Proto‐Urea‐RNA (Wöhler RNA) Containing Unusually Stable Urea Nucleosides

The RNA world hypothesis assumes that life on Earth began with nucleotides that formed information‐carrying RNA oligomers able to self‐replicate. Prebiotic reactions leading to the contemporary nucleosides are now known, but their execution often requires specific starting materials and lengthy reaction sequences. It was therefore proposed that the RNA world was likely proceeded by a proto‐RNA world constructed from molecules that were likely present on the early Earth in greater abundance. Herein, we show that the prebiotic starting molecules bis‐urea (biuret) and tris‐urea (triuret) are able to directly react with ribose. The urea‐ribosides are remarkably stable because they are held together by a network of intramolecular, bifurcated hydrogen bonds. This even allowed the synthesis of phosphoramidite building blocks and incorporation of the units into RNA. Investigations of the nucleotides’ base‐pairing potential showed that triuret:G RNA base pairs closely resemble U:G wobble base pairs. Based on the probable abundance of urea on the early Earth, we postulate that urea‐containing RNA bases are good candidates for a proto‐RNA world.     

Biocatalytic Strategies towards [4+2] Cycloadditions

Long sought after [4+2] cyclases have sprouted up in numerous biosynthetic pathways in recent years, raising hopes for biocatalytic solutions to cycloaddition catalysis, an important problem in chemical synthesis. In a few cases, detailed pictures of the inner workings of these catalysts have emerged, but intense efforts to gain deeper understanding are underway by means of crystallography and computational modelling. This Minireview aims to shed light on the catalytic strategies that this highly diverse family of enzymes employs to accelerate and direct the course of [4+2] cycloadditions with reference to small-molecule catalysts and designer enzymes. These catalytic strategies include oxidative or reductive triggers and lid-like movements of enzyme domains. A precise understanding of natural cycloaddition catalysts will be instrumental for customizing them for various synthetic applications.     

Synergistic Surface Passivation of CH3NH3PbBr3 Perovskite Quantum Dots with Phosphonic Acid and (3-Aminopropyl)triethoxysilane

CH₃NH₃PbBr₃ perovskite quantum dots (PQDs) are synthesized by using four different linear alkyl phosphonic acids (PAs) in conjunction with (3-aminopropyl)triethoxysilane (APTES) as capping ligands. The resultant PQDs are characterized by means of XRD, TEM, Raman spectroscopy, FTIR spectroscopy, UV/Vis, photoluminescence (PL), time-resolved PL, and X-ray photoelectron spectroscopy (XPS). PA chain length is shown to control the PQD size (ca. 2.9–4.2 nm) and excitonic absorption band positions (λ=488–525 nm), with shorter chain lengths corresponding to smaller sizes and bluer absorptions. All samples show a high PL quantum yield (ca. 46–83 %) and high PL stability; this is indicative of a low density of band gap trap states and effective surface passivation. Stability is higher for smaller PQDs; this is attributed to better passivation due to better solubility and less steric hindrance of the shorter PA ligands. Based on the FTIR, Raman, and XPS results, it is proposed that Pb²⁺ and CH₃NH₃⁺ surface defects are passivated by R−PO₃²⁻ or R−PO₂(OH)⁻, whereas Br⁻ surface defects are passivated by R−NH₃⁺ moieties. This study establishes the combination of PA and APTES ligands as a highly effective dual passivation system for the synergistic passivation of multiple surface defects of PQDs through primarily ionic bonding.     

Multisegmented one-dimensional nanorods prepared by hard-template synthetic methods

In the science and engineering communities, the nanoscience revolution is intensifying. As many types of nanomaterials are becoming more reliably synthesized, they are being used for novel applications in all branches of nanoscience and nanotechnology. Since it is sometimes desirable for single nanomaterials to perform multiple functions simultaneously, multicomponent nanomaterials, such as core-shell, alloyed, and striped nanoparticles, are being more extensively researched. Nanoscientists hope to design multicomponent nanostructures and exploit their inherent multiple functionalities for use in many novel applications. This review highlights recent advances in the synthesis of multisegmented one-dimensional nanorods and nanowires with metal, semiconductor, polymer, molecular, and even gapped components. It also discusses the applications of these multicomponent nanomaterials in magnetism, self-assembly, electronics, biology, catalysis, and optics. Particular emphasis is placed on the new materials and devices achievable using these multicomponent, rather than single-component, nanowire structures.     

Understanding adsorption phenomena: investigation of the dye-cellulose interaction

To understand the structural factors that control the adsorption of acid dyes onto cotton (cellulose), the adsorption of 15 acid dyes from water has been studied. An equilibrium exists between dye adsorbed in the cotton and dye in solution, and by measurement of the temperature dependence (277-333K) of the equilibrium constant, the enthalpy and entropy of binding are obtained. For most dyes adsorption is driven by the binding enthalpy, which is ascribed to van der Waals forces. Acid dyes consist of an aromatic core with peripheral solubilizing groups (generally sulfonates). Dyes in which the sulfonates are on one side of the molecule have the largest binding enthalpy. Assuming a binding geometry where the sulfonates protrude into water pools in the bulk amorphous regions and as much as possible of the dye core touches the surface, then a good correlation exists between the binding enthalpy and the summation of 1/r(6) over all the C, N, and O dye atoms, where r is the distance of each atom from the cellulose surface.     

Dithiolene transfer from nickel to a dimolybdenum centre: the first dithiolene alkyne complex

Transfer of dithiolene ligands from [Ni(S₂C₂Ph₂)₂] to the dimolybdenum complex [Mo₂(μ-C₂R₂)(CO)₄Cp₂] (R=CO₂Me, Cp=η-C₅H₅) affords the first example of a dithiolene alkyne complex, [Mo₂(μ-C₂R₂)(μ-S₂C₂Ph₂)₂Cp₂], together with [Mo₂(μ-SCRCR)(μ-SCPhCPh)Cp₂] in which sulfur transfer from dithiolene to alkyne has occurred.     

The structural characteristics of organozinc complexes incorporating N,N'-bidentate ligands

Dimethylzinc reacts with an excess of N-2-pyridylaniline 6 to give the homoleptic species, Zn[PhN(2-C(5)H(4)N)](2) 8. Single crystal X-ray diffraction reveals a solid-state dimer based on an 8-membered (NCNZn)(2) core motif. Zn[CyN(2-C(5)H(4)N)]Me (Cy =c-C(6)H(11)) 10, prepared by the combination of ZnMe(2) with the corresponding cyclohexyl-substituted pyridylamine, is also dimeric in the solid state but reveals a central (ZnN)(2) metallacycle. Employment of (p-Tol)NH(2-C(5)H(4)N)(p-Tol = 4-MeC(6)H(4)) 11 yielded the tris(zinc) adduct Zn(3)[(p-Tol)N(2-C(5)H(4)N)](4)Me(2) 12, which incorporates a central chiral molecule of 'Zn[(p-Tol)N(2-C(5)H(4)N)](2)' 12a, that bridges two 'Zn[(p-Tol)N(2-C(5)H(4)N)]Me' 12b units. A similar trimetallic structure is noted when the pyridylaniline substrate 11 is replaced with the bicyclic guanidine 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH), affording Zn(3)(hpp)(4)Me(2) 13. Spectroscopic studies point to retention of the solid-state structure of in hydrocarbon solution. Reaction of 13 with dimesityl borinic acid, Mes(2)BOH (Mes = mesityl), affords Zn(3)(hpp)(4)(OBMes(2))(2) 14 in which the trimetallic core is retained. This reactivity is in contrast to the closely related reaction of dimeric Zn[Me(2)NC[N(i)Pr](2)]Me 15 with Mes(2)BOH, which yielded Zn[Me(2)NC[N(i)Pr](2)][OBMes(2)].Me(2)NC[N(i)Pr][NH(i)Pr] 16 as a result of protonation at the guanidine ligand in addition to the Zn-Me bond.     

Study of Nb2O(y) (y = 2-5) anion and neutral clusters using anion photoelectron spectroscopy and density functional theory calculations

A study combining anion photoelectron spectroscopy and density functional theory calculations on the transition metal suboxide series, Nb(2)O(y)(-) (y = 2-5), is described. Photoelectron spectra of the clusters are obtained, and Franck-Condon simulations using calculated anion and neutral structures and frequencies are used to evaluate the calculations and assign transitions observed in the spectra. The spectra, several of which exhibit partially resolved vibrational structure, show an increase in electron affinity with increasing cluster oxidation state. Hole-burning experiments suggest that the photoelectron spectra of both Nb(2)O(2)(-) and Nb(2)O(3)(-) have contributions from more than one structural isomer. Reasonable agreement between experiment and computational results is found among all oxides.     

Effects of blue light irradiation on human dermal fibroblasts

Previous studies have reported that separately from UV-radiation also blue light influences cellular physiology in different cell types. However, little is known about the blue light action spectrum. The purpose of this study was to investigate effects of blue light at distinct wavelengths (410, 420, 453, 480 nm) emitted by well defined light-emitting-diodes on viability, proliferation and antioxidative capacity of human dermal fibroblasts. We found that irradiation with blue light (410, 420 nm) led to intracellular oxidative stress and toxic effects in a dose and wavelength dependent manner. No toxicity was observed using light at 453 nm and 480 nm. Furthermore, blue light (410, 420, 453 nm) at low doses reduced the antioxidative capacity of fibroblasts. At non-toxic doses, irradiations at 410, 420 and 453 nm reduced proliferation indicating a higher susceptibility of proliferating fibroblasts to blue light. Our results show that blue light at different wavelengths may induce varying degrees of intracellular oxidative stress with different physiological outcome, which could contribute to premature skin photoaging. On the other hand, the use of blue light due to its antiproliferative and toxic properties may represent a new approach in treatment and prevention of keloids, hypertrophic scars and fibrotic skin diseases.