Flavonoid constituents and free radical scavenging activity of Alchemilla mollis

Antioxidant capacity of the methanolic extract of Alchemilla mollis was measured by its ability to scavenge the DPPH radical. The EtOAc fraction obtained after partition of the total extract was found to be the most active radical scavenger (IC50 9.8 +/- 1.8 microg/mL) and was subjected to fractionation by Sephadex LH-20 CC. Further purification by RP-18 CC led to the isolation of eight flavonoid glycosides: cis- and trans-tiliroside (1 and 2), rhodiolgin (3), hyperoside (4), isoquercitrin (5), miquelianin (6), sinocrassoside D2 (7), and gossypetin-3-O-beta-D-galactopyranosyl-7-O-alpha-L-rhamnopyranoside (8). It was found that 8 is a new compound and its antioxidant activity is also reported. Identification of the isolated compounds was carried out by spectroscopic and spectrometric analysis (1D and 2D NMR, UV and MS).     

Protein–polymer hybrids: Conducting ARGET ATRP from a genetically encoded cleavable ATRP initiator

Protein–polymer hybrids are an important class of biomaterials. Described is the preparation of a genetically incorporated a non-canonical amino acid (nCAA) containing an ester linked atom transfer radical polymerization (ATRP) initiator, followed by a controlled “grafting from” polymerization. A Methanococcus jannaschii tyrosyl-tRNA synthetase/tRNA_CUA pair was selected to genetically encode p-bromoisobutyryloxymethyl-l-phenylalanine (biF) in response to an amber codon. This biF was directly incorporated into green fluorescent protein (GFP) at residue 134 generating biF-GFP. Activators regenerated by electron transfer (ARGET) ATRP was conducted under biologically relevant conditions to graft well-defined poly(oligo ethylene oxide methacrylate) from the biF-GFP. The biF-GFP retained its biofluorescence properties throughout the polymerization indicating the utility of ARGET ATRP for preparing protein–polymer hybrids. The presence of a base-labile ester bond in the initiator, allowed cleavage of the grafted polymer from the protein and directly analyze their molecular weight and molecular weight distribution using gel permeation chromatography (GPC). The cleaved final polymer had a M_n = 27,000 and a molecular weight distribution of M_w/M_n = 1.27.     

Synthesis of the new ring system pyrrolizino[2,3-b]indol-4(5H)-one

Derivatives of the new ring system pyrrolizino[2,3-b]indol-4(5H)-one were prepared in four steps starting from substituted benzonitriles bearing a functionalized amino group in the adjacent position. The unsubstituted- and the dimethoxy-pyrrolizinoindolones 5a and 5b exhibited modest activity against the HL-60(TB) human leukemia cell line, whereas the N-methylated dimethoxy-pyrrolizinoindolone 6b showed to be selective against MOLT-4 leukemia, A549/ATCC, HOP-92, and NCI-H460 non-small cell lung cancer, and CAKI-1 renal cancer cell lines.     

A Computational Quantum-Based Perspective on the Molecular Origins of Life’s Building Blocks

The search for the chemical origins of life represents a long-standing and continuously debated enigma. Despite its exceptional complexity, in the last decades the field has experienced a revival, also owing to the exponential growth of the computing power allowing for efficiently simulating the behavior of matter—including its quantum nature—under disparate conditions found, e.g., on the primordial Earth and on Earth-like planetary systems (i.e., exoplanets). In this minireview, we focus on some advanced computational methods capable of efficiently solving the Schrödinger equation at different levels of approximation (i.e., density functional theory)—such as ab initio molecular dynamics—and which are capable to realistically simulate the behavior of matter under the action of energy sources available in prebiotic contexts. In addition, recently developed metadynamics methods coupled with first-principles simulations are here reviewed and exploited to answer to old enigmas and to propose novel scenarios in the exponentially growing research field embedding the study of the chemical origins of life.     

Mapping the Distribution of Melanin Concentration in Different Fitzpatrick Skin Types Using Hyperspectral Imaging Technique

Measuring skin melanin concentration in order to assess skin phototype according to Fitzpatrick's classification is a constant research goal. In this study, a new approach for assessing skin melanin concentration based on hyperspectral imaging combined with an appropriate analytical model that exploits specific spectral bands to generate maps of melanin content distribution on different Fitzpatrick skin phototypes is presented. Hyperspectral images from the proximal inner side of the forearms of 51 young volunteers covering the first four classes of Fitzpatrick's phototypes were acquired using a hyperspectral imaging system. The images were analyzed using a modified Beer–Lambert law that segregates the contribution of melanin from the other constituents to the skin absorption spectrum. The performance of the model was evaluated using the coefficient of determination (r-squared). The results revealed that the approach proposed in this study generated accurate melanin concentration distribution maps that allowed a correct classification of skin phototype. In conclusion, the proposed approach for assessing skin melanin concentration proved to be very reliable for classifying skin phototypes, and, as it provides maps that are easily read, it has the advantage of a possible extension of its applications to other research concerning skin pigmentation.