Rapid phytochemical analysis of birch (Betula) and poplar (Populus) foliage by near-infrared reflectance spectroscopy

Poplar (Populus) and birch (Betula) species are widely distributed throughout the northern hemisphere, where they are foundation species in forest ecosystems and serve as important sources of pulpwood. The ecology of these species is strongly linked to their foliar chemistry, creating demand for a rapid, inexpensive method to analyze phytochemistry. Our study demonstrates the feasibility of using near-infrared reflectance spectroscopy (NIRS) as an inexpensive, high-throughput tool for determining primary (e.g., nitrogen, sugars, starch) and secondary (e.g., tannins, phenolic glycosides) foliar chemistry of Populus and Betula species, and identifies conditions necessary for obtaining reliable quantitative data. We developed calibrations with high predictive power (residual predictive deviations?≤?7.4) by relating phytochemical concentrations determined with classical analytical methods (e.g., spectrophotometric assays, liquid chromatography) to NIR spectra, using modified partial least squares regression. We determine that NIRS, although less sensitive and precise than classical methods for some compounds, provides useful predictions in a much faster, less expensive manner than do classical methods.

The German bakery waste incident; use of a combined approach of screening and confirmation for dioxins in feed and food

During the last six years several incidents have occurred with dioxins in feed, stressing the need for rapid screening methods for these compounds. The most recent incident was the contamination of bakery waste used for animal feed due to the use of waste wood for drying of the material. In addition to Germany, the material was also shipped to the Netherlands. Levels up to 12 ng TEQ/kg have been detected, being about 15 times over the current limit of 0.75 ng TEQ/kg. In the Netherlands a combined strategy of screening with the CALUX-bioassay and the HRGC/HRMS confirmatory method was used to rapidly control the incident. Pigs were contaminated by the incident but only to a very limited extent. Despite the rather low limits for pig meat, the CALUX bioassay showed excellent performance, once again confirming the value of this assay.     

Ultrathin Carbon Film Electrodes from Vacuum‐Carbonised Cellulose Nanofibril Composite

A novel way to produce ultrathin transparent carbon layers on tin‐doped indium oxide (ITO) substrates is developed. The ITO surface is coated with cellulose nanofibrils (from sisal) via layer‐by‐layer electrostatic binding with poly(diallyldimethylammonium chloride) or PDDAC acting as the binder. The cellulose nanofibril‐PDDAC composite film is then vacuum‐carbonised at 500 °C. The resulting carbon films are characterised by atomic force microscopy (AFM), small angle X‐ray scattering (SAXS), wide‐angle X‐ray scattering (WAXS), and Raman methods. Smooth carbon films with good adhesion to the ITO substrate are formed. The electrochemical characterisation of the carbon films is based on the oxidation of hydroquinone and the reduction of benzoquinone in aqueous phosphate buffer media. A modest effect of the cellulose nanofibril‐PDDAC film on the rate of electron transfer is observed. The effect of the film on the rate of electron transfer after carbonisation is more dramatic. For a 40‐layer cellulose nanofibril‐PDDAC film after carbonisation a two‐order of magnitude change in the rate of electron transfer occurs presumably due to a better interaction of the hydroquinone/benzoquinone system with the electrode surface.     

Exploring and characterizing the folding processes of Lys- and Arg-containing Ala-based peptides: a molecular dynamics study

In this study, molecular dynamics simulations were carried out on Lys- and Arg-containing Ala-based peptides (i.e. Ace-(AAAAK)(n)A-NH(2) and Ace-(AAAAR)(n)A-NH(2), where n=1-4), in order to explore and characterize their folding processes. For the oligopeptides, the evolution of α-helical structure with regard to the whole conformation, as well as to each residue was investigated, and the helix-forming propensities were characterized. On the basis of the helicity curves, representing the alteration of average helicity as a function of time, the typical time values describing the folding processes and subprocesses were identified. In the case of each peptide, the evolution and role of helix-stabilizing, non-local and side-chain-to-backbone H-bonds were examined. The appearing i←i+4 H-bonds pointed out the role of these interactions in the stabilization of α-helical conformations, while the occurring i←i+3 H-bonds indicated the presence of β-turn or 3(10)-helical structures. Studying the formation and role of non-local and side-chain-to-backbone H-bonds led to the observation that these types of interactions produced an effect on the evolution of helical conformations, as well as on the folding processes.     

Highly sensitive restriction enzyme assay and analysis: a review

Biological assays at the single molecule level are crucial to fundamental studies of DNA-protein mechanisms. In order to cater for high throughput applications, one area of immense research potential is single-molecule bioassays where miniaturized devices are developed to perform rapid and effective biological reactions and analyses. With the success of various emerging technologies for engineering miniaturized structures down to the nanoscale level, supported by specialized equipment for detection, many investigations in the field of life science that were once thought impossible can now be actively explored. In this review, the significance of downscaling to the single-molecule level is firstly presented in selected examples, with the focus placed on restriction enzyme assays. To determine the effectiveness of single-molecule restriction enzyme reactions, simple and direct analytical methods based on DNA stretching have often been reliably employed. DNA stretching can be realized based on a number of working principles related to the physical forces exerted on the DNA samples. We then discuss two examples of a nanochannel system and a microchamber system where single-molecule restriction enzyme digestion and DNA stretching have been integrated, which possess prospective capabilities of developing into highly sensitive and high-throughput restriction enzyme assays. Finally, we take a brief look at the general trends in technological development in this field by comparing the advantages and disadvantages of performing assays at bulk, microscale and single-molecule levels. Figure Minaturization of Restriction Enzyme Assays and DNA Stretching     

Ultrafast Charge Delocalization Dynamics of Ambient Stable CsPbBr3 Nanocrystals Encapsulated in Polystyrene Fiber

CsPbBr₃ nanocrystals (NCs) encapsulated in a transparent polystyrene (PS) fiber matrix (CsPbBr₃@PS) have been synthesized to protect the NCs. The ultrafast charge delocalization dynamics of the embedded NCs have been demonstrated, and the results are compared with the pristine CsPbBr₃ in toluene. The electrospinning method was employed for the preparation of CsPbBr₃@PS fibers by using a polystyrene solution doped with pre-synthesized CsPbBr₃ and characterized by XRD, HRTEM, and X-ray photoelectron spectroscopy (XPS). Energy level diagrams of CsPbBr₃ and PS suggest that CsPbBr₃@PS fibers make a type I core–shell structure. The carrier cooling for CsPbBr₃@PS fibers is found to be much slower than pure CsPbBr₃ NCs. This observation suggests that photoexcited electrons from CsPbBr₃ NCs get delocalized from the conduction band of the perovskite to lowest unoccupied molecular orbital (LUMO) of the PS fiber matrix. The CsPbBr₃@PS fibers possess remarkable stability under ambient conditions as well as in water over months. The clear understanding of charge carrier relaxation dynamics of CsPbBr₃ confined in PS fibers could help to design robust optoelectronic devices.     

Monobenzylation Of 1,n-Diols via Dibutylstannylene Intermediates

Symmetrical primary l,n-diols, HO(CH_2)nOH, of any chain length from n = 2-10, can be selectively monobenzylated via sequential treatment with dibutyltin oxide and benzyl bromide.     

Bioavailability and biotransformation of sulforaphane and erucin metabolites in different biological matrices determined by LC–MS–MS

The food-related isothiocyanate sulforaphane (SFN), a hydrolysis product of the secondary plant metabolite glucoraphanin, has been revealed to have cancer-preventive activity in experimental animals. However, these studies have often provided inconsistent results with regard to bioavailability, bioaccessibility, and outcome. This might be because the endogenous biotransformation of SFN metabolites to the structurally related erucin (ERN) metabolites has often not been taken into account. In this work, a fully validated liquid chromatography tandem mass spectrometry (LC–MS–MS) method was developed for the simultaneous determination of SFN and ERN metabolites in a variety of biological matrices. To reveal the importance of the biotransformation pathway, matrices including plasma, urine, liver, and kidney samples from mice and cell lysates derived from colon-cancer cell lines were included in this study. The LC–MS–MS method provides limits of detection from 1 nmol L^?1 to 25 nmol L^?1 and a mean recovery of 99 %. The intra and interday imprecision values are in the range 1–10 % and 2–13 %, respectively. Using LC–MS–MS, SFN and ERN metabolites were quantified in different matrices. The assay was successfully used to determine the biotransformation in all biological samples mentioned above. For a comprehensive analysis and evaluation of the potential health effects of SFN, it is necessary to consider all metabolites, including those formed by biotransformation of SFN to ERN and vice versa. Therefore, a sensitive and robust LC–MS–MS method was validated for the simultaneous quantification of mercapturic-acid-pathway metabolites of SFN and ERN.

Open image in new window

Graphical Abstract Biotransformation of sulforaphane and erucin metabolites in mice and cell culture

     

Challenges in determining perchlorate in biological tissues and fluids: implications for characterizing perchlorate exposure

The ability to measure environmental contaminants in biological tissues and fluids is important in the characterization of exposure. However, the analysis of certain contaminants in these matrices presents significant challenges. Perchlorate (ClO₄⁻) has emerged as a potential contaminant of concern primarily in drinking water and also in contaminated food. Significant advances have been made in the analysis of perchlorate in environmental matrices (water, soil) by ion chromatography (IC). In contrast, the analysis of perchlorate in extracts of biological tissues and fluids (vegetation, organs, milk, blood, urine, etc.) presents several challenges including small sample sizes, extracts with high matrix conductivity, and co-elution of other ions during IC analysis. To be able to detect low concentrations of perchlorate in biological samples, interferences must be removed or minimized, such as through the use of preparative chromatography cleanup techniques and/or alternative analytical methods less susceptible to common interferences (preconcentration or mass spectrometric detection). We present discussion and examples of the challenges encountered in the analysis of tissue extracts and fluids for perchlorate by IC and how some of those analytical challenges have been overcome.     

Chlorine interactions with water ice studied by molecular beam techniques

The kinetics of chlorine interactions with ice at temperatures between 103 and 165 K have been studied using molecular beam techniques. The Cl(2) trapping probability is found to be unity at thermal incident energies, and trapping is followed by rapid desorption. The residence time on the surface is less than 25 microg at temperatures above 135 K and approaches 1 s around 100 K. Rate constants for desorption are determined for temperatures below 135 K. The desorption kinetics follow the Arrhenius equation, and activation energies of 0.24 +/- 0.03 and 0.31 +/- 0.01 eV, with corresponding preexponential factors of 10(12.08+/-1.19) and 10(16.52+/-0.38) s(-1), are determined. At least two different Cl(2) binding sites are concluded to exist on the ice surface. The observed activation energies are likely to be the Cl(2)-ice binding energies for these states, and the Cl(2)-surface interactions are concluded to be stronger than earlier theoretical estimates. The surface coverage of Cl(2) on ice under stratospheric conditions is estimated to be negligible, in agreement with earlier work.