Composition and antimicrobial activity of the essential oil of Heracleum thomsonii (Clarke) from the cold desert of the western Himalayas

Volatile oil composition of hydro-distilled (HD) and supercritical carbon dioxide (SC-CO(2)) essential oil of freshly collected aerial parts of Heracleum thomsonii (Umbeliferae) from the western Himalayas was studied by GC-FID and GC-MS. Results revealed qualitative and quantitative dissimilarity in the composition of hydro-distilled and SC-CO(2) extracted oils. Nineteen constituents, which accounted for 89.32% of total constituents in HD oil, represented by limonene (4.31%), (Z)-β-ocimene (3.69%), terpinolene (22.24%), neryl acetate (36.19%), nerol (9.51%) and p-cymene-8-ol (2.61%) were identified. In SC-CO(2) extracted oil, 24 constituents representing 89.95% of total constituents were identified. Terpinolene (5.08%), germacrene D (2.17%), neryl acetate (51.62%), nerol (9.78%), geranyl acetate (2.06%), α-bisabolol (2.48%) and 1-nonadecanol (4.96%) were the dominating constituents. In?vitro antimicrobial activity of hydro-distilled oil was conducted against microrobial strains including two Gram-positive (Staphylococcus aureus and Bacillus subtilis) and five Gram-negative (Burkholderia cepacia, Escherichia coli, Enterobacter cloacae, Klebseilla pneumoniae and Pseudomonas aeruginosa) bacteria as well as seven fungi (Candida albicans, Issatchenkia orientalis, Aspergillus flavus, Aspergillus niger, Aspergillus parasiticus, Aspergillus sydowii and Trichophyton rubrum) using broth microdilution method. The results of bioassay showed that the oil exhibited moderate to high antimicrobial activity against fungi C. albicans (MIC 625 μg?ml(-1)), A. parasiticus (MIC 312.5 μg?ml(-1)), A. sydowii (MIC 312.5 μg?ml(-1)), T. rubrum (MIC 625 μg?ml(-1)), Gram-positive bacteria B. subtilis (MIC 625?μg?ml(-1)) and Gram-negative bacteria P. aeruginosa (MIC 312.5 μg?ml(-1)).     

Improvement in the yield and quality of kalmegh (Andrographis paniculata Nees) under the sustainable production system

Andrographis paniculata Nees is an annual erect herb with wide medicinal and pharmacological applications due to the presence of andrographolide and other active chemical constituents. The large-scale cultivation of the kalmegh is not in practice. The aim of this study was to establish sustainable production systems of A. paniculata cv CIM-Megha with the application of different bioinoculants and chemical fertilisers. A. paniculata herb and andrographolide yield in the dried leaves was found to be highest (218% and 61.3%, respectively) in treatment T₃ (NPK+Bacillus sp.) compared with T₁ (control). The soil organic carbon, soil microbial respiration, soil enzymes activity and available nutrients improved significantly with combined application of bioinoculants and chemical fertilisers.     

Studies on rhizosphere microbial diversity of some commercially important medicinal plants

A preliminary study was made on four medicinal plants viz., Ocimum sanctum L., Coleus forskholii Briq, Catharanthus roseus (L.) G. Don. and Aloe vera in order to identify and enumerate the rhizosphere, non-rhizosphere and diazotrophic microorganisms in soil. The diazotrophic bacterial population studied includes Azospirillum, Azotobacter and Pseudomonas. The rhizosphere bacterial populations were 23.33 x 10(6)g(-1) in O. sanctum followed by C. roseus (20.46 x 10(6)g(-1)), A. vera (18.44 x 10(6)g(-1)) and C. forskholii (16.64 x 10(6)g(-1)). The fungi populations were 19.44 x 10(4)g(-1) in C. roseus, 18.66 x 10(4)g(-1) in O. sanctum, 16.44 x 10(4)g(-1) in A. vera and 14.22 x 10(4)g(-1) in C. forskholii. The actinomycetes population was 12.22 x 10(5)g(-1) in O. sanctum, 10.44 x 10(5)g(-1) in C. roseus, 8.44 x 10(5)g(-1) in A. vera and 6.22 x 10(5)g(-1) in C. forskholii. The diazotrophic bacterial population of Azospirillum, Azotobacter and Pseudomonas is 8.2 x 10(4)g(-1), 12 x 10(4)g(-1), 6 x 10(4)g(-1) in the rhizosphere soil. In all the four medicinal plants the microbial population is more in the rhizosphere soil, when compared to non-rhizosphere soil. These results are helpful in developing a biofertilizer consortium for these commercially grown medicinal plants.     

Simultaneous determination of four plant hormones in bananas by molecularly imprinted solid-phase extraction coupled with high performance liquid chromatography

A highly selective molecularly imprinted solid-phase extraction (MISPE) combined with liquid chromatography-ultraviolet detection was developed for the simultaneous isolation and determination of four plant hormones including indole-3-acetic acid (IAA), indole-3-propionic acid (IPA), indole-3-butyric acid (IBA) and 1-naphthaleneacetic acid (NAA) in banana samples. The new molecularly imprinted microspheres (MIMs) prepared by aqueous suspension polymerization using 3-hydroxy-2-naphthoic acid and 1-methylpiperazine as mimic templates performed with high selectivity and affinity for the four plant hormones, and applied as selective sorbents of solid-phase extraction could effectively eliminate the interferences of the banana matrix. Good linearity was obtained in a range of 0.04-4.00 μg g(-1) and the recoveries of the four plant hormones at three spiked levels ranged from 78.5 to 107.7% with the relative standard deviations (RSD) of less than 4.6%. The developed MISPE-HPLC protocol obviously improved the selectivity and eliminated the effect of template leakage on quantitative analysis, and could be applied for the determination of plant hormones in complicated biological samples.     

Carotenoid composition in Rhinacanthus nasutus (L.) Kurz as determined by HPLC-MS and affected by freeze-drying and hot-air-drying

Rhinacanthus nasutus (L.) Kurz (Trade name: Bai he ling zhi), a traditional medicinal herb, has been reported to possess anticancer and antioxidant activities. However, the composition of the major functional compounds, carotenoids, remains uncertain. The objectives of this study were to develop a high performance liquid chromatography-mass spectrometry (HPLC-MS) method for carotenoid composition determination in R. nasutus and for carotenoid change by freeze-drying and hot-air-drying. A total of 24 carotenoids were separated within 54 min by using a YMC C(30) column and a gradient mobile phase of methanol-acetonitrile-water (82?:?14?:?4, v/v/v) (A) and methylene chloride (100%) (B): 100% A initially, maintained for 10 min, decreased to 95% A in 25 min, 84% A in 30 min, 75% A in 37 min, 68% A in 40 min, 65% A in 47 min, and 55% A in 50 min with flow rate at 1 mL min(-1) and detection wavelength at 450 nm. The various carotenoids were identified by comparing the retention time, absorption spectra, Q-ratio and mass spectra of unknown peaks with reference standards as well as photoisomerized standards. Quantitation was carried out using an internal standard β-apo-8'-carotenal, with all-trans-lutein and its cis isomers being present in the largest amount (862 μg g(-1)) in freeze-dried R. nasutus, followed by all-trans-violaxanthin (494 μg g(-1)), all-trans-β-carotene and its cis isomers (479 μg g(-1)), all-trans-neoxanthin and its cis isomers (251 μg g(-1)), all-trans-α-carotene and its cis isomers (85.2 μg g(-1)), luteoxanthin (14.3 μg g(-1)), all-trans-zeaxanthin (3.94 μg g(-1)), β-carotene-5,6-epoxide (3.45 μg g(-1)) and all-trans-β-cryptoxanthin (1.03 μg g(-1)). Comparatively, some more carotenoids including cis-violaxanthin, luteoxanthin, cis-neoxanthin, neochrome, 13- or 13'-cis-lutein, 9- or 9'-cis-lutein, β-carotene-5,6-epoxide, 9- or 9'-cis-β-carotene, 13- or 13'-cis-β-carotene, 15- or 15'-cis-β-carotene and 13- or 13'-cis-α-carotene were generated in R. nasutus during hot-air-drying.     

Cadmium Tolerance and Bioaccumulation of 18 Hemp Accessions

Hemp (Cannabis sativa L.) is a fast-growing and high biomass producing plant species, which has been traditionally grown as multiple-use crop and recently considered as an energy crop. In order to screen accessions that can be cultivated in cadmium (Cd)-contaminated soils for biodiesel production, the ability of Cd tolerance and bioaccumulation of 18 hemp cultivars or ecotypes were evaluated in pot experiment under 25?mg Cd kg(-1) (dry weight, DW) soil condition, in terms of plant growth, pigment contents, chlorophyll fluorescence, and Cd accumulation at 45?days after seedling emergence. Results showed that seedlings of all cultivars, except USO-31, Shenyang and Shengmu, could grow quite well under 25?mg Cd kg(-1) (DW) soil condition. Among them, Yunma 1, Yunma 2, Yunma 3, Yunma 4, Qujing, Longxi, Lu'an, Xingtai, and Shuyang showed great biomass (>0.5?g plant(-1)), high tolerance factors (68.6-92.3%), and little reduction of pigment content and chlorophyll fluorescence under 25?mg Cd kg(-1) (DW) soil stress, indicating these cultivars had a strong tolerance to Cd stress and could be cultivated in Cd-contaminated soils. Cultivars Longxi, Lu'an, Xingtai, Yunma 2, Yunma 3, Yunma 4, and Qujing exhibited higher Cd concentrations and total Cd in shoots. These cultivars, therefore, are good candidates for the implementation of the new strategy of cultivating biodiesel crops for phytoremediation of Cd-contaminated soils.     

Determination of cyclic and linear siloxanes in soil samples by ultrasonic-assisted extraction and gas chromatography-mass spectrometry

A rapid method, based on sonication-assisted extraction in small columns (SAESC) and subsequent quantification and identification by gas chromatography-mass spectrometry (GC-MS), was developed for the determination of cyclic and linear siloxanes in soil. In the experiments with spiked samples (10-50 ng g(-1)), the recovery of cyclic and linear siloxanes ranged from 87.7 to 108.0% and from 84.9 to 107.6%, respectively. The validated method was used to determine the levels of these compounds in various types of soil samples collected from different locations in Spain. The cyclic siloxanes, decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were detected in all the soil samples analyzed at concentrations from 9.2 to 56.9 ng g(-1) for D5 and from 5.8 to 27.1 ng g(-1) for D6 in agricultural soils and from 22 to 184 ng g(-1) for D5 and from 28 to 483 ng g(-1) for D6 in industrial soils. The total linear siloxanes concentrations (L5-L14) (sum of the 10 congeners) ranged from 191 to 292 ng g(-1) in agricultural soils and from 1411 to 8532 ng g(-1) in industrial soils.     

Antifungal activity of the essential oil of Illicium verum fruit and its main component trans-anethole

In order to identify natural products for plant disease control, the essential oil of star anise (Illicium verum Hook. f.) fruit was investigated for its antifungal activity on plant pathogenic fungi. The fruit essential oil obtained by hydro-distillation was analyzed for its chemical composition by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). trans-Anethole (89.5%), 2-(1-cyclopentenyl)-furan (0.9%) and cis-anethole (0.7%) were found to be the main components among 22 identified compounds, which accounted for 94.6% of the total oil. The antifungal activity of the oil and its main component trans-anethole against plant pathogenic fungi were determined. Both the essential oil and trans-anethole exhibited strong inhibitory effect against all test fungi indicating that most of the observed antifungal properties was due to the presence of trans-anethole in the oil, which could be developed as natural fungicides for plant disease control in fruit and vegetable preservation.     

Supercapacitor electrodes with especially high rate capability and cyclability based on a novel Pt nanosphere and cysteine-generated graphene

In the present work, supercapacitors based on graphene/Pt films show especially high rate capability (120 F g(-1) even at 50 A g(-1)) and cyclability (no attenuation over 10,000 cycles) and peculiar nanosphere morphology after electrochemical cycling. Furthermore, supercapacitors based on the graphene powder with a binder exhibit high specific capacitance (249 F g(-1) at 0.1 A g(-1)), long cycle life (no attenuation over 40,000 cycles) and high rate capability (150 F g(-1) even at 50 A g(-1)), which are much better than those of most graphene electrode materials. These indicate the great potential of the cysteine reduced graphene electrodes in energy storage.     

Production of Plant Beneficial and Antioxidants Metabolites by Klebsiella variicola under Salinity Stress

Bacteria that surround plant roots and exert beneficial effects on plant growth are known as plant growth-promoting rhizobacteria (PGPR). In addition to the plant growth-promotion, PGPR also imparts resistance against salinity and oxidative stress and needs to be studied. Such PGPR can function as dynamic bioinoculants under salinity conditions. The present study reports the isolation of phytase positive multifarious Klebsiella variicola SURYA6 isolated from wheat rhizosphere in Kolhapur, India. The isolate produced various plant growth-promoting (PGP), salinity ameliorating, and antioxidant traits. It produced organic acid, yielded a higher phosphorous solubilization index (9.3), maximum phytase activity (376.67 ± 2.77 U/mL), and copious amounts of siderophore (79.0%). The isolate also produced salt ameliorating traits such as indole acetic acid (78.45 ± 1.9 µg/mL), 1 aminocyclopropane-1-carboxylate deaminase (0.991 M/mg/h), and exopolysaccharides (32.2 ± 1.2 g/L). In addition to these, the isolate also produced higher activities of antioxidant enzymes like superoxide dismutase (13.86 IU/mg protein), catalase (0.053 IU/mg protein), and glutathione oxidase (22.12 µg/mg protein) at various salt levels. The isolate exhibited optimum growth and maximum secretion of these metabolites during the log-phase growth. It exhibited sensitivity to a wide range of antibiotics and did not produce hemolysis on blood agar, indicative of its non-pathogenic nature. The potential of K. variicola to produce copious amounts of various PGP, salt ameliorating, and antioxidant metabolites make it a potential bioinoculant for salinity stress management.     

In-situ separation of the matrix for the direct determination of traces of chromium, cobalt, and nickel in titanium dioxide powder by electrothermal atomic-absorption spectrometry with slurry sampling

A novel method has been developed for the direct determination of traces of chromium, cobalt, and nickel in TiO2 powder; it entails slurry sampling and electrothermal atomic-absorption spectrometry (ETAAS) with a polytetrafluoroethylene (PTFE) slurry (6% m/v) as fluorinating reagent. The factors which could affect the vaporization of the matrix and analytes were studied in detail; the fluorinating vaporization behavior of the analyte both in the slurry and in solution were also investigated. Owing to the in-situ separation of the matrix, the matrix influences were reduced significantly. The proposed method has been applied to the direct determination of traces of chromium, cobalt, and nickel in high-purity TiO2 powder without chemical pretreatment. Under the optimum experimental conditions the detection limits of the analytes (Cr, Co, and Ni) were 1.9 ng g(-1), 2.4 ng g(-1) and 5.4 ng g(-1), respectively, the relative standard deviations (RSD) were 3.4% (n=6, c=7.0 ng mL(-1)), 2.9% (n=6, c=0.70 ng mL(-1)), and 7.6% (n=6, c=4.0 ng mL(-1)), again respectively, and the characteristic masses for Cr, Co, and Ni were 8.4 pg/ 0.0044A, 9.3 pg/0.0044A, and 40.0 pg/0.0044A, respectively.     

Glyphosate affects soybean root exudation and rhizosphere micro-organisms

Glyphosate is a non-selective, broad-spectrum herbicide that kills plants by inhibiting the enzyme 5-enolpyruvylshikimic acid-3-phosphate synthase (EPSPS), which is necessary for synthesis of aromatic amino acids. A secondary mode of action involves infection of roots of glyphosate-susceptible plants by soil-borne micro-organisms due to decreased production of plant protection compounds known as phytoalexins. Varieties of several crops, including glyphosate-resistant (GR) or Roundup Ready soybean, are genetically modified to resist the herbicidal effects of glyphosate and provide farmers with an effective weed-management tool. After glyphosate is applied to GR soybean, glyphosate that is not bound to glyphosate-resistant EPSPS is translocated throughout the plant and accumulates primarily in meristematic tissues. We previously reported that fungal colonization of GR soybean roots increased significantly after application of glyphosate but not after conventional postemergence herbicides. Because glyphosate may be released into soil from GR roots, we characterized the response of rhizosphere fungi and bacteria to root exudates from GR and non-GR (Williams 82; W82) cultivars treated with and without glyphosate at field application rates. Using an immunoassay technique, glyphosate at concentrations >1000 ng plant-1 were detected in exudates of hydroponically grown GR soybean at 16 days post-glyphosate application. Glyphosate also increased carbohydrate and amino acid contents in root exudates in both soybean cultivars. However, GR soybean released higher carbohydrate and amino acid contents in root exudates than W82 soybean without glyphosate treatment. In vitro bioassays showed that glyphosate in the exudates stimulated growth of selected rhizosphere fungi, possibly by providing a selective C and N source combined with the high levels of soluble carbohydrates and amino acids associated with glyphosate treatment of the soybean plants. Increased fungal populations that develop under glyphosate treatment of GR soybean may adversely affect plant growth and biological processes in the soil and rhizosphere.     

High throughput development of selective oxidation catalysts at Süd-Chemie

The Temkin reactor concept was successfully extended to the high throughput operation mode and it could be considerably improved as compared to the original design with respect to an optimized gas flow pattern over the full size beads. This improved parallel reactor design was successfully used for the high throughput optimization of an innovative new class of physically coated VAM shell catalysts. Exploiting this novel, improved Temkin reactor concept allowed Süd-Chemie not only to optimize the multiparameter compositional space of noble metal and promoter loadings on the support spheres but for the first time to combine this "chemical optimization" with the high throughput improvement of catalytically decisive parameters as the active shell thickness, the metal distribution cross the shell, the pore diameters, and the pore volumes. This new class of physically impregnated VA catalysts, called VAM2ax, impress by its exceptionally high VA selectivity of above 94% at 50% oxygen conversion and the very high space time yields of > 1000 g VAM/l*h which easily can be reached over these shell catalysts with optimized mass and heat transport properties.     

Labile rhizosphere soil solution fraction for prediction of bioavailability of heavy metals and rare earth elements to plants

A labile rhizosphere soil solution fraction has been recommended to predict the bioavailability of heavy metals and rare earth elements to plants. This method used moist rhizosphere soil in combination with a mixture of 0.01 mol L(-1) of low-molecular-weight organic acids (LMWOAs) as extractant. The extracted soil solutions were fractionated into two colloidal fractions of <0.45 microm (F(3)) and <0.2 microm (F(2)), and one truly dissolved fraction including free metal ions and inorganic and organic complexes (fractionr(0.2 microm, LMWOAs) approximately r(0.45 microm, LMWOAs). In the case of rare earth elements the good correlation was obtained for both the wheat roots and shoots. Generally, the correlation coefficients obtained by LMWAOs were better than that obtained by the first step of BCR method. Therefore, LMWAOs and F(lrss) were strongly recommended to predict the bioavailability of metals in soil pools to plants.     

Micropropagation and production of Camptothecin from in vitro plants of Ophiorrhiza rugosa var. decumbens

Camptothecin and its derivatives are used as anticancer alkaloids. At present, they are obtained by the extraction from the Chinese tree Camptotheca acuminata and the indigenous tree Nothapodytes foetida. Identification of alternate species of plants like Ophiorrhiza species and development of tissue culture methods may be a suitable alternative for large-scale micropropagation as well as for the production of camptothecin. Plantlets were successfully regenerated from shoot cultures of Ophiorrhiza rugosa initiated from axillary meristems on medium containing benzyladenine (BA) (4.0 mg L(-1)) + alpha-naphthalene acetic acid (NAA) (0.05 mg L(-1)). Rooting was initiated in half concentration of Murashige and Skoog's (MS) basal medium devoid of growth hormones. Tissue culture derived plants of O. rugosa were similar to the normal plants in their morphological characteristics and chemical constitution. Ten O. rugosa plants that were obtained through micropropagation showed when analysed a higher alkaloid content compared to the normal plant. Chemical analysis of the different organs of the tissue culture plant of O. rugosa established in soil indicated 0.002% dry weight of camptothecin in the roots, 0.011% dry weight in the stems, 0.090% dry weight in the leaves and 0.015% in the floral parts.     

Liquid chromatographic method for the micro-quantitative determination of clodinafop in soil, wheat and Phalaris minor

A liquid chromatographic method was developed for the determination of clodinafop-propargyl herbicide. Clodinafop-propargyl was converted to clodinafop acid by alkaline hydrolysis as clodinafop-propargyl rapidly forms bioactive clodinafop acid in soil and plant environment. Recovery methods for both the acid and ester from different matrices were standardized. The sensitivity of the method for ester and acid was 5 and 2 ng, respectively, with limits of detection of 0.5 and 0.1 microg ml(-1). The method was standardized for the determination of clodinafop residues in soil and plant samples using HPLC. The recovery of clodinafop from soil and plant samples with ethyl acetate was significantly higher (78-83%) than those with dichloromethane, toluene and methanol (60-70%). The limit of determination of clodinafop in soil and plant samples ranged between 1 and 1.2 ng g(-1). In field soil, residues of clodinafop dissipated with a half-life of 3.44 days.     

Effects of velvet antler with blood on bone in ovariectomized rats

In traditional Chinese medicine (TCM), both velvet antlers (VA) and VA blood can tonify qi, essence, and marrow, nourish the blood, and invigorate bones and tendons. In TCM, the combination of VA and VA blood is believed to have superior pharmacological effects. Scientific evidence supporting the traditional therapeutic preference for redder antler is needed. The effectiveness of the combination therapy of VA middle sections (VAMs) and VA blood (VAM-B) was first examined in promoting proliferation of mouse osteoblastic cells (MC3T3-E1). The anti-osteoporotic activity of VAM-B (ratio of VAM:VA blood = 1:0.2) was evaluated with ovariectomized (OVX) rats at a dose of 0.2 g/kg. In VAM-B-treated OVX rats, the body weight decreased 10.7%, and the strength of vertebrae and the femur respectively increased 18.1% and 15.4%, compared to the control. VAM-B treatment also recovered the estrogen-related loss of the right tibial trabecular bone microarchitecture. Alkaline phosphatase (ALP) significantly decreased, but estradiol did not significantly change in serum of VAM-B-treated OVX rats. We also provide an effective strategy to enhance the anti-osteoporotic activity of VAM. In conclusion, our results provide scientific evidence supporting the traditional therapeutic preference of redder antler and indicate that VAM-B is a potential therapeutic agent for managing osteoporosis.     

Functional Properties of Banana Starch (Musa spp.) and Its Utilization in Cosmetics

Unripe banana fruit of Musa acuminata (Musa AAA; Hom Khieo) and Musa sapientum L. (Musa ABB; Namwa) growing in Chiang Rai (Thailand) were used for extraction. The yield of the starches was 16.88% for Hom Khieo (HK) and 22.73% for Namwa (NW) based on unripe peeled banana fruit. The amylose contents of HK and NW were 24.99% and 26.23%, respectively. The morphology of starch granules was oval shape with elongated forms for large granules and round shape for small granules. The HK and NW showed B-type crystalline structure and the crystallinities were 23.54% and 26.83%, respectively. The peak temperature of gelatinization was around 77 °C and the enthalpy change (ΔH) was 3.05 and 7.76 J/g, respectively. The HK and NW banana starches showed 1.27 ± 0.12 g/g and 1.53 ± 0.12 g/g water absorption capacity, and 1.22 ± 0.11 g/g and 1.16 ± 0.12 g/g oil absorption capacity, respectively. The swelling power of the banana starches was 17.23 ± 0.94 g/g and 15.90 ± 0.15 g/g, respectively, and the percentage of solubility in water showed 26.43 ± 2.50 g/g and 20.54 ± 0.94 g/g, respectively. The banana starches showed very poor flow character. The HK and NW starches have the potential to be used in powder base preparations with no effect on the sensory texture of the product at 15% w/w maximum.     

Carbazole endcapped heterofluorenes as host materials: theoretical study of their structural, electronic, and optical properties

By mimicking the molecular structure of 4,4'-bis(N-carbazolyl)-2,2'-biphenyl (CBP), which is a widely used host material, a new series of host molecules (carbazole-endcapped heterofluorenes, CzHFs) were designed by linking the hole-transporting carbazole to the core heterofluorene molecules in either meta or para positions of the heterofluorene. The aromatic cores considered in this study are biphenyl, fluorene, silafluorenes, germafluorenes, carbazole, phosphafluorene, oxygafluorene, and sulfurafluorene. To reveal their molecular structures, optoelectronic properties and structure-property relationships of the proposed host materials, an in-depth theoretical investigation was elaborated via quantum chemical calculations. The electronic structures in the ground states, cationic and anionic states, and lowest triplet states of these designed molecules have been studied with emphasis on the highest occupied molecular orbitals (HOMOs), the lowest unoccupied molecular orbitals (LUMOs), energy gaps (E(g)), triplet energy gaps ((3)E(g)), as well as some other electronic properties including ionization potentials (IPs), electron affinities (EAs), reorganization energies (λ), triplet exciton generation fraction (χ(T)), spin density distributions (SD), and absorption spectra. These photoelectronic properties can be tuned by chemical modifications of the heteroatom and the carbazole substitution at different positions. This study provides theoretical insights into the nature of host molecules, and shows that the designed CzHFs can meet the requirements of the host materials for triplet emitters.     

Rapid analysis of the nitrification inhibitor 3,4-dimethylpyrazole phosphate in soil using LC-MS/MS

Nitrate from the biological nitrification of ammonium fertilisers causes environmental damage via groundwater contamination and nitrous oxide emission. To limit nitrate formation, nitrification inhibitors (NIs) are used in conjunction with ammonium-based fertilisers in agricultural land management. The NI 3,4-dimethyl-1H-pyrazole phosphate (DMPP), with an active constituent 3,4-dimethyl-1H-pyrazole (3,4-DMP), is commercially available and its effectiveness and behaviour in soils have been studied. However, only one method for the analysis of 3,4-DMP in soil has been reported and relies on extensive sample preparation to remove matrix interferences prior to HPLC analysis. A new method was developed to allow monitoring of 3,4-DMP residues in soil after appliaction, which utilises the greater selectivity and sensitivity of LC-MS/MS. A 3,4-DMP limit of quantitation of 0.5 ng/g was achieved, which is 10 times more sensitive than the published method, and was achieved using 10,000 times less 3,4-DMP injected on-column, with an injection volume 100 times smaller. Four internal standards were evaluated to improve the accuracy of the extraction method. The isotope-substituted structural isomer 3,5-dimethyl pyrazole-¹⁵N₂ provided the best and most consistent recoveries over the 300-fold concentration range tested. The new method was employed to investigate the persistence and mobility of 3,4-DMP in an agricultural soil. 3,4-DMP had a half-life of 5 days in the top 0.5 cm of soil at normal and double recommended application rates, while half-lives in the 2.5 cm soil profile were 28 and 21 days, respectively. 3,4-DMP mobility in the clay loam soil tested was low, with only 15–25% of applied 3,4-DMP detected below the top 0.5 cm, suggesting the loss of 3,4-DMP was either due to volatilisation or degradation, rather than leaching into the soil profile.