Progress in the Study of Bioluminescent Earthworms

Even though bioluminescent oligochaetes rarely catch people's eyes due to their secretive lifestyle, glowing earthworms sighting reports have come from different areas on all continents except Antarctica. A major breakthrough in the research of earthworm bioluminescence occurred in the 1960s with the studies of the North American Diplocardia longa. Comparative studies conducted on 13 earthworm species belonging to six genera showed that N‐isovaleryl‐3‐aminopropanal (Diplocardia luciferin) is the common substrate for bioluminescence in all examined species, while luciferases appeared to be responsible for the color of bioluminescence. The second momentous change in the situation has occurred with the discovery in Siberia (Russia) of two unknown luminous enchytraeids. The two bioluminescent systems belong to different types, have different spectral characteristics and localization, and different temperature and pH optima. They are unique, and this fact is confirmed by the negative results of all possible cross‐reactions. The bioluminescent system of Henlea sp. comprises four essential components: luciferase, luciferin, oxygen and calcium ion. For Friderica heliota, the luminescent reaction requires five components: luciferase, luciferin, ATP, magnesium ion and oxygen. Along with luciferin, more than a dozen analogues were isolated from worm biomass. These novel peptide‐like natural compounds represent an unprecedented chemistry found in terrestrial organisms.     

Composition of essential oil from <Emphasis Type="Italic">Artemisia glauca</Emphasis> from western Siberia

The composition of essential oil from Artemisia glauca (Asteraceae) growing in southern Siberia was studied. More than 60 oil components consisting of 99.0–99.7% of the total volatile components were identified by GC—MS by comparison of full mass spectra and retention times. The main components of the essential oil were acetylene derivatives of capillene (11–60%) and benzyldiacetylene (1–31%). Other acetylene derivatives such as capillin, (E)-hex-4-en-2-ynylbenzene, 1-(4-methoxyphenyl)-2,4-pentadiyne, and capillarin were also identified in the oil. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 446–449, September–October, 2007.     

Gas-chromatographic determination of mutual solubility of components in heterophase binary systems of organic solvents

A general gas-chromatographic method is proposed for determining mutual solubility of partially miscible organic solvents. The method involves gradual increase of the concentration of one component in the other component in the region below their mutual solubility limit, determining parameters of the linear regression c = aS + b (c is the concentration, and S is the peak area), analysis of saturated solutions of components of binary systems in each other (at S ≈ const), and calculating c values from the obtained equation. The method was tested by known data on mutual solubility of components of the hexane-acetonitrile and hexane-nitromethane binary systems. Data for the hexane-2,2,2-trifluoroethanol and perfluorodecalin-acetonitrile binary systems are obtained for the first time; in the latter case, abnormally low mutual solubility of components is revealed.     

Dynamics of radiationless transitions in large molecules: 2. Recurrence cycles in population evolution of the initial state

Evolution of the population of the initial state S is due to radiationless transitions into a dense discrete spectrum of intramolecular vibrations {R _n } (reservoir R) and spontaneous decay of S and R _n by virtue of coupling with a continuous spectrum of intermolecular vibrations (reservoir Q). An exact solution to the dynamic problem has been found, which indicates that in contrast to the Fermi approximation, which reproduces only the exponential decay of S, the evolution consists of recurrence cycles such that Loschmidt echo (partial recovery of the population of S via back transitions from R _n ) appears in each cycle. The width and number of echo components depend upon average characteristics of the spectrum of R. With an equidistant spectrum and the same coupling constants of S with all R states, the decay of S is exponential in the initial cycle and the number of echo components and echo width increase proportionally to the cycle number in subsequent cycles. The increase in the width causes mixing of the echo components and the transition from regular to quasi-stochastic dynamics. Deformation of the equidistant spectrum leads to nonexponential decay in the initial cycle, an increase in the number of components, and a reduction in the number of cycles with regular dynamics.     

Comparative Analysis of the Volatile Components in the Fresh Roots and Rhizomes of Curcuma wenyujin by Static Headspace Gas Chromatography Mass Spectrometry

Static headspace GC-MS method coupled with H/D exchange was firstly developed to determine and identifythe volatile components in the fresh root and rhizome of Curcuma wenyujin.The TIC chromatograms of 3 batchesof fresh roots harvested at different time showed significant difference in the volatile components:the constitutionwas the same but the content of them was different.More than 60 volatile components in fresh roots(Root of C.wenyujin)and rhizomes(Rhizome of C.wenyujin)of C.wenyujin were detected,of which 51 and 48 volatile com-ponents were identified respectively.The fresh roots and rhizomes of C.wenyujin were found to have the similarvolatile components.The contents of these components were calibrated by the response of β-elemene.In addition,the principal active component,β-elemene,was further confirmed and relatively quantified by its standard.γ-terpinene showed obvious allylic hydrogen/deuterium exchange using deuterium oxide which gave a new methodto identify some compounds containing allylic hydrogen.At the same time,the active hydrogen compounds werealso further confirmed.The results show that HS-GC-MS method is a fast,simple and efficient way for the analysisof volatile components from medical plants.     

Differentiation of essential oils in Atractylodes lancea and Atractylodes koreana by gas chromatography with mass spectrometry

Atractylodes rhizome is a valuable traditional Chinese medicinal herb that comprises complex several species whose essential oils are the primary pharmacologically active component. Essential oils of Atractylodes lancea and Atractylodes koreana were extracted by hydrodistillation, and the yield was determined. The average yield of essential oil obtained from A. lancea (2.91%) was higher than that from A. koreana (2.42%). The volatile components of the essential oils were then identified by a gas chromatography with mass spectrometry method that demonstrated good precision. The method showed clear differences in the numbers and contents of volatile components between the two species. 41 and 45 volatile components were identified in A. lancea and A. koreana, respectively. Atractylon (48.68%) was the primary volatile component in A. lancea, while eudesma‐4(14)‐en‐11‐ol (11.81%) was major in A. koreana. However, the most significant difference between A. lancea and A. koreana was the major component of atractylon and atractydin. Principal component analysis was utilized to reveal the correlation between volatile components and species, and the analysis was used to successfully discriminate between A. lancea and A. koreana samples. These results suggest that different species of Atractylodes rhizome may yield essential oils that differ significantly in content and composition.     

Comprehensive identification and structural characterization of target components from Gelsemium elegans by high‐performance liquid chromatography coupled with quadrupole time‐of‐flight mass spectrometry based on accurate mass databases combined with MS/MS spectra

This study reports an applicable analytical strategy of comprehensive identification and structure characterization of target components from Gelsemium elegans by using high‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry (LC‐QqTOF MS) based on the use of accurate mass databases combined with MS/MS spectra. The databases created included accurate masses and elemental compositions of 204 components from Gelsemium and their structural data. The accurate MS and MS/MS spectra were acquired through data‐dependent auto MS/MS mode followed by an extraction of the potential compounds from the LC‐QqTOF MS raw data of the sample. The same was matched using the databases to search for targeted components in the sample. The structures for detected components were tentatively characterized by manually interpreting the accurate MS/MS spectra for the first time. A total of 57 components have been successfully detected and structurally characterized from the crude extracts of G. elegans , but has failed to differentiate some isomers. This analytical strategy is generic and efficient, avoids isolation and purification procedures, enables a comprehensive structure characterization of target components of Gelsemium and would be widely applicable for complicated mixtures that are derived from Gelsemium preparations. Copyright © 2017 John Wiley & Sons, Ltd.     

Spin-Dependent operators in the spin-free quantum chemistry

The two-particle spatial density matrix components introduced by McWeeny are expressed in terms of the Fock coordinate wave function, which is constructed from an arbitrary function of N spatial coordinates. The integral relations for these components are verified. The necessary matrix elements of a standard representation of the S_N group are calculated.     

Biodegradation of Polyhydroxyalkanoate Films in Natural Environments

Summary: Biodegradation of film specimens from polyhydroxyalkanoates (PHAs) of two types – poly-3-hydroxybutyrate (PHB) and poly-3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV) – was analysed in different environments: tropical sea waters of the South China Sea (Nha Trang, Vietnam) and soils in the environs of Hanoi (Vietnam), Nha Trang (Vietnam) and Krasnoyarsk (Siberia, Russia). In seawater, the mass loss of the specimens of both types was almost equal. However, in tropical soils, PHB degraded quicker than PHBV. In the Siberian soil, the degradation rate of the PHBV was generally higher than that of PHBV. Analysis of molecular mass of PHA specimens showed its decreasing during biodegradation. In the tropical sea conditions, PHA degrading microorganisms were represented by bacteria of Enterobacter, Bacillus and Gracilibacillus genera. Among PHA degrading bacteria, Burkholderia, Alcaligenes, Bacillus, Mycobacterium and Streptomyces genera were identified in Vietnamese soils, and Variovorax, Stenotrophomonas, Acinetobacter, Pseudomonas, Bacillus and Xanthomonas genera in Siberian soils. Micromycetes of Gongronella, Paecilomyces, Penicillium and Trichoderma genera exhibited PHA degrading activity in Vietnamese soils, and Paecilomyces, Penicillium, Acremonium, Verticillium and Zygosporium genera – in Siberian soils.     

Use of Two-Dimensional Liquid Chromatography Combined with Diode-Array and Mass Spectrometric Detection for Analysis of Compounds in Flos Lonicera

Comprehensive two-dimensional liquid chromatographic separation by means of a combination of ion-exchange chromatography (IEC) and reversed-phase liquid chromatography (RPLC) has been realized and applied to the analysis of components of a traditional Chinese medicine Flos Lonicera. In the first dimension the components of a Flos Lonicera extract is separated on strong anion-exchange (SAX) column according to the charge-exchange properties of the components. In the second dimension the components are further fractionated by reversed-phase liquid chromatography (on ODS) on the basis of their hydrophobicity. The RPLC effluent is desalted and split and the components are identified on-line by use of both diode-array detection and mass spectrometry with atmospheric pressure chemical ionization (APCI–MS). In this way, the extract of Flos Lonicera can be rapidly separated, desalted, and analyzed, with determination of molecular weight. More than 58 components of an extract of Flos Lonicera were well resolved and six were tentatively identified from their UV and mass spectra.     

Helicity Control in the Preparation of Chiral Co-crystals from Tryptamine and Achiral Carboxylic Acids by Pseudo-seeding

Abstract

Chiral crystals of tryptamine and achiral carboxylic acids such as p-chlorobenzoic acid, cinnamic acid, p-chlorocinnarnic acid and p-methylcinnamic acid were prepared by crystallization from the solutions of both components. All the crystals belonged to typical chiral space group P2₁2₁2₁. The crystal chirality is generated through the formation of a unidirectional twofold helix between the two components through quaternary ammonium salt interaction and hydrogen bonding in the lattice. This kind of spontaneous crystallization necessarily gives crystals of both clockwise and counterclockwise helicites. Here, pseudo-seeding based on utilizing these crystals as seed crystals was examined, resulting in successful helicity control in crystallization from solutions of tryptamine and different carboxylic acids.     

Identification and Biological Activity of Volatile Organic Compounds Emitted by Plants and Insects. IV. Composition of Vapor Isolated from Certain Species of Artemisia Plants

The components of fragrance from four wormwood species of theArtemisiaL. genus were analyzed by GC-MS. The major and minor components of volatile essential oils typical of the studied plant species were determined.     

Quantitative and fingerprinting analysis of Atractylodes rhizome based on gas chromatography with flame ionization detection combined with chemometrics

This study assessed the feasibility of gas chromatography with flame ionization detection fingerprinting combined with chemometrics for quality analysis of Atractylodes rhizome. We extracted essential oils from 20 Atractylodes lancea and Atractylodes koreana samples by hydrodistillation. The variation in extraction yields (1.33–4.06%) suggested that contents of the essential oils differed between species. The volatile components (atractylon, atractydin, and atractylenolide I, II, and III) were quantified by gas chromatography with flame ionization detection and confirmed by gas chromatography with mass spectrometry, and the results demonstrated that the number and content of volatile components differed between A. lancea and A. koreana. We then calculated the relative peak areas of common components and similarities of samples by comparing the chromatograms of A. lancea and A. koreana extracts. Also, we employed several chemometric techniques, including similarity analysis, hierarchical clustering analysis, principal component analysis, and partial least‐squares discriminate analysis, to analyze the samples. Results were consistent across analytical methods and showed that samples could be separated according to species. Five volatile components in the essential oils were quantified to further validate the results of the multivariate statistical analysis. The method is simple, stable, accurate, and reproducible. Our results provide a foundation for quality control analysis of A. lancea and A. koreana.     

HPLC Determination of Flavonoids in Hairy-Root Cultures of <Emphasis Type="Italic">Scutellaria baicalensis</Emphasis> Georgi

A simple and sensitive liquid chromatographic method has been established for determination of the main flavonoid components of Scutellaria baicalensis Georgi (Lamiaceae) roots and hairy-root cultures. Wogon, the dried root of the plant, is used in traditional Chinese medicine for treatment of bronchitis, hepatitis, tumors, and inflammatory diseases. Lyophilized hairy roots were extracted with methanol. The crude extracts were purified by SPE on Supelco LC-8 cartridges. HPLC separations were performed on a Eurospher 100-C₈ reversed-phase column. The mobile phase was a gradient prepared from mixtures of acetonitrile and 0.1% trifluoroacetic acid. Peaks were identified by addition of standards and/or by diode-array detection. Baicalein 7-O-glucuronide (baicalin), wogonin 7-O-glucuronide (wogonoside), baicalein, wogonin, and acteoside were determined by the external standard method at 280 nm. We found that the aglycon (baicalein and wogonin) content of the transformed roots was consistently higher than that of the intact root from Siberia.     

Kinetics of Photochemical Systems with Modulated Optical Excitation

The kinetic equations of a photochemical system are discussed in which the transitions from the ground to the first excited state are produced by a sinusoidally modulated photon source. The system includes irreversible reactions starting from the first excited singlet state S₁ and the first triplet state T₁ (cf. Fig. 1). Explicit solutions are given for a linear approximation of the equations of motion for the parametrically modulated system. The solutions apply only when there is weak optical pumping, low quantum yields of the photochemical end-products and for certain conditions, of the modulation frequency. The concentrations of all particles occurring are shown to consist of modulated and unmodulated components where the amplitudes of the modulated components are slowly decaying exponentials. Thc phases of the modulated components are shown to be non-decreasing along a sequence of irreversible steps. Formulae are given which permit determination of the photochemical system rate constants and location of a particle in a sequence of irreversible reactions.     

Stress relaxation of polybutadiene at large deformation. Measurements of stress and birefringence in shear and elongation

The rheological behavior of an uncrosslinked polybutadiene on sudden application of finite strain was examined. The shear stress σ, two components of birefringence, and the extinction angle were measured in shear (magnitude of shear γ ≤ 3.5) and tensile stress and the birefringence were measured in uniaxial elongation (elongation ratio λ ≤ 3.8). Measurements were performed at 30°C with a tensile tester equipped with appropriate sample holders. The stress-optical coefficient was 3.01 × 10^?9Pa^?1. The first and second normal-stress differences v₁ and v₂ were separately evaluated with the use of stress-optical law. The Lodge—Meissner relation v₁ = γσ held good. The ratio v₂/v₁ was independent of time and varied from about ?0.3 to ?0.2 with increasing γ in the range of measurements. Each of the stress components was factored into a function of strain and one of time, and the latter was common to all the stress components. Simple formulas were proposed to represent stress components in step deformations.     

Compositional studies of human RPE lipofuscin

Age‐related macular degeneration (AMD) is an ocular disease that causes visual loss and legal blindness in the elderly population. The etiology of AMD is complex and may include genetic predispositions, accumulation of lipofuscin and drusen, local inflammation and neovascularization. The accumulation of lipofuscin has been shown to precede the death of photoreceptor cells and the deterioration of the RPE. As a result, the determination of the photosensitive components of lipofuscin has been of major interest. One of these components, previously identified as a bis‐retinoid pyridinium compound, is referred to as A2E. A2E has been characterized by mass spectrometry and is known to have a mass of 592 Da. Most remaining chromophores in RPE lipofuscin are structurally related to A2E as determined by their fragmentation pattern with losses of M ± 190, 174 and/or 150 Da. Analysis of lipofuscin from various donors indicated that the extracts consist of as many as 15 of these hydrophobic components, which are also observed to form spontaneously in vitro over extended periods of time. These consist of ca 90% of the A2E‐like components in RPE lipofuscin and correspond to derivatized A2E with discrete molecular weights of 800–900 m/z, 970–1080 m/z and above 1200 m/z regions. It was determined that these species are formed from self‐reaction of A2E oxidation products or their reaction with A2E itself to form higher molecular weight products. The majority of modifications are much more hydrophobic than A2E and exhibit increasingly higher values of log P. This acts as a driving force for the sequestering of A2E into granules resulting in a concomitant diminution of its reactivity in vivo. Copyright © 2010 John Wiley & Sons, Ltd.     

Chemical diversity and anti-acne inducing bacterial potentials of essential oils from selected Elsholtzia species

Essential oils from the aerial parts of four Elsholtzia species; Elsholtzia stachyodes, Elsholtzia communis, Elsholtzia griffithii and Elsholtzia beddomei were obtained by steam distillation and their chemical components were analysed by gas chromatography-mass spectrometry (GC-MS). Principle Component Analysis was used to identify the chemical variations in the essential oils from these plants, which could be categorised into two groups according to their main chemical components which are acylfuran derivatives and oxygenated monoterpenes. Additionally, the anti-acne inducing bacterial activity against Staphylococcus aureus and Staphylococcus epidermidis were evaluated. The oil from E. stachyodes was the most efficacious against the growth of S. aureus and S. epidermidis having MIC values of 0.78 and 1.56 μL/mL, respectively, and exhibited five times more effective than erythromycin (standard antibiotic).     

What Caused the Formation of the Absorption Maximum at 421 nm in vivo Spectra of Rhodopseudomonas palustris

A spectral peak at ~421 nm appeared in vivo spectrum of Rhodopseudomonas palustris CQV97 cultured in acetate–glutamate medium (M1) but not in acetate–ammonium sulfate medium (M2). However, the spectral origin of 421 nm peak was not clear and frequently attributed to carotenoid component(s). In this study, comparative analysis of the extracted components showed that magnesium protoporphyrin IX monomethylester (MPE) was accumulated as one of the predominate components in M1 culture. The amounts of bacteriochlorophyll a in M1 culture were higher than that in M2, whereas the amounts of carotenoids were nearly identical in both cultures. A simple, rapid and minimum interference with carotenoid and bacteriochlorophyll method to efficiently extract the compounds involving in the formation of 421 nm peak was developed in this study. Assembly of purified MPE with protein components from R. palustris in vitro demonstrated that MPE caused the formation of 421 nm peak. The localization analysis in vivo demonstrated it is MPE associating to protein components and accounting for the peak at ~421 nm. This work clarified the 421 nm peak in vivo mainly originated from MPE accumulation, and will be very helpful to further explore the physiological roles of MPE or its derivatives in photosynthesis.     

Time-reversal symmetry in molecular rovibronic states and in second-order processes

A unified treatment of time-reversal symmetry is given for molecular systems. The treatment allows for interconversion of electronic, rotational, and vibrational angular momenta on equal footing because of a coherent phase choice. It also allows for correlation from a continuous group (of spherical or cylindrical symmetry) to lower point groups (such as C₃, C₄, C₆, S₄, S_g, T, etc.). General, many-electron molecular states that form time-reversal degenerate components are constructed. Attention is called to the Kramers' doublets as the special odd-electron case of such double degeneracy. Specific examples of a spiropentane and a 5-azoniaspiro(4.4) nonane with S₄ symmetry and possible time-reversal degeneracy are given. The optical rotation due to a time-odd polarizability tensor in one of the two time-degenerate components is shown to be of an opposite sign to that in the other component. The above result is from a second-order matrix element (over the polarizability tensor) and is proved to be independent of even- or odd-number of electron spins. It is shown to hold also for Kramers' doubly degenerate components. This result is contrasted with that of a first-order Jahn-Teller effect which depends on the number of electron spins.