Liquid Crystals Anchored on Mixed Monolayers of Chiral versus Achiral Molecules: Continuous Change in Orientation as a Function of Enantiomeric Excess

The orientations of liquid crystals (LCs) anchored on monolayers formed from mixtures of chiral versus achiral molecules were compared. Changes in the enantiomeric excess of mixed monolayers of chiral dipeptides gave rise to continuous changes in the orientations of nematic LCs, allowing arbitrary tuning of the azimuthal orientations of LCs over a range of ≈100°. In contrast, the same LCs exhibited discontinuous changes in orientation on surfaces presenting mixtures of achiral molecules. These striking differences in the anchoring of LCs on surfaces presenting chiral versus achiral molecules provide insights into the molecular origins of ordering transitions of LCs, and provide new principles based on chiral monolayers for the rational design of surfaces that permit continuous tuning of the orientations of LCs.     

Theoretical Study of the Interactions between Isolated <Emphasis Type="Italic">DNA</Emphasis> Bases and Various Groups IA and IIA Metal Ions by <Emphasis Type="Italic">Ab Initio</Emphasis> Calculations

Summary. Interactions of the DNA bases adenine (A), guanine (G), cytosine (C), and thymine (T) with various metal ions (M) of groups IA and IIA of the periodic table of the elements were studied at the HF, MP2, and DFT levels of theory. The structures and thermodynamic stabilities of these species were studied at the gas phase. The calculations uphold that there exist two active sites in G and one in A, C, and T. The calculations also show that the O² atom in T is a more active site for metal ion bindings than that in C. The stability energies for G … M complexes are larger than those for A … M complexes and the stability energies for T … M complexes are larger than those for C … M complexes. As z/r ratio for the metal ion increases, the interaction energy for the complex increases systematically. Thermodynamic quantities such as ΔH, ΔG, ΔS, and ln K were determined for each complexation reaction, [Base+M ⁿ⁺ →(Base … M) ⁿ⁺]. A, G, and C complexation reactions except for C … Rb⁺ are exothermic. The situation is quite different for T complexation reactions and all except for T … Be²⁺ and T … Mg²⁺ are endothermic.     

Real-Time pH-Dependent Self-Assembly of Ionisable Lipids from COVID-19 Vaccines and In Situ Nucleic Acid Complexation

Ionisable amino-lipid is a key component in lipid nanoparticles (LNPs), which plays a crucial role in the encapsulation of RNA molecules, allowing efficient cellular uptake and then releasing RNA from acidic endosomes. Herein, we present direct evidence for the remarkable structural transitions, with decreasing membrane curvature, including from inverse micellar, to inverse hexagonal, to two distinct inverse bicontinuous cubic, and finally to a lamellar phase for the two mainstream COVID-19 vaccine ionisable ALC-0315 and SM-102 lipids, occurring upon gradual acidification as encountered in endosomes. The millisecond kinetic growth of the inverse cubic and hexagonal structures and the evolution of the ordered structural formation upon ionisable lipid-RNA/DNA complexation are quantitatively revealed by in situ synchrotron radiation time-resolved small angle X-ray scattering coupled with rapid flow mixing. We found that the final self-assembled structural identity, and the formation kinetics, were controlled by the ionisable lipid molecular structure, acidic bulk environment, lipid compositions, and nucleic acid molecular structure/size. The implicated link between the inverse membrane curvature of LNP and LNP endosomal escape helps future optimisation of ionisable lipids and LNP engineering for RNA and gene delivery.     

Gibberellic Acid Increases Secondary Metabolite Production in Echinacea purpurea Hairy Roots

Gibberellic acid (GA₃) is reported to have diverse effects on hairy root cultures of many plant species; therefore, the effects of GA₃ on the growth, secondary metabolite production (caffeic acid derivatives and lignin), phenylalanine ammonia lyase (PAL) activity, and free radical scavenging activity of light-grown Echinacea purpurea L. hairy roots were investigated. Eight concentrations of GA₃, ranging from 0.005 to 1.0 μM, were added to shake flask cultures. The moderate GA₃ concentration, 0.025 μM, resulted in the highest concentrations of cichoric acid, caftaric acid, and chlorogenic acid, as well as increased PAL activity, cell viability, and free radical scavenging activity, while higher and lower GA₃ concentrations resulted in reduced levels compared to the control (lacking GA₃). The moderate GA₃ concentration also affected root morphogenesis; supplementation with 0.025 μM GA₃ resulted in the development of thick, dense, purple-colored roots, while roots exposed to the higher and lower concentrations of GA₃ were thin and off-white. This study demonstrates that supplementation with GA₃ may be an excellent strategy to optimize the production of secondary metabolites from E. purpurea hairy root cultures; however, the GA₃ concentration is a critical factor.     

Liquid–liquid extraction of scandium with nalidixic acid in dichloromethane

The extraction behavior of nalidixic acid (HNA) in CH₂Cl₂ has been studied for various di- and trivalent metal ions such as Cu(II), Fe(II), Ni(II), Mn(II), Sb(II), Co(II), Sc(III), Y(III), Nd(III) and Eu(III) from aqueous buffer solutions of pH 1–7 with 0.1 mol dm⁻³ nalidixic acid in dichloromethane. Separation factors of Sc(III) from these metals has shown that its clean separation is possible at pH 3.4–4. The parameters affecting the extraction of Sc(III) were optimized. The composition of the extracted adduct was determined by slope analysis method that came out to be Sc(NA)₃. Extraction of Sc(III) was studied in the presence of various cations and anions. Among the anions studied only fluoride, citrate and oxalate have significant interference whereas, Fe(III) has reduced the extraction to 53% that can be removed by using ascorbic acid as reducing agent. The proposed extraction system proved good stability up to six extraction-stripping stages for the extraction of Sc(III).     

An investigation into the role of polarity of diamines in controlling the electron migration mechanism of photoluminescent poly(amide–imide)s

Several diamines with remarkable different polarities were used to produce photoactive poly(amide–imide)s (PAI)s in a quantitative yield. The absorption, fluorescence and photophysical properties of series of poly(amide–imide)s containing fused aromatic systems as energy donor and energy acceptor with different diamines cores are described. Poly(amide–imide)s exhibit broad fluorescent characteristic, and its fluorescent intensity is related to the intermolecular chain–chain or chain–solvent interaction. The fluorescence spectra confirmed an efficient singlet–singlet energy transfer between fused aromatic systems. The self-quenching mechanism was studied according to the specific behavior of these polymers in different solvents. The self-quenching rate constant for the association reaction in the excited state (Kq) could be measured from the Stern–Volmer equation. The kind of fused system and diamines show different electron migration mechanisms and photoluminescent properties in the singlet-excited states. By using the exothermic energy transfer as a function of diamine polarity, the electron transfer mechanism was evaluated for aromatic poly(amide–imide)s. In principle, the fluorescence energy is absorbed by different (PAI)s and raises the molecules to one of its excited states. Afterwards this excitation energy transfers through the different relaxation channels, i.e. columbic or exchange energy transfer.     

Dense coating of surface mounted CuBTC Metal-Organic Framework nanostructures on silk fibers, prepared by layer-by-layer method under ultrasound irradiation with antibacterial activity

The growth of Cu₃(BTC)₂ (BTC = 1,3,5-benzenetricarboxylate), also known as CuBTC and HKUST-1, Metal-Organic Framework (MOF) nanostructures on silk fibers were achieved by layer-by-layer technique in alternating bath of Cu(OAc)₂·2H₂O and H₃BTC solutions under ultrasound irradiation. The effect of pH, reaction time, ultrasound irradiation and sequential dipping steps in growth of the CuBTC Metal-Organic Framework nanostructures has been studied. These systems depicted a decrease in the size accompanying a decrease in the sequential dipping steps. In addition, dense coating of silk fibers with CuBTC MOF results in decrease the emission intensity of silk fibers. The silk fibers containing CuBTC Metal-Organic Framework exhibited high antibacterial activity against Escherichia coli and Staphylococcus aureus. The samples were characterized with powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) spectra and scanning electron microscopy (SEM). XRD analyses indicated that the prepared CuBTC MOF nanostructures on silk fibers were crystalline.     

Ultrasound-assisted coating of polyester fiber with silver bromide nanoparticles

The growth of silver bromide nanoparticles on polyester fiber was achieved by sequential dipping steps in alternating bath of potassium bromide and silver nitrate under ultrasound irradiation. The effects of ultrasound irradiation, concentration and sequential dipping steps in growth of the AgBr nanoparticles have been studied. Particle sizes and morphology of nanoparticle are depending on power of ultrasound irradiation, sequential dipping steps and concentration. These systems depicted a decrease in the particles size accompanying an increase in the sonication power. Results suggest that an increasing of sequential dipping steps and concentration led to an increasing of particle size. The physicochemical properties of the nanoparticles were determined by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM).     

Synthesis and characterization of Ag nanoparticles@Polyethylene fibers under ultrasound irradiation

The polyethylene fibers containing Ag nanoparticles were prepared through the chemical reduction under ultrasound irradiation. The effect of reducing reagent, power of ultrasound irradiation, reaction time and temperature in growth of the nanometric Ag were studied. Particle sizes and morphology of nanoparticle are depending on power of ultrasound irradiation. Results show a decrease in the particles size as increasing power of ultrasound irradiation. Also, an increase in temperature led to increase of particle size. The polyethylene fibers containing Ag nanoparticles were characterized with powder X-ray diffraction (XRD) and scanning electron microscopy (SEM).