Programmed Recognition between Complementary Dinucleolipids To Control the Self-Assembly of Lipidic Amphiphiles

One of the major goals in systems chemistry is to create molecular assemblies with emergent properties that are characteristic of life. An interesting approach toward this goal is based on merging different biological building blocks into synthetic systems with properties arising from the combination of their molecular components. The covalent linkage of nucleic acids (or their constituents: nucleotides, nucleosides and nucleobases) with lipids in the same hybrid molecule leads, for example, to the so-called nucleolipids. Herein, we describe nucleolipids with a very short sequence of two nucleobases per lipid, which, in combination with hydrophobic effects promoted by the lipophilic chain, allow control of the self-assembly of lipidic amphiphiles to be achieved. The present work describes a spectroscopic and microscopy study of the structural features and dynamic self-assembly of dinucleolipids that contain adenine or thymine moieties, either pure or in mixtures. This approach leads to different self-assembled nanostructures, which include spherical, rectangular and fibrillar assemblies, as a function of the sequence of nucleobases and chiral effects of the nucleolipids involved. We also show evidence that the resulting architectures can encapsulate hydrophobic molecules, revealing their potential as drug delivery vehicles or as compartments to host interesting chemistries in their interior.     

Tuning percolation speed in layer-by-layer assembled polyaniline–nanocellulose composite films

Polyaniline of low molecular weight (ca. 10 kDa) is combined with cellulose nanofibrils (sisal, 4–5 nm average cross-sectional edge length, with surface sulphate ester groups) in an electrostatic layer-by-layer deposition process to form thin nano-composite films on tin-doped indium oxide (ITO) substrates. AFM analysis suggests a growth in thickness of ca. 4 nm per layer. Stable and strongly adhering films are formed with thickness-dependent coloration. Electrochemical measurements in aqueous H₂SO₄ confirm the presence of two prominent redox waves consistent with polaron and bipolaron formation processes in the polyaniline–nanocellulose composite. Measurements with a polyaniline–nanocellulose film applied across an ITO junction (a 700 nm gap produced by ion beam milling) suggest a jump in electrical conductivity at ca. 0.2 V vs. SCE and a propagation rate (or percolation speed) two orders of magnitude slower compared to that observed in pure polyaniline This effect allows tuning of the propagation rate based on the nanostructure architecture. Film thickness-dependent electrocatalysis is observed for the oxidation of hydroquinone.

     

Electrical and interface characteristics of nanocrystalline n-Zn0.5Cd0.5S/p-Cu2S heterojunction structure prepared by dip coating

Nanocrystalline of n-Zn_0.5Cd_0.5S/p-Cu₂S heterojunctions were successfully prepared by the dip coating method. The surface morphology and the composition analysis were made by scanning electron microscopy (SEM) and energy dispersive x-ray (EDX) technique, respectively. Temperature dependent current–voltage characteristics of the heterojunctions were measured in the temperature range 300–400 K with a step of 25 K. The current–voltage (I–V) characteristics exhibit electrical rectification behavior. The zero bias barrier height (Φ_B0) and the ideality factor (n) are affected by temperature. Interface states at the n-Zn_0.5Cd_0.5S/p-Cu₂S heterojunction play a crucial role in determining the electrical characteristics of the heterojunction. The high value of n can be ascribed to the presence of an interfacial layer. The energy distribution profile of the density of interface states (N_ss) was extracted from the forward bias I–V measurements using the width of the depletion region deduced from the capacitance -voltage characteristics at high frequency (1MHz).     

Cationic Carbosilane Dendritic Systems as Promising Anti-Amyloid Agents in Type 2 Diabetes

The most common denominator of many of the neurodegenerative diseases is badly folded protein accumulation, which results in the formation of insoluble protein deposits located in different parts of the organism, causing cell death and tissue degeneration. Dendritic systems have turned out to be a promising new therapeutic approach for the treatment of these diseases due to their ability to modulate the folding of these proteins. With this perspective, and focused on type 2 diabetes (T2D), characterized by the presence of deposits containing the amyloidogenic islet amyloid polypeptide (IAPP), we demonstrate how different topologies of cationic carbosilane dendrimers inhibit the formation of insoluble protein deposits in pancreatic islets isolated from transgenic Tg-hIAPP mice. Also, the results obtained by the modification of dendritic carbosilane wedges with the chemical chaperone 4-phenylbutyric acid (4-PBA) at the focal point confirmed their potential as anti-amyloid agents with a concentration efficiency in their therapeutic action five orders of magnitude lower than that observed for free 4-PBA. Computational studies, which determined the main interaction between IAPP and dendrimers at the atomic level, support the experimental work.     

Green synthesis and characterization of silver nanoparticles using Juniperus communis leaf extract: Catalytic activity in real-outdoor conditions and electrochemical properties

The present study investigates the green synthesis of stable silver nanoparticles using Juniperus communis leaf aqueous extract at room temperature. Synthesized silver nanoparticles (AgNPs) were characterized with different techniques such as UV–vis spectroscopy, Fourier transforms infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), Scanning electron microscopy (SEM-EDAX) and electrochemical method. Photocatalytic and anti-bacterial activities of synthesized AgNPs are evaluated based on the obtained result showed an efficient inhibition growth for gram negative P. Aeruginosa, E. Coli, and gram positive bacteria S.aureus. The AgNPs exhibited an excellent photocatalytic activity toward the degradation of methylene blue both indoor and outdoor, under sunlight, an efficiency of 95% was achieved. As an easy and environmentally friendly process, AgNPs based on Juniperus communis leaf extract could be applied for the degradation of pollutants and wastewater treatment.     

Gold-Catalyzed Regiospecific Annulation of Unsymmetrically Substituted 1,5-Diynes for the Precise Synthesis of Bispentalenes

Precise control of the selectivity in organic synthesis is important to access the desired molecules. We demonstrate a regiospecific annulation of unsymmetrically substituted 1,2-di(arylethynyl)benzene derivatives for a geometry-controlled synthesis of linear bispentalenes, which is one of the promising structures for material science. A gold-catalyzed annulation of unsymmetrically substituted 1,2-di(arylethynyl)benzene could produce two isomeric pentalenes, but both electronic and steric effects on the aromatics at the terminal position of the alkyne prove to be crucial for the selectivity; especially a regiospecific annulation was achieved with sterically blocked substituents; namely, 2,4,6-trimetyl benzene or 2,4-dimethyl benzene. This approach enables the geometrically controlled synthesis of linear bispentalenes from 1,2,4,5-tetraethynylbenzene or 2,3,6,7-tetraethynylnaphthalene. Moreover, the annulation of a series of tetraynes with a different substitution pattern regioselectively provided the bispentalene scaffolds. A computational study revealed that this is the result of a kinetic control induced by the bulky NHC ligands.