Polyoxometalate-Engineered Building Blocks with Gold Cores for the Self-Assembly of Responsive Water-Soluble Nanostructures

The controlled assembly of gold nanoparticles (AuNPs) with the size of quantum dots into predictable structures is extremely challenging as it requires the quantitatively and topologically precise placement of anisotropic domains on their small, approximately spherical surfaces. We herein address this problem by using polyoxometalate leaving groups to transform 2 nm diameter gold cores into reactive building blocks with hydrophilic and hydrophobic surface domains whose relative sizes can be precisely tuned to give dimers, clusters, and larger micelle-like organizations. Using cryo-TEM imaging and ¹H DOSY NMR spectroscopy, we then provide an unprecedented “solution-state” picture of how the micelle-like structures respond to hydrophobic guests by encapsulating them within 250 nm diameter vesicles whose walls are comprised of amphiphilic AuNP membranes. These findings provide a versatile new option for transforming very small AuNPs into precisely tailored building blocks for the rational design of functional water-soluble assemblies.     

An Efficient Approach to Spirosesquiterrenes. Synthesis of (±)β-Vetivone.

(±)β-Vetivone and (±) 10-epi-β-vetivone have been synthesized in 6 steps via an efficient spiroannelation-functionalization sequence.     

The run-up of nonlinearly deformed sea waves on the coast of a bay with a parabolic cross-section

The run-up of long waves on the coast of a bay with a parabolic cross-section, where the region of constant depth along the principal axis of the bay is connected with the linearly inclined segment, is considered. The study is carried out analytically in the framework of the nonlinear shallow-water theory under the approximation that the height of the initial wave is small compared to the basin depth, and the reflection from the inflection point of the bottom is negligibly small. Three types of incident waves, viz., a sinusoidal wave and solitary waves of positive and negative polarities, are considered in detail. It is shown that a sinusoidal wave undergoes nonlinear deformation at a segment of constant depth faster than solitary waves of positive and negative polarities. Solitary waves of negative polarity steepen somewhat faster than solitary waves of positive polarity. Waves of positive polarity steepen at wave front, while waves of negative polarity steepen at wave rear. These differences in steepness may become crucial at the wave run-up stage, since the wave run-up height on the coast of a bay with a parabolic cross-section is directly proportional to the steepness of a wave that arrives at the slope and can lead to the anomalous run-up of waves on the coast.     

Functionalization of Polyethyleneimine with Hollow Cyclotriveratrylene and Its Subsequent Supramolecular Interaction with Doxorubicin

In this paper, a modified Cyclotriveratrylene was synthesized and linked to a branched Polyethylenimine, and this unique polymeric material was subsequently examined as a potential supramolecular carrier for Doxorubicin. Spectroscopic analysis in different solvents had shown that Doxorubicin was coordinated within the hollow-shaped unit of the armed Cyclotriveratrylene, and the nature of the host–guest complex revealed intrinsic Van der Waals interactions and hydrogen bonding between the host and guest. The strongest interaction was detected in water because of the hydrophobic effect shared between the aromatic groups of the Doxorubicin and Cyclotriveratrylene unit. Density functional theory calculations had also confirmed that in the most stable coordination of Doxorubicin with the cross-linked polymer, the aromatic rings of the Doxorubicin were localized toward the Cyclotriveratrylene core, while its aliphatic chains aligned closer with amino groups, thus forming a compact supramolecular assembly that may confer a shielding effect on Doxorubicin. These observations had emphasized the importance of supramolecular considerations when designing a novel drug delivery platform.     

Catalytic pyrolysis of propane-butane hydrocarbon mixture on the composite ceramic materials in an open system

Catalytic pyrolysis of propane-butane hydrocarbon mixture on the composite ceramic materials with the surface modified with zinc-, cadmium- phosphorus- and silicon-containing compounds in an open system was studied in the temperature range 500–850°C, at the rate of the gas mixture flow 20–200 ml min⁻¹, contact duration 0.75–155 s, and the values of the heterogeneity factor 2.0 to 2.9×10⁵ cm⁻¹. The catalytic activity of the systems under similar conditions was compared, the influence of various factors on the yield of ethylene and propylene was investigated and the sooting was estimated.     

Derivatization of peptides and small proteins for improved identification and detection in capillary zone electrophoresis (CZE)

Peptides and small proteins, of limited molecular weight (MW) can be derivatized with a 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (6-AQC) reagent, leading to a single capillary zone electrophoresis (CZE) peak, suggestive of a completely tagged product. The number of tags per molecule was demonstrated by matrix assisted, laser desorption, time-of-flight mass spectrometry (MALDI-TOFMS) studies. In CZE, these species have greatly improved plate count and peak shape, improved (lowered) detectabilities, and in general, improved identification properties in the CZE mode in high performance capillary electrophoresis (HPCE). The formation of what appears to be a single, homogeneously tagged product is a function of how the derivatizations are performed. Once these conditions are optimized, virtually all peptides and small proteins tested (limited MW) can form single, fully tagged products, with the desirable CZE properties. These derivatization approaches thus lead to products that perform and are detected much better in CZE than their precursors (native, untagged peptides). The determined plate counts for these tagged peptides were as high as 6 million plates/m, which was very reproducible, and 59–12,000 times higher than the untagged (native) molecules. The peak symmetry was also improved greatly. The limit of detection (LOD) of some tested 6-AQC tagged peptides were nine to 209 times improved (lower) with ultraviolet (UV) absorption detection, again as compared with that for the native species. The LOD could be further lowered via laser induced fluorescence (LIF) detection in CZE, especially when acetonitrile (ACN) containing buffers were used.     

Long Wave Run-up on Plane and “Non-Reflecting” Slopes

The long wave run-up on two types of slopes is investigated numerically within the framework of nonlinear shallow water theory using the CLAWPACK software. One of the slopes represents a plane slope widely used in the laboratory and numerical experiments; the second is the so-called “non-reflecting” slope (h ~ x^4/3, where h is the basin depth and x is the distance from the shoreline). In the case of very low wave amplitudes when there is no wave breaking, the run-up height is greater on the non-reflecting beach than that on the plane slope. As the wave amplitude increases, the breaking effects have the stronger impact in the case of non-reflecting beach and the run-up height becomes smaller.     

Untersuchung verschiedener Lebensmittel

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