Efficient synthesis of pyrano[2,3-b]pyridine derivatives using microwave or solar energy

Pyranopyridine derivatives are an important class of heterocyclic compounds due to their biological activities such as antitumor and antibacterial. However, conventional procedures for their synthesis produce large amounts of toxic by-products. Therefore, there is a need to develop simple, efficient and environmentally benign procedures. Here, a one-pot multicomponent protocol is designed for the synthesis of pyrano[2,3-b]pyridone derivatives by reaction of equimolar amounts of 6-hydroxy-1,4-dimethyl-1,2-dihydropyridines, aryl aldehydes and malononitrile, using both microwave heating and solar thermal energy in aqueous EtOH (50%) in the presence of a catalytic amount of K₂CO₃. The products were obtained in 84–90% yields in 10–20 min by microwave heating, and in 90–96% yields in 2–3 h using solar energy.     

Direct synthesis of 2,4,5-trisubstituted imidazoles from alcohols and α-hydroxyketones by microwave

This article reports a fast, simple and efficient method to synthesize highly substituted imidazoles. Green organic synthesis is needed to face current environmental pollution. For instance the replacement of hazardous organic compounds by safe alternatives is particularly relevant. Ionic liquids are an environmentally friendly alternative to conventional organic solvents due to their unique physicochemical properties. Substituted imidazoles have been widely used to prepare pharmaceuticals. Many synthetic approaches have been developed to produce substituted imidazoles. However, despite considerable efforts only a few green methods are reported for the synthesis of highly substituted imidazoles. Here a straightforward and atom-economic approach is reported to synthesize a series 2,4,5-trisubstituted imidazoles directly from α-hydroxyketones and alcohols employing 1-methyl-3-H-imidazolium nitrate as a promoter and medium under microwave irradiation. The protocol has several advantages such as high yields of 77–91 %, short reaction times of 6–8 min, easy purification processes, and methodological simplicity due to the formation of carbon–carbon and carbon–heteroatom bonds in a single step. The methodology has been further extended towards the facile synthesis of Trifenagrel in good yield. This method provides new opportunities for the rapid screening of a wide range of compounds, either for the development of new drugs or total synthesis of natural products.     

林木根系衰老研究方法与机制

根系衰老研究方法主要有根窗直接观测和挖根取样间接观测。在整株水平上,树木同化碳的能力,碳在不同器官间的分配,尤其是在地上部分和地下部分间的分配比例,对根的萌生和衰老起着重要作用;地上部分的生长过程和健康状况也对根系的生长和寿命有很大影响;当树木的生长环境受到某种胁迫时,树木的抵抗力下降,容易招致病原菌的危害,造成根系衰老和死亡。在生态系统水平上,干旱洪涝、干扰等胁迫和树木一土壤间的养分循环都会引起树木生长环境的改变,对根系的衰老过程发生作用;季节变化使树木的地上部分和地下部分的生理活动处于不同的旺盛期,从而使碳的分配方式有些改变,影响到根系的生长;土壤中养分的存在形式,某些离子的浓度也直接影响到根的寿命;病原菌对根系的危害与土壤中养分含量变化有关。所以,衰老过程受环境条件的影响,伴随着代谢,RNA和蛋白质合成速率的下降和(或)膜与细胞器结构的改变。     

Synthesis of carboxylic dithiocarbamic anhydride and substituted thiourea derivatives in water

The use of water as a solvent has sometimes benefits such as improving reactivities and selectivities, simplifying work-up procedures, and environmentally benign. Many carboxylic dithiocarbamic anhydride products are valuable building blocks in heterocycles and natural products. Here we present a simple one-pot synthesis of carboxylic dithiocarbamic anhydride by condensation of amines, carbon disulfide, acyl halide, or acetic anhydride in water. We obtained a variety of biologically important acyl dithiocarbamate derivatives in 82–93% yields in 10–30 min. This procedure can be used for the synthesis of thioureas from dithiocarbamates. Here, the sequential, one-pot three-component reaction of amines, carbon disulfide, and isothiocyanates provides unsymmetrical substituted thioureas in 81–91% yields.     

Application of Zr(IV) tungstate for removal of metal ions from aqueous solutions

A heteropolyacid Zr(IV) tungstate-based cation exchanger has been synthesized. An amorphous sample, prepared at pH 1.2 and having a Na⁺ ion exchange capacity of 0.92?meq?g^?1, was selected for further studies. Its physicochemical properties were determined using Fourier transform infrared spectrometer, X-ray diffraction, thermogravimetric, and scanning electron studies. To understand the cation exchange behavior of the material, distribution coefficients (K _d) for metal ions in various solvent systems were determined. Some important binary separations of metal ions, namely Mg²⁺–Bi³⁺, Cd²⁺–Bi³⁺, Fe³⁺–Bi³⁺, Th⁴⁺–Bi³⁺, and Fe³⁺–Zn²⁺, were achieved on such columns. The practical utility of these separations was demonstrated by separating Fe³⁺ and Zn²⁺ ions quantitatively in commercial pharmaceutical formulation. The cation exchanger has been successfully applied also for the treatment of industrial wastewater and a synthetic mixture. All the results suggests that Zr(IV) tungstate has excellent potential for the removal of metals from aqueous systems using packed columns of this material.     

Fast 62–92 % yield preparation of amino acid dithiocarbamates in green solvent at room temperature

Dithiocarbamate and their derivatives are of importance in medicinal chemistry due to their biological activities, in agriculture as fungicides and in organic synthesis as versatile synthetic intermediates. Green solvents such as deep eutectic solvents and polyethylene glycol are new emerging alternatives to conventional harmful organic solvents. Here, we report the synthesis of amino acid–based dithiocarbamates by one-pot three-component reaction of the electrophilic reagent, carbon disulfide and α-amino acids in deep eutectic solvent and polyethylene glycol as a catalyst and reaction media. In situ preparation of dithiocarbamates by the reaction of different amino acids and carbon disulfide, followed by addition reaction with epoxides, alkyl halides and α, β-unsaturated enones at room temperature, gave the corresponding products in 62–92 % yield with a short reaction time without any tedious workup procedures. The deep eutectic solvents and polyethylene glycol were recycled without activity or yield decrease. Therefore, the synthesis of amino acid–based dithiocarbamates in green solvents is a promising alternative to previously used procedures.     

Governing trade-offs in ecosystem services and disservices to achieve human–wildlife coexistence

Sustaining wildlife populations, which provide both ecosystem services and disservices, represents a worldwide conservation challenge. The ecosystem services and Ostrom's social–ecological systems frameworks have been adopted across natural and social sciences to characterize benefits from nature. Despite their generalizability, individually they do not include explicit tools for addressing the sustainable management of many wildlife populations. For instance, Ostrom's framework does not specifically address competing perspectives on wildlife, whereas the ecosystem services framework provides a limited representation of the social and governance context wherein such competing perspectives are embedded. We developed a unified social–ecological framework of ecosystem disservices and services (SEEDS) that advances both frameworks by explicitly acknowledging the importance of competing wildlife perspectives embedded in the social and governance contexts. The SEEDS framework emulates the hierarchical structure of Ostrom's social–ecological systems, but adds subsystems reflecting heterogeneous stakeholder views and experiences of wildlife-based services and disservices. To facilitate operationalizing SEEDS and further broader analyses across human–wildlife systems, we devised a list of variables to describe SEEDS subsystems, such as types and level of services and disservices, cost and benefit sharing, and social participation of stakeholders. Steps to implement SEEDS involve engaging local communities and stakeholders to define the subsystems, analyze interactions and outcomes, and identify leverage points and actions to remedy unwanted outcomes. These steps connect SEEDS with other existing approaches in social–ecological research and can guide analyses across systems or within individual systems to provide new insights and management options for sustainable human–wildlife coexistence.     

A facile eco-friendly approach for the one-pot synthesis of 3,4-dihydro-2<Emphasis Type="Italic">H</Emphasis>-naphtho[2,3-<Emphasis Type="Italic">e</Emphasis>][1,3]oxazine-5,10-diones using glycerol as a green media

1,3-Oxazines have a wide variety of biological activities. Naphthoquinone scaffolds also exhibit several biological responses such as antithrombotic, apoptosis and lipoxygenase inhibitors. There is, therefore, a need to develop efficient green methodologies for hybridizing the two scaffolds in a single entity. Herein, we report a novel protocol for the synthesis of 3-aryl-3,4-dihydro-2H-naphtho[2,3-e][1,3]oxazine-5,10-diones by one-pot three-component condensation of 2-hydroxy-1,4-naphthoquinone, aromatic amines and formaldehyde in glycerol at 50 °C. After separation of products, the glycerol–water layer was extracted using ethyl acetate and the dried glycerol layer was successfully reused several times. The products were obtained in 85–95 % yields in 5–10 min. This environmentally benign protocol holds advantages of high yields, operational simplicity and easy workup over our earlier report.     

Assessing environmental factors in red spruce (Picea rubens Sarg.) growth in the Great Smoky Mountains National Park, USA: From conceptual model, envirogram, to simulation model

This study provides a method for assessing a multiplicity of environmental factors in red spruce growth in the Great Smoky Mountains National Park (GSMNP) of Southeastern USA. Direct and indirect factors in the annual growth increment are first organized into a schematic input-output envirogram (ARIRS), and this information is then used to construct a simulation model (ARIM). The envirogram represents a structured conceptualization of most environmental factors involved in growth, as developed from relevant literature. This interdisciplinary synthesis distinguishes direct vs. indirect factors in growth and takes account of the systems ecology concept that indirect factors may be as important as or more important than direct ones in regulating growth. The ARIRS envirogram summarizes hierarchically organized, within- and cross-scale, local-to-global interactions, and its construction makes it obvious that growth is influenced by many cross-scale spatiotemporal interactions. More research on genecology is still needed to clarify the role of phenotypic plasticity and adaptive capacity in nutrient cycling, global change, and human disturbance.     

Evidence of new particle formation during post monsoon season over a high-altitude site of the Western Ghats,India

The formation of ultrafine particles, their growth, and associated characteristic features has been studied during new particle formation events over a high-altitude station of the Western Ghats during the 2014 post-monsoon season. Most of the events were observed during noon time where particle bursts in the nucleation-mode size range from 5 to 25 nm followed by sustained growth in size. This phenomenon persists for ～4–8 h with a growth rate of 1–2 nm h^–1. Peak concentrations of nucleation-mode particles during the event generally vary from 2300 to 5000 cm^–3. The mean growth rate is 1.4 ± 0.42 nm h^–1, particle formation rate is 1.14 ± 0.22 cm^–3 s^–1, coagulation sink is 0.35 ± 0.22 cm^–3 s^–1, and condensational sink is 15.4 ± 2.6?×?10^–3 s^–1. All these values are comparable with earlier results from Indian region. Comparison of size-segregated particle number concentration during days of new particle formation events and those without new particle formation were carried out showing a distinct variation in nucleation and Aitken mode with least variability associated with the accumulation mode.     

Protein synthesis and growth inOctopus vulgaris

Rates of protein synthesis in the whole body and tissues ofOctopus vulgaris collected in September 1985 and 1986 from the Bay of Naples were measured following a flooding dose injection of³H phenylalanine. There were stable phenylalanine free pool-specific radioactivities and linear incorporation of radiolabel into arm-tip protein from 10 to 30 min after the injection. In starved individuals there were no significant differences between the fractional rates of protein synthesis of the following tissues: ventricle, brain, branchial heart, arm tip, gill, stomach, arm, renal appendage and mantle. The mean value (± SE) for all the tissues was 3.02 ± 0.17% d^–1. In individuals fed varying amounts of crab, resulting in differing growth rates, there was a linear increase in fractional rates of whole-body protein synthesis with growth rate. A standard 148 g octopus growing at 3.0% d^–1 synthesised 0.54 g of protein, with 0.43 g of this protein retained as growth. The proportion of the total protein synthesis which was retained as growth increased with increasing growth rate; at a maximum growth rate of 6% d^–1, over 90% of the protein synthesised was retained as growth. The ventricle, arm tip, gill, arm and mantle also showed similar patterns of a linear increase in fractional rates of protein synthesis with increased growth rates. The RNA concentrations in the whole body and tissues increased with increasing growth rates, but the major change was an increase in the efficiency of translation. It is concluded that rapid growth rates inO. vulgaris are brought about by high rates of protein synthesis and high efficiencies of retention of synthesised protein and, therefore, little protein degradation.     

Toxicity,degradation and analysis of the herbicide atrazine

Excessive use of pesticides and herbicides is a major environmental and health concern worldwide. Atrazine, a synthetic triazine herbicide commonly used to control grassy and broadleaf weeds in crops, is a major pollutant of soil and water ecosystems. Atrazine modifies the growth, enzymatic processes and photosynthesis in plants. Atrazine exerts mutagenicity, genotoxicity, defective cell division, erroneous lipid synthesis and hormonal imbalance in aquatic fauna and nontarget animals. It has threatened the sustainability of agricultural soils due to detrimental effects on resident soil microbial communities. The detection of atrazine in soil and reservoir sites is usually made by IR spectroscopy, ELISA, HPLC, UPLC, LC–MS and GC–MS techniques. HPLC/LC–MS and GC–MS techniques are considered the most effective tools, having detection limits up to ppb levels in different matrices. Biodegradation of atrazine by microbial species is increasingly being recognized as an eco-friendly, economically feasible and sustainable bioremediation strategy. This review presents the toxicity, analytical techniques, abiotic degradation and microbial metabolism of atrazine.     

Highly efficient microwave-assisted one-pot synthesis of 4-aryl-2-aminothiazoles in aqueous medium

The thiazole ring system is one of the most important heterocycles in nature, as it represents an important structural motif of many biological compounds, including vitamin B₁ (Thiamin), carboxylase and penicillin. There is, therefore, an urgent need to design rapid, efficient and environmentally benign protocols for the synthesis of thiazoles. Herein, we have developed a one-pot protocol for the synthesis of 4-aryl-2-aminothiazoles from the reaction of aromatic ketones, NBS (N-Bromosuccinimide) and thioureas under microwave irradiation at 80–85 °C in PEG (polyethylene glycol)-400 and water as a green reaction medium. The products were obtained in 84–89% yields in 28–32 min. The method has several advantages such as use of green solvent, easy work-up, excellent yield and avoiding use of lachrymatric α-haloketones.     

Salicylic acid to decrease plant stress

Pollution and climate change degrade plant health. Plant stress can be decreased by application of salicylic acid, an hormone involved in plant signaling. Salicylic acid indeed initiates pathogenesis-related gene expression and synthesis of defensive compounds involved in local resistance and systemic acquired resistance. Salicylic acid may thus be used against pathogen virulence, heavy metal stresses, salt stress, and toxicities of other elements. Applied salicylic acid improves photosynthesis, growth, and various other physiological and biochemical characteristics in stressed plants. Salicylic acid antagonizes the oxidative damaging effect of metal toxicity directly by acting as an antioxidant to scavenge the reactive oxygen species and by activating the antioxidant systems of plants and indirectly by reducing uptake of metals from their medium of growth. We review here the use of exogenous salicylic acid in alleviating bacterial, fungal, and viral diseases, heavy metal toxicity, toxicity of essential micronutrients, and salt stress.     

Pretreatment for dissolved organic nitrogen testing by gas stripping

ABSTRACT

Total dissolved nitrogen (TDN), including dissolved inorganic nitrogen (DIN) and dissolved organic nitrogen (DON), is of significant importance in aquatic systems due to its roles in numerous environmental processes, such as nutrients for agriculture activities, sources for lake and estuary eutrophication, and one of the major factors contributing to disinfection byproduct formation. The distribution and impact of DIN on these processes are relatively well-understood; however, information on DON is extremely limited, as there is no direct method for its quantification. DON is conventionally determined by subtracting DIN from TDN. However, significant errors may be introduced if DIN is the predominant species in samples with high concentrations of TDN. In order to deal with this challenge, pretreatment method for nitrogen gas stripping was investigated using 56 water samples collected from various ecosystems. The results indicated that after nitrogen gas stripping pretreatment, removal % of ammonia nitrogen (NH₃–N) was more than 87.5%, and the ratios of removal of NH₃–N/removal of TDN (β) were over 86.5% for most of 56 samples with high [NH₃–N], indicating a high efficiency for removal of NH₃–N, and that NH₃–N was the predominant nitrogen species removed for the samples with high [NH₃–N]. Therefore, nitrogen gas stripping is an appropriate pretreatment method for DON testing when NH₃–N is the dominant inorganic nitrogen species.     

Catalyst-free synthesis of imidazo [1,2-a] pyridines via Groebke multicomponent reaction

Deep eutectic solvents are becoming more popular nowadays since they are green, safe and often save raw materials and energy compared to organic solvent. Due to the importance of environmentally compatible solvent in multicomponent reactions, herein we report an efficient and sustainable catalyst-free synthesis of imidazo [1,2-a] pyridines via Groebke multicomponent reaction in choline chloride-based deep eutectic solvent. One-pot, three-component reaction of 2-amino pyridine, aromatic aldehydes and cyclohexyl isocyanide in six different choline chloride-based deep eutectic solvents in the absence of catalyst were examined. Urea–choline chloride was selected as an efficient solvent for this isocyanide-based multicomponent reaction and afforded the imidazo [1,2-a] pyridines in good yields of 57–87 % and reaction times of 2–6 h. The method has several advantages such as environmentally benign and biodegradable solvent, easy purification processes by a simple filtration and methodological simplicity.     

Synthesis and potential applications of cyclodextrin-based metal–organic frameworks: a review

Metal–organic frameworks are porous polymeric materials formed by linking metal ions with organic bridging ligands. Metal–organic frameworks are used as sensors, catalysts for organic transformations, biomass conversion, photovoltaics, electrochemical applications, gas storage and separation, and photocatalysis. Nonetheless, many actual metal–organic frameworks present limitations such as toxicity of preparation reagents and components, which make frameworks unusable for food and pharmaceutical applications. Here, we review the structure, synthesis and properties of cyclodextrin-based metal–organic frameworks that could be used in bioapplications. Synthetic methods include vapor diffusion, microwave-assisted, hydro/solvothermal, and ultrasound techniques. The vapor diffusion method can produce cyclodextrin-based metal–organic framework crystals with particle sizes ranging from 200 nm to 400 μm. Applications comprise food packaging, drug delivery, sensors, adsorbents, gas separation, and membranes. Cyclodextrin-based metal–organic frameworks showed loading efficacy of the bioactive compounds ranging from 3.29 to 97.80%.

     

The effects of alginate microspheres on phytoremediation and growth of Lemna minor in the presence of Cd

Today, the removal of increased amount of contaminant concentrations in nature such as metals, nanoparticles, has become an essential issue to struggle with. In this paper, both the toxic effects of non-essential Cd on Lemna minor in presence of alginate microspheres and metal removal capacity of Cd-exposed L. minor and microspheres were investigated. Three test groups were constructed: group (L) containing Lemna, group (M) containing alginate microsphere and group (L?+?M) containing alginate microsphere and Lemna. Five different levels of Cd concentrations were added into these groups. Estimation models were constructed to estimate Cd removal capacities of L. minor and microspheres, and time-concentration-dependent growth (GRC) rates of both microsphere-containing and non-containing groups were modelled by regression analysis. It was seen that microspheres alone only had no positive or negative effects on Lemna growth. It was observed that, for all test groups the time-dependent growth rate has both increase–decrease trends in general. The toxicity effect of Cd on Lemna growth was reduced by adding microspheres into medium. Furthermore, the results stated that test groups containing only microspheres (M, 0–97.56%) and consortium groups (M?+?L, 0–98.26%) were slightly more successful in Cd removal process compared to Lemna (L) groups (L, 0–97.32%).     

Temporal, spatial, and body size effects on growth rates of loggerhead sea turtles (Caretta caretta) in the Northwest Atlantic

In response to a call from the US National Research Council for research programs to combine their data to improve sea turtle population assessments, we analyzed somatic growth data for Northwest Atlantic (NWA) loggerhead sea turtles (Caretta caretta) from 10 research programs. We assessed growth dynamics over wide ranges of geography (9–33°N latitude), time (1978–2012), and body size (35.4–103.3 cm carapace length). Generalized additive models revealed significant spatial and temporal variation in growth rates and a significant decline in growth rates with increasing body size. Growth was more rapid in waters south of the USA (<24°N) than in USA waters. Growth dynamics in southern waters in the NWA need more study because sample size was small. Within USA waters, the significant spatial effect in growth rates of immature loggerheads did not exhibit a consistent latitudinal trend. Growth rates declined significantly from 1997 through 2007 and then leveled off or increased. During this same interval, annual nest counts in Florida declined by 43 % (Witherington et al. in Ecol Appl 19:30–54, 2009) before rebounding. Whether these simultaneous declines reflect responses in productivity to a common environmental change should be explored to determine whether somatic growth rates can help interpret population trends based on annual counts of nests or nesting females. Because of the significant spatial and temporal variation in growth rates, population models of NWA loggerheads should avoid employing growth data from restricted spatial or temporal coverage to calculate demographic metrics such as age at sexual maturity.     

Green synthesis of symmetrical N, N′-disubstituted thiourea derivatives in water using solar energy

Thioureas are of importance in medicinal chemistry due to their biological activities such as antituberculosis, anti-HIV, analgesic, anti-inflammatory, antimicrobial, antiarrhythmic, fungicide, herbicides, rodenticides and as phenoloxidase enzymatic inhibitors. Treatment of primary and secondary amines with thiophosgene is the common method of making symmetrical disubstituted thioureas. However, this method is hazardous due to the toxic properties of thiophosgene. Here, we report a green, operationally simple approach for the synthesis of 1, 3-disubstituted thiourea derivatives in moderate to excellent yields of 57–99 %. We use primary amines and CS₂ in water without any catalyst and solar thermal energy. This method is more environmentally benign and energy-saving compared with previously reported methods.