Dual catalytic performance of arene-ruthenium amine complexes for norbornene ring-opening metathesis and methyl methacrylate atom-transfer radical polymerizations

Arene ruthenium(II) complexes bearing the cyclic amines RuCl₂(η⁶-p-cymene)(pyrrolidine)] ( 1 ), [RuCl₂(η⁶-p-cymene)(piperidine)] ( 2 ), and [RuCl₂(η⁶-p-cymene)(peridroazepine)] ( 3 ) were successfully synthesized. Complexes 1 – 3 were fully characterized by means of Fourier transform infrared, UV–visible, and NMR spectroscopy, elemental analysis, cyclic voltammetry, computational methods, and one of the complexes was further studied by single crystal X-ray crystallography. These compounds were evaluated as catalytic precursors for ring-opening metathesis polymerization (ROMP) of norbornene (NBE) and atom-transfer radical polymerization (ATRP) of methyl methacrylate (MMA). NBE polymerization via ROMP was evaluated using complexes 1 – 3 as precatalysts in the presence of ethyl diazoacetate (EDA) under different [NBE]/[EDA]/[Ru] ratios, temperatures (25 and 50°C), and reaction times (5–60 min). The highest yields of polyNBE were obtained with [NBE]/[EDA]/[Ru] = 5000/28/1 for 60 min at 50°C. MMA polymerization via ATRP was conducted using 1 – 3 as catalysts in the presence of ethyl-α-bromoisobutyrate (EBiB) as initiator. The catalytic tests were evaluated as a function of the reaction time using the initial molar ratio of [MMA]/[EBiB]/[Ru] = 1000/2/1 at 95°C. The increase in molecular weight as function of time indicates that complexes 1–3 were able to mediate the MMA polymerization with an acceptable rate and some level of control. Differences in the rate of polymerization were observed in the order 3 > 2 > 1 for the ROMP and ATRP.     

Highly Efficient α‐Sialylation by Virtue of Fixed Dipole Effects of N‐Phthalyl Group: Application to Continuous Flow Synthesis of α(2‐3)‐and α(2‐6)‐Neu5Ac‐Gal Motifs by Microreactor

Highly α‐selective sialylation of sialic acid N‐phenyltrifluoroacetimidate with various galactose and lactose acceptors has been achieved by introducing the C‐5 N‐phthalyl group on the donor. The “fixed dipole effect” of the N‐phthalyl group was proposed to explain the high reactivity and α‐selectivity. The microfluidic system was applied to the present α‐sialylation, which is amenable to large‐scale synthesis. The N‐phthalyl group was removed by treatment with methylhydrazine acetate, for which protocol can be readily applied to the synthesis of a variety of sialic acid‐containing oligosaccharides.      

The impact of the natural sciences on archaeology

This article reviews some of the applications of physics to the solution of archaeological problems. The use of magnetic, resistivity and electromagnetic surveying techniques for the location of buried features is described. Various methods of age determination are outlined while the problems associated with radiocarbon dating of organic material and thermoluminescent dating of pottery are discussed in detail. The techniques, including petrological examination, chemical analysis and isotopic analysis, employed in the physical examination of archaeological artefacts are described. Examples of the application of these techniques in establishing the source of the raw materials used in pottery, metal and stone implements and in elucidating the techniques of manufacture of pottery and metal objects are also given.     

Reductive coupling of hydantoins with benzophenones by low-valent titanium: Synthesis of 4-substituted 1H-imidazol-2(3H)-ones and unusual two-to-two coupled products

The reductive coupling of 1,3-dimethyhydantoin with benzophenones by TiCl₄-Zn in THF gave 4-diarylmethyl-1H-imidazol-2(3H)-ones as four-electron reduced one-to-one coupled products and their dimers as two-to-two coupled products predominantly by controlling the reaction conditions. The reductive coupling of 5-alkyl-1,3-dimethyhydantoins with benzophenones produced 5-alkyl-4-diarylmethyl-1H-imidazol-2(3H)-ones as the sole products irrespective to the reaction conditions. On the other hand, the reductive coupling of 1,3-dimethyhydantoin with cyclic benzophenones selectively 4-arylhydroxymethyl-1H-imidazol-2(3H)-ones as two-electron reduced one-to-one coupled products and they were further reduced to 4-diarylmethyl-1H-imidazol-2(3H)-ones.     

The photophysical determination of the minimum hydrotrope concentration of aromatic hydrotropes

A method based on the aggregate to monomol emission ratio, I(aggr)/I(monomol), was used to determine the minimal hydrotropic concentration (MHC) of aromatic hydrotropes. The main advantage of this method is that it does not require the use of probes or other additives, which might disrupt the aggregation process. Also, it relies on spectrophotometric measurements, which are more sensitive and less arduous than others, like conductivity, light scattering and surface tension.     

Phenolic compounds,essential oil composition,and antioxidant activity of Angelica purpurascens (Avé-Lall.) Gill

In this study, methanol extracts (MEs) and essential oil (EO) of Angelica purpurascens (Avé-Lall.) Gill obtained from different parts (root, stem, leaf, and seed) were evaluated in terms of antioxidant activity, total phenolics, compositions of phenolic compound, and essential oil with the methods of 2,2-azino-bis(3ethylbenzo-thiazoline-6-sulfonic acid (ABTS•⁺), 2,2-diphenyl-1-picrylhydrazil (DPPH•) radical scavenging activities, and ferric reducing/antioxidant power (FRAP), the Folin–Ciocalteu, liquid chromatography−tandem mass spectrometry (LC−MS/MS), and gas chromatography-mass spectrometry (GC−MS), respectively. The root extract of A. purpurascens exhibited the highest ABTS•⁺, DPPH•, and FRAP activities (IC₅₀: 0.05 ± 0.0001 mg/mL, IC₅₀: 0.06 ± 0.002 mg/mL, 821.04 ± 15.96 µM TEAC (Trolox equivalent antioxidant capacity), respectively). Moreover, EO of A. purpurascens root displayed DPPH• scavenging activity (IC₅₀: 2.95 ± 0.084 mg/mL). The root extract had the highest total phenolic content (438.75 ± 16.39 GAE (gallic acid equivalent), µg/mL)). Twenty compounds were identified by LC−MS/MS. The most abundant phenolics were ferulic acid (244.39 ± 15.64 μg/g extract), benzoic acid (138.18 ± 8.84 μg/g extract), oleuropein (78.04 ± 4.99 μg/g extract), and rutin (31.21 ± 2.00 μg/g extract) in seed, stem, root, and leaf extracts, respectively. According to the GC−MS analysis, the major components were determined as α-bisabolol (22.93%), cubebol (14.39%), α-pinene (11.63%), and α-limonene (9.41%) among 29 compounds. Consequently, the MEs and EO of A. purpurascens can be used as a natural antioxidant source.