Arboricine and arboricinine, unusual tetracyclic indole regioisomers from Kopsia

A pair of unusual regioisomeric tetracyclic indoles of the corynantheine-type, arboricine and arboricinine were obtained from the Malayan Kopsia arborea. The structures were established by spectroscopic analysis and a possible biogenetic link between the alkaloids is presented.     

Spectrophotometric flow-injection determination of zinc in plant digests based on a spot test

A spot test was implemented in a flow-injection system for the spectrophotometric determination of zinc in digests of plant materials. It is based on the influence of Zn²⁺ on the oxidation rate of 1-naphthylethylenediamine (NED) by hexacyanoferrate(III) under acidic conditions. In order to control the precipitate formation and to maintain the resulting suspension, a micellar medium was established by adding Triton X-100. The proposed system handles about 65 samples per hour, meaning 72 μg NED and 9.0 mg K₃[Fe(CN)₆] per determination. Baseline drift is usually <0.01 absorbance per hour and the analytical signals for 0.5-2.5 mg l⁻¹ Zn range within ca. 0.07-0.45 absorbance. Linearity of the analytical curve is fair (r>0.999, n=6) and detection limit was estimated as 0.2 mg l⁻¹ Zn. Results are precise (R.S.D.<1%, n=10) and in agreement with flame atomic absorption spectrometry and with certified values of standard reference materials.     

Arbophylline, a novel heptacyclic indole with a cage skeleton incorporating an acetal moiety

A new indole alkaloid, arbophylline, possessing a novel heptacyclic cage skeleton, and incorporating an acetal function, was obtained from the Malayan Kopsia arborea. The structure was established by spectroscopic analysis and a possible biogenetic pathway from an akuammiline-type precursor is presented.     

Correction of iron interface in the spectrophotometric flow injection catalytic determination of molybdenum in plants

Iron interference in the spectrophotometric catalytic determination of molybdenum based on the iodide-hydrogen peroxide reaction can be corrected by using sulphosalicylic acid as masking and color-forming reagent. The catalytic influence of iron ions is circumvented to the extent of about 90% and correction of any remaining iron ions is possible by monitoring the colored iron(III)-salicylate complex at 490 nm. In this way, iron is also determined. With the proposed system, molybdenum can be determined in plant and food digests within the 0–100 μg Mo 1⁻¹ range in the presence of up to 25 mg Fe 1⁻¹, at a sampling rate of about 50 determinations h⁻¹. The relative standard deviation of 10 consecutive measurements was estimated as < 2%. Results for samples were comparable with those obtained by graphite furnace atomic absorption spectrometry. In addition, recoveries within the range 94–100% were calculated.     

SPME – A valuable tool for investigation of flower scent

A novel Headspace Solid Phase Microextraction (HS‐SPME) protocol is proposed for the analysis of floral scent. Volatile compounds emitted from the flower are collected on a Carboxen/PDMS fiber for 1 hour, transferred to the GC, and analyzed by GC/MS. The method completely eliminates the use of organic solvents, does not require special instrumentation, and may readily be performed in the field without access to mains electricity and other energy supplies. The method is robust, sensitive, and reduces the sampling stress on the investigated plant. Since enzymatic reactions in living flowers may cause changes in the composition of emitted fragrance, dried rosemary (Rosmarinus officinalis L.) was used as a stable standard for the method development and optimization. In addition, grape wine was also suggested as homogeneous, bio‐compatible, and relatively stable standard of pronounced and typical scent for the same purpose. The optimized method was used for the comparative investigation of the fragrances emitted by two different species – Lathyrus vernus (L.) and Orchis pallens (L.). Several monoterpenes (C10 compounds) were found as the main fragrance components of lathyrus, while sesquiterpenes (C15 compounds) were typical for the orchid.     

Unusual spirocyclic macroline alkaloids, nitrogenous derivatives, and a cytotoxic bisindole from Alstonia

The bark extract of the Malayan A. macrophylla provided several novel indoles with unprecedented carbon skeletons, an unusual nitrogenous compound, a cytotoxic bisindole, several new macroline alkaloids, in addition to other known alkaloids. The structures of the new compounds were established by spectroscopic analysis.     

Biogenic synthesis of gold and silver nanoparticles used in environmental applications: A review

Due to their physical, chemical, optical, and mechanical properties, metallic nanoparticles (MNPs) are increasingly being used, with an emphasis on silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs). In recent years, green synthesis has gained prominence for exploring the use of naturally available biological sources for the obtention of metallic nanoparticles. Among these, algae and plants stand out due to the presence of polysaccharides, proteins, polyphenols, and vitamins (among others) in their composition, which can act in the reduction and stabilisation of MNPs, and these biogenic materials have been characterised mainly by spectrometric and microscopic techniques. In addition, due to the numerous advantages of nanoparticles (NPs) synthetize from biogenic source, such as their simplicity and cost benefits, they have been used in the development of sensors applied in the determination of contaminants present in environmental samples and in the catalytic reduction of organic and inorganic contaminants. Therefore, this review describes the synthesis, mechanisms, characterization, and environmental analytical applications of NPs obtained by biogenic synthesis as well as the perspectives and challenges of these NPs.     

Organic-coated silver nanoparticles in biological and environmental conditions: Fate,stability and toxicity

This review paper presents the overview of processes involved in transformation of organic-coated silver nanoparticles (AgNPs) in biological systems and in the aquatic environment. The coating on AgNPs greatly influences the fate, stability, and toxicity of AgNPs in aqueous solutions, biological systems, and the environment. Several organic-coated AgNP systems are discussed to understand their stability and toxicity in biological media and natural water. Examples are presented to demonstrate how a transformation of organic-coated AgNPs in an aqueous solution is affected by the type of coating, pH, kind of electrolyte (mono- or divalent), ionic strength, organic ligands (inorganic and organic), organic matter (fulvic and humic acids), redox conditions (oxic and anoxic), and light. Results of cytotoxicity, genotoxicity, and ecotoxicity of coated AgNPs to food chain members (plants, bacteria, and aquatic and terrestrial organisms) are reviewed. Key factors contributing to toxicity are the size, shape, surface coating, surface charge, and conditions of silver ion release. AgNPs may directly damage the cell membranes, disrupt ATP production and DNA replication, alternate gene expressions, release toxic Ag⁺ ion, and produce reactive oxygen species to oxidize biological components of the cell. A progress made on understanding the mechanism of organic-coated AgNP toxicity using different analytical techniques is presented.     

Green synthesis of biogenic metal nanoparticles by terrestrial and aquatic phototrophic and heterotrophic eukaryotes and biocompatible agents

The size, shape and controlled dispersity of nanoparticles play a vital role in determining the physical, chemical, optical and electronic properties attributing its applications in environmental, biotechnological and biomedical fields. Various physical and chemical processes have been exploited in the synthesis of several inorganic metal nanoparticles by wet and dry approaches viz., ultraviolet irradiation, aerosol technologies, lithography, laser ablation, ultrasonic fields, and photochemical reduction techniques. However, these methodologies remain expensive and involve the use of hazardous chemicals. Therefore, there is a growing concern for the development of alternative environment friendly and sustainable methods. Increasing awareness towards green chemistry and biological processes has led to a necessity to develop simple, cost-effective and eco-friendly procedures. Phototrophic eukaryotes such as plants, algae, and diatoms and heterotrophic human cell lines and some biocompatible agents have been reported to synthesize greener nanoparticles like cobalt, copper, silver, gold, bimetallic alloys, silica, palladium, platinum, iridium, magnetite and quantum dots. Owing to the diversity and sustainability, the use of phototrophic and heterotrophic eukaryotes and biocompatible agents for the synthesis of nanomaterials is yet to be fully explored. This review describes the recent advancements in the green synthesis and applications of metal nanoparticles by plants, aquatic autotrophs, human cell lines, biocompatible agents and biomolecules.     

Evaluation of different column types for the hydrophilic interaction chromatographic separation of iron-citrate and copper-histidine species from plants

Hydrophilic interaction chromatography (HILIC) has emerged as a very useful separation method for polar analytes, including non-covalent metal species. Several types of stationary phases are available for HILIC applications, differing mainly in their chemical functionalities that supply additional interaction modes and alternative selectivities for the separation of special analytes. With regard to the separation of metal species only few of these stationary phases have been applied to date, and it is not completely clear what are their differences with respect to the chromatographic separation of metal species, but also with respect to species stability during chromatography. Here, a comparison of different column types for the HILIC separation of iron citrate and copper histidine species is presented and the results are discussed with respect to retention mechanisms and chromatographic stability of these metal species. It is shown that different stationary phases display very different separation patterns. In particular, three types of HILIC columns enable successful separation of iron citrates and copper histidine at pH 5.5, namely a crosslinked diol phase, a zwitterionic phase, and an amide phase. Two groups of iron-citrates are separated on all three columns, consisting of a species of 3:3 stoichiometry and another one of mainly 3:4 stoichiometry (plus 1:2 and 2:2 species). For copper-histidine only one stable species is found based on the 1:2 stoichiometry. Detection and unambiguous identification of the different species is possible by employing electrospray mass spectrometry in the negative ionization mode. Species found in standard solutions are consistent with species found in spiked plant samples. Also in unspiked solutions iron citrate of 3:4 stoichiometry (plus 1:2 and 2:2) is detectable, but no species of 3:3 stoichiometry. Significant differences of related species patterns are found in real plant samples.