane dyes would provide significant advantage, particularly for applications in fluorescence microscopy, which usually implies high local excitation intensities. We applied steady-state fluorescence spectroscopy techniques to several UV and non-UV membrane dyes to detect and compare dynamically relevant excitation and emission characteristics. Small unilamellar liposomes (composed of egg yolk phosphatidylcholine) served as a model system for biological membranes. The dynamic properties of the membranes were varied by two independent parameters: the intrinsic cholesterol content (0–50 mol%) and temperature (10–50°C). We tested four non-UV–sensitive membrane dyes: 9-diethylamino-5H-benzophenoxazine-5-one (Nile Red), 4-(dicyanovinyl)julolidine (DCVJ), N-(3-triethylammoniumpropyl)-4-(4-(dibutylamino)styryl) pyridinium dibromide (FM 4-64), and 1,1-dioctadecyl-3,3,3,3-tetramethylindocarbocyanine perchlorate (DiIC₁₈). We also tested three derivatives of DiIC₁₈: DiIC₁₆ and DiIC₁₂ differ in acyl chain length and Fast-DiIC₁₈ provides double bonds between hydrocarbon atoms. The spectral results were compared to established fluorescence characteristics of four UV membrane dyes: the anisotropy of 1-6-phenyl-1,3,5,-hexatrien (DPH), two derivatives of DPH (TMA-DPH and COO^–-DHP), and the generalized polarization of 6-dodecanoyl-2-dimethyl-aminonaphthalene (Laurdan). Our results indicate that the tested non-UV dyes do not reveal dynamically relevant membrane parameters in a direct manner. However, spectral characteristics make DiIC₁₈, Nile Red, and DCVJ promising probes for the microscopic detection of lateral lipid organization, an indirect indicator of membrane dynamics. In particular, DiIC₁₈ showed very selective shifts in the emission spectra at defined temperatures and cholesterol contents that have not been reported elsewhere.     

Charge transfer in the collision system He<Superscript>2+</Superscript> + C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack>: Theory and experiment

Fullerenes are a direct link between atoms with discrete electronic energy levels and solids with a band structure and a well-defined surface. In this paper, we report on a quantum mechanical treatment of charge transfer and ionization in the ion-ion collision system ³He²⁺ + C ₆₀ ⁺ . This approach considers under- and over-barrier transitions through the one-dimensional barrier between the collision partners. The calculated cross sections for charge transfer compare favorably with experimental data measured in the center-of-mass energy range from 27 to 196 keV employing the crossed beams technique.