Gold catalysis in quinoline synthesis.

Quinolines are biologically and pharmaceutically important N-heterocyclic aromatic compounds, which have broad applications in medicinal chemistry. Thus, their efficient synthesis has attracted extensive attention, and a broad range of synthetic strategies have been established. Of note, gold-catalyzed methodologies for the synthesis of quinolines have greatly advanced this field. Various gold-catalyzed intermolecular annulation reactions, such as annulations of aniline derivatives with carbonyl compounds or alkynes, annulations of anthranils with alkynes, and annulations based on A3-coupling reactions, as well as intramolecular cyclization reactions of azide-tethered alkynes, 1,2-diphenylethynes, and 2-ethynyl N-aryl indoles, have been developed. This review provides an overview of this exciting research area. Typical achievements in reaction methodologies and plausible reaction mechanisms are summarized.

Gold-Catalyzed Cyclization/Hydroboration of 1,6-Enynes: Synthesis of Bicyclo[3.1.0]hexane Boranes.

The gold-catalyzed cyclization/hydroboration of 1,6-enynes offers facile, versatile, and atom-economical one-step access to bicyclo[3.1.0]hexane boranes. This new protocol proceeds in moderate to good yields under mild conditions. Different from bicyclo[3.1.0]hexane borates, these products are stable in air and during chromatography. Moreover, the borane moiety of the products can readily undergo a diverse array of transformations. The kinetic isotope effect experiment indicates that the hydrogen-transfer step is a fast process, which is not involved in the rate-limiting step.

Stereoselective ZnCl2-Catalyzed B-H Bond Insertion of Vinyl Carbenes Generated from Cyclopropenes for the Synthesis of Allylboranes.

Zinc-catalyzed insertion of vinyl carbenes generated from cyclopropenes into the B-H bonds of Lewis base-borane adducts for concise and efficient access to allylboranes has been developed. This protocol represents the first zinc-catalyzed B-H bond insertion of carbenes for organoborane compounds. In this protocol, inexpensive ZnCl2, with low toxicity, is used as the catalyst. This simple ligand-free catalytic system affords allylboranes in yields up to 92%, with E/Z ratios of >20:1. Besides, this new protocol offers a broad scope of Lewis base-borane adducts, which are not easily obtained by other catalytic methods for metal carbene insertion into B-H bonds. The potential synthetic applicability of this new methodology is exemplified by a gram-scale experiment and synthetic transformation of the products.

Root growth and architecture of Tamarix chinensis in response to the groundwater level in the Yellow River Delta.

AIMS: Investigate the growth adaptation law of the Tamarix chinensis root system in response to the groundwater level in a muddy coastal zone. METHODS: The high groundwater level (0.7-0.9 m), medium groundwater level (1.1-1.3 m) and low groundwater level (1.5-1.7 m) T. chinensis forests on the beaches of the Yellow River Delta were used as the research objects. Full excavation methods were used to excavate root systems with different groundwater levels; then, the aboveground biomass, root biomass, root spatial distribution, root topological structure and fractal characteristics of T. chinensis response characteristics to groundwater level were measured and analysed. RESULTS: The results showed that with the decrease in the groundwater level, the soil water content and soil salt content showed upward trends. At high groundwater levels, T. chinensis reduced root biomass allocation to reduce the damage to roots caused by salinity. At low groundwater levels, T. chinensis strengthened the development of root systems, which greatly enhanced the ability of T. chinensis to balance its water intake. The root biomass at the high groundwater level was 43.06% lower than that at the low groundwater level. The relationship between root and shoot growth of T. chinensis at high groundwater levels and medium groundwater levels indicated allometric growth, and at low groundwater levels, roots and shoots grew uniformly. The root distribution of T. chinensis tended to be shallow at the different groundwater levels, showing the characteristics of a horizontal root type. At high groundwater levels, the root topological structure tended to be dichotomous, and the fractal dimension and fractal abundance values were both large, at 1.31 and 2.77, respectively. The branch complexity increased to achieve spatial expansion and increase plant stability. However, the topological structure of the medium and low groundwater level T. chinensis tended to be herringbone-like, the fractal dimension and fractal abundance values were small, the second branch was limited, and the structure was simple. The topological structure and fractal characteristics of the T. chinensis root system responded to different groundwater levels in a coordinated manner. CONCLUSIONS: Based on the differences in the growth and architecture of the T. chinensis root system, the T. chinensis root system has strong phenotypic plasticity to the heterogeneous water-salt habitat of the groundwater-soil system, and the T. chinensis root system shows strong root adaptability to water and salt stress.

Copper(I)-catalyzed tandem synthesis of 2-acylquinolines from 2-ethynylanilines and glyoxals.

An efficient one-step synthesis of 2-acylquinolines using a copper-catalyzed tandem reaction of 2-ethynylanilines with glyoxals in the presence of piperidine has been developed. This new protocol successfully avoids multi-step operation and the use of highly toxic cyanides required in traditional methods, and provides a practical tool for synthetic and pharmaceutical chemists. Various 2-acylquinolines are obtained with perfect regioselectivity in moderate to good yields (up to 86%). The potential synthetic utility of this method is exemplified by a large-scale experiment and synthetic transformation of the products.

[Soil amelioration of different vegetation types in saline-alkali land of the Yellow River Delta, China]. / 黄河三角洲盐碱地不同植被模式的土壤改良效应.

Yellow River Delta is an important distribution area of coastal saline-alkali land in China. Revegetation is the main technology for ecological restoration during saline-alkali land amelioration. To explore the effects of different vegetation types on soil improvement in saline-alkali land and get the suitable model in the Yellow River Delta, four tree-grass compound models, Salix americana+Distichlis spicata, S. matsudana+D. spicata, Tamarix chinensis+Medicago sativa, and Fraxinus chinensis+T. chinensis+M. sativa, were set up, with pure S. americana forest as the control. Twenty indicators, including soil moisture physical parameters, saline-alkali content, soil nutrient contents, and microorganism quantity etc. were measured. Principal component analysis, cluster analysis and fuzzy mathematics were used to evaluate soil modification effect of different vegetation combinations. The results showed that all compound models significantly improved soil physical and che-mical properties in coastal saline-alkali land by increasing soil porosity, soil water storage, soil organic matter content, available nutrient content and soil microorganism quantity and reducing soil density. Among all the models, the tree-shrub-grass mixed model of F. chinensis+T. chinensis+M. sativa was the most effective in inhibiting salt and alkali stress and increasing soil nutrients and microorganism abundance, whereas the tree-grass mixed model of S. matsudana+D. spicata was the most effective in improving soil water physical properties. The combined effects of different vegetation patterns on soil amelioration in coastal saline-alkali land of the Yellow River Delta were arranged in order of F. chinensis+T. chinensis+M. sativa> S. matsudana+D. spicata> S. americana+D. spicata> T. chinensis+M. sativa.

Dual gold catalysis - an update.

This review summarizes the recent developments in the field of dual gold activation chemistry. New developments including synthetic strategies, latest mechanistic insights, computational studies and the identification and isolation of key intermediates, are discussed.

Transport characteristics of salt ions in soil columns planted with Tamarix chinensis under different groundwater levels.

The groundwater level is the main factor affecting the distribution of soil salinity and vegetation in the Yellow River Delta (YRD), China, but the response relationship between the spatial distribution of soil salt ions and the groundwater level in the soil-Tamarix chinensis system remains unclear. In order to investigate the patterns of soil salt ions responding to groundwater levels, in the 'groundwater-soil-T. chinensis' system. Soil columns planted with T. chinensis, a constructive species in the YRD, were taken as the study object, and six groundwater levels (0.3, 0.6, 0.9, 1.2, 1.5 and 1.8 m) were simulated under saline mineralization. The results demonstrated the following: As affected by groundwater, Na+ and Cl- were the main ions in the T. chinensis-planted soil column, with a trend of decreasing first and then increasing by the increase of soil depth. However, the contents of K+ and NO3- gradually decreased and CO32-+HCO3- gradually increased. As affected by groundwater evaporation, all the salt ions except CO32-+HCO3- exhibited different degrees of surface aggregation in the 0-20 cm layer. However, due to the impact of root uptake, the contents of the salt ions rapidly decreased in the root distribution layer (20-50 cm soil layer), which rendered a turning-point layer that was significantly lower than the surface soil layer; such decreases in ion contents showed a relatively large rate of variation. In the whole T. chinensis-planted soil column, with increasing groundwater level, the contents of Na+, Cl-, Ca2+, Mg2+, and NO3- all tended to first decrease, then increase and decrease again, but the content of CO32-+HCO3- first decreased and then increased. Therefore, the 0.9 m groundwater level was the turning point at which the main salt ions underwent significant changes. The contents of Na+, Cl-, Ca2+ and Mg2+ in the T. chinensis planted soil column exhibited moderate variability (14.46%111.36%) at most groundwater level except less than 0.9 m. Therefore, planting T. chinensis could effectively reduce the accumulation of salt ions in the 20-50 cm soil layer with a concentrated root distribution, suggesting that the planting depth of T. chinensis should be greater than 20 cm under saline mineralization. This study can provide references for the control of soil secondary salinization and the management of T. chinensis seedling cultivation under saline mineralization.

Molecular Insights into the Potential Insecticidal Interaction of ß-Dihydroagarofuran Derivatives with the H Subunit of V-ATPase.

Celangulin V (CV), one of dihydroagarofuran sesquiterpene polyesters isolated from Chinese bittersweet (Celastrus angulatus Maxim), is famous natural botanical insecticide. Decades of research suggests that is displays excellent insecticidal activity against some insects, such as Mythimna separata Walker. Recently, it has been validated that the H subunit of V-ATPase is one of the target proteins of the insecticidal dihydroagarofuran sesquiterpene polyesters. As a continuation of the development of new pesticides from these natural products, a series of ß-dihydroagarofuran derivatives have been designed and synthesized. The compound JW-3, an insecticidal derivative of CV with a p-fluorobenzyl group, exhibits higher insecticidal activity than CV. In this study, the potential inhibitory effect aused by the interaction of JW-3 with the H subunit of V-ATPase c was verified by confirmatory experiments at the molecular level. Both spectroscopic techniques and isothermal titration calorimetry measurements showed the binding of JW-3 to the subunit H of V-ATPase was specific and spontaneous. In addition, the possible mechanism of action of the compound was discussed. Docking results indicated compound JW-3 could bind well in 'the interdomain cleft' of the V-ATPase subunit H by the hydrogen bonding and make conformation of the ligand-protein complex become more stable. All results are the further validations of the hypothesis, that the target protein of insecticidal dihydroagarofuran sesquiterpene polyesters and their ß-dihydroagarofuran derivatives is the subunit H of V-ATPase. The results also provide new ideas for developing pesticides acting on V-ATPase of insects.

Exploration of Novel Botanical Insecticide Leads: Synthesis and Insecticidal Activity of ß-Dihydroagarofuran Derivatives.

The discovery of novel leads and new mechanisms of action is of vital significance to the development of pesticides. To explore lead compounds for botanical insecticides, 77 ß-dihydroagarofuran derivatives were designed and synthesized. Their structures were mainly confirmed by (1)H NMR, (13)C NMR, DEPT-135°, IR, MS, and HRMS. Their insecticidal activity was evaluated against the third-instar larvae of Mythimna separata Walker, and the results indicated that, of these derivatives, eight exhibited more promising insecticidal activity than the positive control, celangulin-V. Particularly, compounds 5.7, 6.6, and 6.7 showed LD50 values of 37.9, 85.1, and 21.1 µg/g, respectively, which were much lower than that of celangulin-V (327.6 µg/g). These results illustrated that ß-dihydroagarofuran ketal derivatives can be promising lead compounds for developing novel mechanism-based and highly effective botanical insecticides. Moreover, some newly discovered structure-activity relationships are discussed, which may provide some important guidance for insecticide development.

Design, synthesis and cytotoxic activity of a novel series of steroidal phenylpyrazoles.

Thirty novel steroidal pyrazole derivatives were designed and synthesized via a highly efficient route from pregnenolone (1) as starting material. The key intermediates 3a-c were obtained under Vilsmeier conditions, and the subsequent hydrolysis, acetylation or Borch reduction afforded thirty target compounds. These compounds were mainly characterized by (1)H NMR, (13)C NMR, DEPT135°. The structure of compound 3a was also confirmed by X-ray single crystal diffraction. The cytotoxicity of these compounds was evaluated by the SRB method against four cancer cell lines, including A549, Hela, MCF-7 and HepG2, and the results indicated that compounds 5a, 6a, 7a and 8a exhibited significant cytotoxicity with IC50 values ranging from 0.91 to 5.44 µM. Most importantly, compound 5a exhibited excellent cytotoxicity against A549 with an IC50 value of 0.91 µM. On the basis of our research the structure-activity relationships (SAR) of these compounds were discussed. This work provides some important hints for further structural modification of steroids towards developing novel and highly effective anticancer drugs.

Responses of Water and Salt Parameters to Groundwater Levels for Soil Columns Planted with Tamarix chinensis.

Groundwater is the main water resource for plant growth and development in the saline soil of the Yellow River Delta in China. To investigate the variabilities and distributions of soil water and salt contents at various groundwater level (GL), soil columns with planting Tamarix chinensis Lour were established at six different GL. The results demonstrated the following: With increasing GL, the relative soil water content (RWC) declined significantly, whereas the salt content (SC) and absolute soil solution concentration (CS) decreased after the initial increase in the different soil profiles. A GL of 1.2 m was the turning point for variations in the soil water and salt contents, and it represented the highest GL that could maintain the soil surface moist within the soil columns. Both the SC and CS reached the maximum levels in these different soil profiles at a GL of 1.2 m. With the raise of soil depth, the RWC increased significantly, whereas the SC increased after an initial decrease. The mean SC values reached 0.96% in the top soil layer; however, the rates at which the CS and RWC decreased with the GL were significantly reduced. The RWC and SC presented the greatest variations at the medium (0.9-1.2 m) and shallow water levels (0.6 m) respectively, whereas the CS presented the greatest variation at the deep water level (1.5-1.8 m).The RWC, SC and CS in the soil columns were all closely related to the GL. However, the correlations among the parameters varied greatly within different soil profiles, and the most accurate predictions of the GL were derived from the RWC in the shallow soil layer or the SC in the top soil layer. A GL at 1.5-1.8 m was moderate for planting T. chinensis seedlings under saline groundwater conditions.

Insecticidal Pregnane Glycosides from the Root Barks of Periploca sepium.

To explore novel lead compounds for botanical pesticides from natural sources, a new pregnane glycoside (periplocoside) P2 as well as its isomer, a known pregnane glycoside P1, were isolated from the root barks of Periploca sepium using a bioactivity-guided method, and their structures were confirmed by ID NMR, 2D NMR, IR, ESI-MSn and HRMS. Their insecticidal activities were evaluated against 3rd instar larvae of M separata, and the results indicated that P2 exhibited excellent insecticidal activity with LC50 values of 2.9 and 2.2 mg/mL after 24 and 48 h, respectively, much lower than those of the positive control celangulin-V (24.7 and 21.0 mg/mL after 24 and 48 h, respectively). This work demonstrated that pregnane glycosides from Periploca sepium could be promising lead compounds for developing botanical pesticides urgently needed in agriculture.

Synthesis and insecticidal activity of ß-dihydroagarofuran ether analogues.

BACKGROUND: 1ß, 2ß, 4α, 6α, 8ß, 9α, 12-hepthydroxyl-ß-dihydroagarofuran is the main skeleton of ß-dihydroagarofuran sesquiterpenoids, which exhibit excellent insecticidal activity. To study further the structure-activity relationship of ß-dihydroagarofuran sesquiterpenoids towards finding novel botanical pesticides, two series of new structurally modified ether analogues were designed and synthesised, and their insecticidal activities were evaluated. RESULTS: Twenty-two ether derivatives were synthesised using 1ß, 2ß, 4α, 6α, 8ß, 9α, 12-hepthydroxyl-ß-dihydroagarofuran as starting material. Bioassay results indicated that most of the derivatives, particularly compounds 5.1.2, 5.1.3, 5.1.7, 5.2.3, 5.2.6 and 5.2.7, exhibited significant insecticidal activity against the third-instar larvae of the oriental armyworm Mythimna separata. Most importantly, compound 5.2.7 showed the lowest LD50 value of 29.2 µg g(-1) among these synthesised compounds, which provides some important hints for further design, synthesis and structural modification of ß-dihydroagarofuran sesquiterpenoids towards developing novel botanical insecticides. CONCLUSION: The structure-activity relationship illustrated that the moiety at the 1-position affected the insecticidal activity significantly, and that specifically the derivatives with two or three carbon atoms at the 1-position showed promising insecticidal activity, with mortality over 60%, while those with o-F-Bn and p-F-Bn at the 6-position showed similar activity.

[Using atomic fluorescence spectrometry to study the spatial distribution of As and Hg in orchard soils].

Aqua regia digestion, double channels-atomic fluorescence spectrometry method was used to determine the concentrations of As and Hg in orchard soils of Qixia City - the main apple production area of Shandong province. Validate The detection limitation, accuracy and precision of the method were validated, the spatial distribution was analyzed, and the characteristics of As and Hg pollution in Qixia orchard soils were assessed. The results showed that the range of As concentration in Qixia soils is between 2.79 and 20.93 mg x kg(-1), the average concentration is 10.59 mg x kg(-1), the range of Hg concentration in Qixia soil is between 0.01 and 0.79 mg x kg(-1), the average concentration is 0.12 mg x kg(-1). The variation of As concentration in soils is small, whereas that of Hg concentration is large. Frequency distribution graphics of As and Hg showed that the concentration of As in soils is according with the normal distribution approximately and the concentrations are mostly between 7 and 15 mg x kg(-1), the concentration of Hg in soil isn't according with the normal distribution and the concentrations are mostly between 0.03 and 0.21 mg x kg(-1). The correlations between the concentrations of As or Hg in soils and the nutrient are not significant and there is no significant correlation even between As and Hg. Based on the environmental technical terms for green food production area, the As concentration in orchard soil of Qixia City is at clean level, but there are 4.76% of sample points with Hg pollution index exceeding 1, and this should be attracted the attention of the administrators.

[Research on fuzzy proportional-integral-derivative control of master-slave minimally invasive operation robot driver].

Robotic catheter minimally invasive operation requires that the driver control system has the advantages of quick response, strong anti-jamming and real-time tracking of target trajectory. Since the catheter parameters of itself and movement environment and other factors continuously change, when the driver is controlled using traditional proportional-integral-derivative (PID), the controller gain becomes fixed once the PID parameters are set. It can not change with the change of the parameters of the object and environmental disturbance so that its change affects the position tracking accuracy, and may bring a large overshoot endangering patients' vessel. Therefore, this paper adopts fuzzy PID control method to adjust PID gain parameters in the tracking process in order to improve the system anti-interference ability, dynamic performance and tracking accuracy. The simulation results showed that the fuzzy PID control method had a fast tracking performance and a strong robustness. Compared with those of traditional PID control, the feasibility and practicability of fuzzy PID control are verified in a robotic catheter minimally invasive operation.

[Study of arsenic concentration and distribution in shell sand of the shell ridge islands by hydride generation atomic fluorescence spectrometry].

The present paper determined the As concentration in shell sand of the shell ridge islands by hydride generation atomic fluorescence spectrometry, studied the distribution of As in shell sand of the shell ridge islands, analysed the correlations of As with other nutrient elements, and discussed the probably influencing factors affecting the As concentration and distribution in shell sand. The results showed that the range of the arsenic concentration in shell sand is between 0.78 and 8.76 mg x kg(-1), the average concentration is 3.11 mg x kg(-1), and this indicated that the As contamination of the shell ridge island is in clean level. The As concentration of the shell sand has a increasing trend followed by the increase with profile depth or the decrease with the particle size, and the difference in As concentrations in shell sand of different particle sizes reached the significant level (p < or = 0.05). The As concentration in shell sand has a very significant positive correlation with the concentrations of Cu, Zn and Mn as well as the TP and TK, whereas the correlations between As and TN or Fe are not significant. The pollutant of As in the shell sand mainly comes from the absorption and fixation by shell sand from the environment but not the accumulation of the shell organism during their growing up.

Automatic identification and morphometry of optic nerve fibers in electron microscopy images.

The neuroanatomical morphology of the optic nerve is an important description for understanding different aspects like topological distribution of nerves. Manual identification and morphometry has been usually considered as tedious, time consuming, and susceptible to error. A method that automates the identification and analysis of axons from electron micrographic images is presented. First, using region growing approach binarizes the image by combining the feature information together with spatial information, and obtains a coarse classification between myelin and non-myelin pixels. Next, identifies the axon candidates by region labeling and remove false axons on the basis of the identification ruler. Then the connected myelin sheaths are separated from each other using the maximum gradient magnitude of the outer annulus. Finally, analyses the morphological data of fibers. The developed method has been tested on a number of optic nerve images and results were presented. Regional distributions of axon caliber were unimodal. The thickness of the myelin sheath was highly correlated with the fiber diameter; hence, myelin sheath width was also distributed in a unimodal manner.

[Extraction of organochlorine pesticides using ASE from wastewater irrigated agricultural soil].

The extraction efficiency of accelerated solvent extraction (ASE) was studied for organochlorine pesticide residuals in soil and compared with that of Soxhlet. The results showed that the efficiency of ASE was generally better than Soxhlet when used for DDT measurement, and equivalent to Soxhlet for BHCs. With ASE, organochlorine pesticide residues were detected in wastewater irrigated and non-wastewater irrigated soils from Tianjin. alpha-BHC, beta-BHC, delta-BHC, gamma-BHC, p,p'-DDE, p,p'-DDD, p,p'-DDT, o,p'-DDT ranged from 7.5 to 71.1 ng/g in wastewater irrigated vegetable and maize field and from 3.0 to 16.5 ng/g in wastewater irrigated paddy field. The eight pesticide residues from non-wastewater irrigated vegetable and maize field was in a range of 3.1-17.6 ng/g.