New Triterpenoid and Ergostane Glycosides from the Leaves of Hydrocotyle umbellata L.

Two new triterpenoid glycosides, together with two new ergostane glycosides, umbellatosides A–D ( 1 – 4 , resp.), have been isolated from the leaves of Hydrocotyle umbellata L. Their structures were established by 2D‐NMR spectroscopic techniques (¹H,¹H‐COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry as 3β,22β‐dihydroxy‐3‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucuronopyranosyl]olean‐12‐en‐28‐oic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 1 ), 3‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucuronopyranosyl]oleanolic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 2 ), (3β,11α,26)‐ergosta‐5,24(28)‐diene‐3,11,26‐triol 3‐O‐(β‐D ‐glucopyranosyl)‐11‐O‐(α‐L ‐rhamnopyranosyl)‐26‐O‐β‐D ‐glucopyranoside ( 3 ), and (3β,11α,21,26)‐ergosta‐5,24(28)‐diene‐3,11,21,26‐tetrol 3‐O‐(β‐D ‐glucopyranosyl)‐11‐O‐(α‐L ‐rhamnopyranosyl)‐26‐O‐β‐D ‐glucopyranoside ( 4 ).     

Aerosol-assisted self-assembly of hybrid Layered Double Hydroxide particles into spherical architectures

Over the last decade, the use of nanocellulose in advanced technological applications has been promoted both due the excellent properties of this material in combination with its renewability. In this study, multilayered thin films composed of nanofibrillated cellulose (NFC), polyvinyl amine (PVAm) and silica nanoparticles were fabricated on polydimethylsiloxane (PDMS) using a layer-by-layer adsorption technique. The multilayer build-up was followed in situ by quartz crystal microbalance with dissipation, which indicated that the PVAm-SiO(2)-PVAm-NFC system adsorbs twice as much wet mass material compared to the PVAm-NFC system for the same number of bilayers. This is accompanied with a higher viscoelasticity for the PVAm-SiO(2)-PVAm-NFC system. Ellipsometry indicated a dry-state thickness of 2.2 and 3.4 nm per bilayer for the PVAm-NFC system and the PVAm-SiO(2)-PVAm-NFC system, respectively. Atomic force microscopy height images indicate that in both systems, a porous network structure is achieved. Young's modulus of these thin films was determined by the Strain-Induced Elastic Buckling Instability for Mechanical Measurements (SIEBIMM) technique. The Young's modulus of the PVAm/NFC films was doubled, from 1 to 2 GPa, upon incorporation of silica nanoparticles in the films. The introduction of the silica nanoparticles lowered the refractive index of the films, most probably due to an increased porosity of the films.     

The reduction of Ag+ in metallic silver on pseudomelanin films allows for antibacterial activity but does not imply unpaired electrons

Dopamine-melanin films produced through the oxidation of dopamine in the presence of oxygen as an oxidant allow to reduce silver ions onto silver particles as already described in the paper by Lee et al. (H. Lee, S.M. Dellatore, W.M. Miller, P.B. Messersmith, Science 318 (2007) 426.). This reduction process has to occur through the oxidation of moieties present in the melanin film. This investigation shows that the free radicals present in the pseudomelanin film, quantified by means of electron spin resonance spectroscopy (ESR) for the first time, are not used in the transformation of Ag(+) cations to deposit silver. The ESR signal is hardly affected by the deposition of silver particles. On the other hand, X-ray photoelectron spectroscopy shows a small increase in the density of quinone groups and a small decrease of catechol groups on the surface of the film during the deposition of silver. This suggests that the deposited pseudomelanin films contain a significant fraction of catechol groups able to trigger reduction processes of metallic cations. These silver nanoparticles remain adherent to the melanin films and allow for a quantitative killing of Escherichia coli over a broad range of bacterial dilutions. However, the presence of the bacteria induces a release of the nanoparticles. The pseudomelanin films cannot be reused again for a silver ion reduction step. Nevertheless, the easy preparation of the pseudomelanin-silver composite and its effective one shot bacterial killing activity renders the strategy presented in this paper attractive. Some fundamental questions about redox process allowed by the pseudomelanin films will also be asked.     

Synthetic and structural studies of donor-functionalized alkoxy derivatives of gallium

The synthesis of a range of alkyl/chloro-gallium alkoxide and amido/alkoxide compounds was achieved via a series of protonolysis and alcoholysis steps. The initial reaction involved the synthesis of [Me(Cl)Ga{N(SiMe(3))(2)}](2) (1) via methyl group transfer from the reaction of GaCl(3) with two equivalents of LiN(SiMe(3))(2). Reaction of 1 with varying amounts of ROH resulted in the formation of [Me(Cl)Ga(OR)](2) (2, R = CH(2)CH(2)OMe; 3, CH(CH(3))CH(2)NMe(2)), [Me(Cl)Ga{N(SiMe(3))(2)}(μ(2)-OR)Ga(Cl)Me] (4, R = CH(2)CH(2)NMe(2)), or [MeGa(OR)(2)] (5, R = CH(CH(3))CH(2)NMe(2)). Compound 4 represents an intermediate in the formation of dimeric complexes, of the type [Me(Cl)Ga(OR)](2), when formed from compound [Me(Cl)Ga{N(SiMe(3))(2)}](2). A methylgallium amido/alkoxide complex [MeGa{N(SiMe(3))(2)}(OCH(2)CH(2)OMe)](2) (6) was isolated when 2 was further reacted with LiN(SiMe(3))(2). In addition, reaction of 2 with HO(t)Bu resulted in a simple alcohol/alkoxide exchange and formation of [Me(Cl)Ga(O(t)Bu)](2) (7). In contrast to the formation of 1, the in situ reaction of GaCl(3) with one equivalent of LiN(SiMe(3))(2) yielded [Cl(2)Ga{N(SiMe(3))(2)}](2) in low yield, where no methyl group transfer has occurred. Reaction of alcohol with [Cl(2)Ga{N(SiMe(3))(2)}](2) was then found to yield [Cl(2)Ga(OR)](2) (8, R = CH(2)CH(2)NMe(2)), and further reaction of 8 with LiN(SiMe(3))(2) yielded the gallium amido alkoxide complex, [ClGa{N(SiMe(3))(2)}(OR)](2) (9, R = CH(2)CH(2)NMe(2)), similar to 6. The structures of compounds 4, 5, 7, and 8 have been determined by single-crystal X-ray diffraction.     

Addition of N-heterocyclic carbenes to a ruthenium(VI) nitrido polyoxometalate: a new route to cyclic guanidines

The scope of N-atom transfer from the electrophilic ruthenium(VI) nitrido containing polyoxometalate [PW(11)O(39)Ru(VI)N](4-) has been extended to the N-heterocyclic carbene {CH(2)(Mes)N}(2)C and the coupling product {CH(2)(Mes)N}(2)CNH(2)(+) characterized by (1)H NMR and high-resolution mass spectrometry. Because guanidines display many fields of applications ranging from biology to supramolecular chemistry, this could afford an original route to the synthesis of cyclic guanidines. This also enlarges the potential of nitrido complexes in the synthesis of heterocycles, mainly illustrated in the literature through the formation of aziridines through N-atom transfer to alkenes. In the course of the reaction, the ruthenium(III)-containing polyoxometallic intermediate [PW(11)O(39)Ru(III){NC{N(Mes)CH(2)}(2)}](5-) has been thoroughly characterized by continuous-wave and pulsed electron paramagnetic resonance, which nicely confirms the presence of the organic moiety on the polyoxometallic framework, Ru K-edge X-ray absorption near-edge structure, and electrochemistry.     

Asymmetric synthesis of (+)-galbelgin, (-)-kadangustin J, (-)-cyclogalgravin and (-)-pycnanthulignenes A and B, three structurally distinct lignan classes, using a common chiral precursor

The enantioselective synthesis of three structurally distinct classes of lignan from a single, aza-Claisen-derived, chiral morpholine amide is reported. The class of lignan formed is dependent on the substitution pattern in the aryl rings and choice of protecting group on a key benzylic hydroxyl group. The methodology has been used to asymmetrically synthesize and determine the absolute stereochemistry of lignans (+)-cyclogalgravin 3, (-)-pycnanthulignene A 4, (-)-pycnanthulignene B 5, and (-)-kadangustin J 8.     

Zn, Ti and Si nanowires by electrodeposition in ionic liquid

An electrochemical route for the fabrication of zinc, titanium and silicon nanowires from ionic liquid (IL) based plating solutions is presented. Thanks to the large potential window of IL and good solubility of the corresponding anhydrous chloride salts, the presented method proceeds by a kinetically controlled electrochemical decoration of step-edges at highly oriented pyrolytic graphite surface. Resulting rather crystalline nanowires are more than a few hundreds of μm long while their diameter can be controlled in the 10 to 100 nm range by the electrolysis duration.     

Generation, characterisation, and applications of atomic and molecular alignment and orientation

The gas phase is generally defined as a state of matter in which atoms or molecules are in constant, rapid, random Brownian motion. However, a range of techniques exist for preparing distributions of gas phase atoms and molecules whose motion is far from random, and whose orientation in space is well defined. In this Perspective, we will explore the nature of atomic and molecular alignment and orientation, the various techniques by which samples of spatially oriented species may be prepared and characterised, and some of the ways in which oriented molecules are being exploited to further our knowledge of molecular structure and dynamics.     

The ubiquity of generalized cluster categories

Associated with a finite-dimensional algebra of global dimension at most 2, a generalized cluster category was introduced in Amiot (2009) [1]. It was shown to be triangulated, and 2-Calabi–Yau when it is Hom-finite. By definition, the cluster categories of Buan et al. (2006) [4] are a special case. In this paper we show that a large class of 2-Calabi–Yau triangulated categories, including those associated with elements in Coxeter groups from Buan et al. (2009) [7], are triangle equivalent to generalized cluster categories. This was already shown for some special elements in Amiot (2009) [1].     

Sharp Hölder continuity of the Lyapunov exponent of finitely differentiable quasi-periodic cocycles

Mathematische Zeitschrift - We show that if the base frequency is Diophantine, then the Lyapunov exponent of a $$C^{k}$$ quasi-periodic $$SL(2,{\mathbb {R}})$$ cocycle is...