Structural elucidation of new ferulic acid-containing phenolic dimers and trimers isolated from maize bran

Four new phenolic dimers and trimers that contain ferulic acid moieties were isolated from the alkaline hydrolyzate of insoluble maize bran fiber and their structures were established by 1D/2D NMR and mass spectrometry. The biological role of one dimer remains unclear whereas the dimeric vanillin-ferulic acid-cross-product probably represents an oxidative degradation product from the corresponding diferulate. Both ferulic acid dehydrotrimers are able to cross-link polysaccharide chains. However, the 5-5/8-O-4(H₂O)-triferulic acid may be a cross-link in its identified structure whereas we assume that the identified 8-O-4/8-5(non-cyclic)-triferulic acid arose from a natural 8-O-4/8-5(cyclic)-triferulate analog during the saponification process.     

Binding and condensation of plasmid DNA onto functionalized carbon nanotubes: toward the construction of nanotube-based gene delivery vectors

Carbon nanotubes (CNTs) constitute a class of nanomaterials that possess characteristics suitable for a variety of possible applications. Their compatibility with aqueous environments has been made possible by the chemical functionalization of their surface, allowing for exploration of their interactions with biological components including mammalian cells. Functionalized CNTs (f-CNTs) are being intensively explored in advanced biotechnological applications ranging from molecular biosensors to cellular growth substrates. We have been exploring the potential of f-CNTs as delivery vehicles of biologically active molecules in view of possible biomedical applications, including vaccination and gene delivery. Recently we reported the capability of ammonium-functionalized single-walled CNTs to penetrate human and murine cells and facilitate the delivery of plasmid DNA leading to expression of marker genes. To optimize f-CNTs as gene delivery vehicles, it is essential to characterize their interactions with DNA. In the present report, we study the interactions of three types of f-CNTs, ammonium-functionalized single-walled and multiwalled carbon nanotubes (SWNT-NH3+; MWNT-NH3+), and lysine-functionalized single-walled carbon nanotubes (SWNT-Lys-NH3+), with plasmid DNA. Nanotube-DNA complexes were analyzed by scanning electron microscopy, surface plasmon resonance, PicoGreen dye exclusion, and agarose gel shift assay. The results indicate that all three types of cationic carbon nanotubes are able to condense DNA to varying degrees, indicating that both nanotube surface area and charge density are critical parameters that determine the interaction and electrostatic complex formation between f-CNTs with DNA. All three different f-CNT types in this study exhibited upregulation of marker gene expression over naked DNA using a mammalian (human) cell line. Differences in the levels of gene expression were correlated with the structural and biophysical data obtained for the f-CNT:DNA complexes to suggest that large surface area leading to very efficient DNA condensation is not necessary for effective gene transfer. However, it will require further investigation to determine whether the degree of binding and tight association between DNA and nanotubes is a desirable trait to increase gene expression efficiency in vitro or in vivo. This study constitutes the first thorough investigation into the physicochemical interactions between cationic functionalized carbon nanotubes and DNA toward construction of carbon nanotube-based gene transfer vector systems.     

Biomedical applications of functionalised carbon nanotubes

The organic functionalisation of carbon nanotubes can improve substantially their solubility and biocompatibility profile; as a consequence, their manipulation and integration into biological systems has become possible so that functionalised carbon nanotubes hold currently strong promise as novel systems for the delivery of drugs, antigens and genes.     

Nanoscale organization of a phthalocyanine-fullerene system: remarkable stabilization of charges in photoactive 1-D nanotubules

Induction of self-organization between zinc phthalocyanine (ZnPc) and C60 moieties in a novel amphiphilic ZnPc-C60 salt results in uniformly nanostructured 1-D nanotubules. Their photoreactivity, in terms of ultrafast charge separation (i.e., approximately 1012 s-1) and ultraslow charge recombination (i.e., approximately 103 s-1), is remarkable. In addition, the observed ZnPc*+-C60*- lifetime of 1.4 ms implies, relative to that of the monomeric ZnPc-C60 ( approximately 3 ns), an impressive stabilization of 6 orders of magnitude.     

Application of accelerated heteronuclear single quantum coherence experiments to the rapid quantification of monosaccharides and disaccharides in dairy products

Monosaccharides and disaccharides are important dietary components, but if insufficiently metabolized by some population subgroups, they are also linked to disease patterns. Thus, the correct analytical identification, quantification, and labeling of these food components are crucial to inform and potentially protect consumers. Enzymatic assays and high-performance anion-exchange chromatography with pulsed amperometric detection are established methods for the quantification of monosaccharides and disaccharides that, however, require long measuring times (60–180 min). Accelerated methods for the identification and quantification of the nutritionally relevant monosaccharides and disaccharides d -glucose, d -galactose, d -fructose, sucrose, lactose, and maltose were therefore developed. To realize this goal, the NMR experiments HSQC (heteronuclear single quantum coherence) and acceleration by sharing adjacent polarization (ASAP)-HSQC were applied. Measurement times were reduced to 27 and 6 min, respectively, by optimizing the interscan delay and applying non-uniform sampling. The optimized methods were used to quantify d -glucose, d -galactose, d -fructose, sucrose, and lactose in various dairy products. Results of the HSQC and ASAP-HSQC methods are equivalent to the results of the reference methods in terms of both precision and accuracy, demonstrating that these methods can be used to correctly analyze nutritionally relevant monosaccharides and disaccharides in short times.     

An electrochemically driven molecular shuttle controlled and monitored by C60

Herein we describe a fullerene rotaxane, in which shuttling between two well-defined and distant co-conformations is both induced and monitored by the C60 stopper.     

Determination of acyclovir in plasma by high performance liquid chromatography with UV detection. Method development and method validation

A HJPLC method for the determination of acyclovir in plasma is described. The method is simple and sensitive enough for bioequiva-lence studies, where a large number of plasma samples with low acyclovir concertration are involved. The procedure is based on the deproteinization of plasma with perchloric acid and separation of acyclovir on a Hypersil ODS Column at pH 5.6 with UV detection. The calibration standards are linear up to at least 4000 ng/mL and the limit of quantification is 10 ng/mL.     

Lepidium graminifolium L.: Glucosinolate Profile and Antiproliferative Potential of Volatile Isolates

Glucosinolates (GSLs) from Lepidium graminifolium L. were analyzed qualitatively and quantitatively by their desulfo-counterparts using UHPLC-DAD-MS/MS technique and by their volatile breakdown products-isothiocyanates (ITCs) using GC-MS analysis. Thirteen GSLs were identified with arylaliphatic as the major ones in the following order: 3-hydroxybenzyl GSL (glucolepigramin, 7), benzyl GSL (glucotropaeolin, 9), 3,4,5-trimethoxybenzyl GSL (11), 3-methoxybenzyl GSL (glucolimnanthin, 12), 4-hydroxy-3,5-dimethoxybenzyl GSL (3,5-dimethoxysinalbin, 8), 4-hydroxybenzyl GSL (glucosinalbin, 6), 3,4-dimethoxybenzyl GSL (10) and 2-phenylethyl GSL (gluconasturtiin, 13). GSL breakdown products obtained by hydrodistillation (HD) and CH₂Cl₂ extraction after hydrolysis by myrosinase for 24 h (EXT) as well as benzyl ITC were tested for their cytotoxic activity using MTT assay. Generally, EXT showed noticeable antiproliferative activity against human bladder cancer cell line UM-UC-3 and human glioblastoma cell line LN229, and can be considered as moderately active, while IC₅₀ of benzyl ITC was 12.3 μg/mL, which can be considered as highly active.     

Light‐Controlled Regioselective Synthesis of Fullerene Bis‐Adducts

Multi‐functionalization and isomer‐purity of fullerenes are crucial tasks for the development of their chemistry in various fields. In both current main approaches—tether‐directed covalent functionalization and supramolecular masks—the control of regioselectivity requires multi‐step synthetic procedures to prepare the desired tether or mask. Herein, we describe light‐responsive tethers, containing an azobenzene photoswitch and two malonate groups, in the double cyclopropanation of [60]fullerene. The formation of the bis‐adducts and their spectroscopic and photochemical properties, as well as the effect of azobenzene photoswitching on the regiochemistry of the bis‐addition, have been studied. The behavior of the tethers depends on the geometry of the connection between the photoactive core and the malonate moieties. One tether lead to a strikingly different adduct distribution for the E and Z isomers, indicating that the covalent bis‐functionalization of C₆₀ can be controlled by light.     

LC–MS methods combination for identification and quantification of trans-sinapoylquinic acid regioisomers in green coffee

The present study aims to both identify and quantify trans-sinapoylquinic acid (SiQA) regioisomers in green coffee by combined UHPLC-ESI-QqTOF-MS/MS and UHPLC-ESI-QqQ-MS/MS methods. Among the various mono-acyl chlorogenic acids found in green coffee, SiQA regioisomers are the least studied despite having been indicated as unique phytochemical markers of Coffea canephora (known as Robusta). The lack of commercially available authentic standards has been bypassed by resorting to the advantages offered by high-resolution LC–MS as far as the identification is concerned. SiQA regioisomers have been identified in several samples of Robusta and Coffea arabica (known as Arabica) commercial lots from different geographical origin and, for the first time, in different samples of coffee wild species (Coffea liberica and Coffea pseudozanguebariae). Quantification (total SiQA ranging from 3 to 5 mg/100 g) let to reconsider these chlorogenic acids as unique phytochemical markers of Robusta being present in the same quantity and distribution in C. liberica as well. Gardeniae Fructus samples (fruits of Gardenia jasminoides) have additionally been characterized as this matrix is recognized as one of the few naturally occurring SiQA sources. The SiQA regioisomer content (total SiQA about 80 mg/100 mg) fully supports the proposal to use this matrix as a surrogate standard for further studies.