Methods for the synthesis of mono- and polynuclear NH-tetrazoles. (Review)

Data on methods for the synthesis of monocyclic and polynuclear NH-unsubstituted tetrazoles are reviewed.Dedicated to Prof. H. Elguero on the occasion of his 65th birthday.St. Petersburg State Technological Institute (Technical University), St. Petersburg 198013, Russia; Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 867–884, July, 2000.     

Brilliant cresyl blue as a new red region fluorescent probe for determination of nucleic acids

A fluorescence quenching method was developed for determination of microamounts of nucleic acids by using brilliant cresyl blue (BCB) as a new red region fluorescent probe. In aqueous hexylmethylene tetramine solution, BCB showed maximum excitation and emission wavelengths at 626 and 670 nm, respectively, and the fluorescence of BCB could be greatly quenched by DNA (or RNA). Under optimal conditions, the calibration graphs are linear over the range of 0.02–0.80 μg/ml for SM DNA and 0.25–1.5 μg/ml for yeast RNA. The corresponding detection limits are 7 ng/ml for SM DNA and 25 ng/ml for yeast RNA, respectively. SM DNA can be determinated in the presence of 40% (w/w) RNA, and the relative standard deviation of six measurements is 2.5% for 500 ng/ml SM DNA. The result of the determination of golden staphylococcus DNA by this method was satisfactory.     

Secondary succession and its effects on soil moisture and nutrition in abandoned old-fields of hilly region of Loess Plateau, China

Floristic composition, community structure and soil moisture and nutrient contents in abandoned fields of different ages were analyzed to clarify the regenerative aspects of succession as a tool for vegetation restoration. The results indicated that secondary succession in this region can be interpreted as an auto-succession: there are main changes in species-relative abundance and species turnover. Annual or biennial species (e.g. Artemisia scoparia), acted as pioneers and strongly dominated the early stages. Then, they underwent a progressive decline, while forbs (e.g. Artemisia sacrorum) and grasses (e.g. Xanthium sibiricum) had their peak abundance at intermediate stages. Dwarf shrubs (e.g. Lespedeza dahurica) and short rhizome grass (e.g. Bothriochloa ischaemum) appeared at mid-succession stage and gradually increased in abundance during succession, becoming dominant at late stages. The first axis of detrended correspondence canonical analysis arranged the sites according to their fallow time, indicating a successional sere. The second axis, associated with diverging pathways of regeneration, correlated with topographic factors and soil moisture and nutrition. Structural divergence between plots increased as succession went on, attained the highest at the mid-succession stage, decreased at the late stage.

Soil moisture and available phosphorus content decreased steadily with field age after their abandonment, whereas pools of organic matter, total and available nitrogen, potassium and total phosphorus increased with field age. The pace and direction of recovery of native vegetation and natural soil properties in these abandoned fields resembled classic old-field succession, which is a form of secondary succession that often serves as a template for guiding restoration efforts. Interface between the abandoned field soil and plant system was crucial to the above process. Our current study supported the generally accepted hypothesis in the succession literature.     

Thin‐Film Infrared Spectroscopy of Acetonitrile

Acetonitrile and [D₃]acetonitrile in the vicinal region of a planar AgX fiber contain linear dipole–dipole linked oligomers as shown by 1) comparison of infrared band intensity ratios in the gaseous and condensed phases and 2) remarkable plots of absorbance (C? N stretch) versus time during evaporation from an AgX planar fiber element. The plots (CH₃CN 2252 cm^?1, CD₃CN 2262 cm^?1) reveal the presence of octamers, hexamers, tetramers, and dimers along with some heptamer, trimer, and monomer structures. A novel isotope effect arises from the somewhat smaller size of the CD₃CN resulting in an increase in the CN band intensity. The organized oligomers may be termed pseudocrystals and are the main components responsible for absorption intensity in the infrared spectrum of acetonitrile, on the AgX planar fiber or in an IR cell.     

Energy transfer rates and impact sensitivities of two classes nitramine explosives molecules

Some explosives are stable molecules with large energy barriers to chemical reaction, and in shock or impact initiation, a sizable amount of phonon energy must be converted to the molecular internal higher vibrations by multiphonon up pumping. To investigate the relationship between impact sensitivities and energy transfer rates, the number of doorway modes of explosive molecules is estimated by a simple theory in which the rate is proportional to the number of normal mode vibrations. We evaluated frequencies of normal mode vibrations of 13 explosive molecules which are CHNO nitramine-contained and have not been analyzed previously. The number of doorway modes in the regions of 200–700 cm⁻¹ was evaluated by the direct counting method. For more clear investigation of the relationship we have classified these 13 nitramine explosive molecules, by the number of nitramine group they contained, into two groups. There are eight molecules that contained one nitramine group and five molecules that contained poly-nitramine groups. It is found that the number of doorway modes shows a linearly correlation to the impact sensitivities derived from drop hammer tests. This result is in agreement with that of several previous works. Besides, it is also noted in our study that in those nitramine explosives molecules with similar molecular structure (similar number nitramine group they contained) and similar molecular weight, the correlation between the sensitivity and the number of doorway modes is higher. We found that the vibrational frequency of ω corresponds to nitro group motions of every molecule is contributed to the number of doorway modes in the regions of 200–700 cm⁻¹.     

The ring opening of cyclopropylidene to allene: global features of the reaction surface

Summary The global features of the groundstate ring opening of cyclopropylidene to allene are studied by means ofab-initio FORS MCSCF calculations based on a minimal AO basis set. The energy surface is completely mapped out in terms of three reaction coordinates, namely the CCC ring-opening angle and two angles describing the rotations of the CH₂ groups. For each choice of these three variables, the twelve remaining internal coordinates are optimized by energy minimization. In the initial phase of the reaction, as the CCC angle opens, the CH₂ groups rotate in a disrotatory manner, maintainingC _s symmetry. This uphill reaction path leads to a transition region which occurs early, for a CCC angle of about 84°. In this transition region the reaction path branches into two pathways which are each others' mirror images. The system exhibits thus abifurcating transition region. Passed this region, the two pathways are overall conrotatory in character. However, these downhill reaction paths to the products are poorly defined because, from a CCC opening angle of about 90° on,the CH ₂ groups can rotate freely and isoenergetically in a synchronized, cogwheel-like manner and this disrotatory motion can mix unpredictably with the conrotatory downhill motion. There is no preference for any one of the two reaction pathways yielding the two stereoisomers of allene and the reaction is thereforenonstereospecific with respect to the numbered hydrogen atoms. The global surface is documented by means of contour maps representing slices corresponding to constant CCC angles. The bifurcating transition region is mapped in detail.Operated for the U.S. Department of Energy by Iowa State University under Contract No. 7405-ENG-82. This work was supported by the office of Basic Energy Sciences     

UHPLC-DAD Characterization of Origanum vulgare L. from Atacama Desert Andean Region and Antioxidant,Antibacterial and Enzyme Inhibition Activities

The Lamiaceae family is an important source of species among medicinal plants highly valued for their biological properties and numerous uses in folk medicine. Origanum is one of the main genera that belong to this family. The purpose of the study was to determine the phenolic composition of the Origanum vulgare extract and evaluate the antimicrobial, antioxidant, and inhibitory activities of this species that grows in the Andean region of the Atacama Desert. High-performance liquid chromatography was performed to determine the main phenols. Rosmarinic acid was identified as the predominant phenolic compound in this species (76.01 mg/100 g DW), followed by protocatechuic acid, which to our knowledge, no previous study reported similar concentrations in O. vulgare. The oregano extract exhibited a content of total phenolic (3948 mg GAE/100 g DW) and total flavonoid (593 mg QE/100 g DW) with a higher DPPH antioxidant activity (IC₅₀ = 40.58 µg/mL), compared to the same species grown under other conditions. Furthermore, it was found to inhibit α-glucosidase activity with an IC₅₀ value (7.11 mg/mL) lower than acarbose (129.32 mg/mL). Pseudomonas syringae and Pantoea agglomerans (both MIC 0.313 mg/mL and MBC 1.25 mg/mL) were the bacteria most susceptible to oregano extract with the lowest concentration necessary to inhibit bacterial growth. These results open the door for the potential use of this plant to manage chronic diseases, and they expand the knowledge of the species cultivated in arid environmental conditions.     

Screening of exon methylation biomarkers for colorectal cancer via LC‐MS/MS strategy

The identification of biomarkers would be of benefit for the diagnosis and treatment of colorectal cancer. DNA methylation in specific genomic regions, which had shown strongly association with disease genotypes, was an effective indicator to reveal the occurrence and development of cancers. To screen out methylation biomarkers for colorectal cancer (CRC), genomic DNA was isolated from colorectal cancerous and corresponding cancer‐adjacent tissues collected from 30 CRC patients and then bisulfite‐converted. The exon regions of 5 targeted genes (CNRIP1 , HIC1 , RUNX3 , p15 , and SFRP2 ) were amplified by using nested polymerase chain reaction with specific primers, and the amplicon was purified and hydrolyzed. The methylation levels of these specific regions were detected by liquid chromatography tandem mass spectrometry (LC‐MS/MS). The results showed that 5 targeted exon regions were successfully amplified and confirmed by sequencing. The methodological validations indicated that LC‐MS/MS was highly sensitive and accurate. The methylation levels of CNRIP1 and RUNX3 were remarkably high in CRC tissues with statistical difference when compared with corresponding cancer‐adjacent individuals, while that of HIC1 , p15 , and SFRP2 had no difference between 2 subjects. These findings supported CNRIP1 and RUNX3 as potential DNA methylation biomarkers for CRC diagnosis and treatment, and our LC‐MS/MS approach exhibited great advantages in the identification of regional DNA methylation biomarkers.     

一种解无约束优化问题的新的非单调自适应信赖域方法

本文提出了一种解无约束优化问题的新的非单调自适应信赖域方法.这种方法借助于目标函数的海赛矩阵的近似数量矩阵来确定信赖域半径.在通常的条件下,给出了新算法的全局收敛性以及局部超线性收敛的结果,数值试验验证了新的非单调方法的有效性.