Effect of Solvents on the Spectra of Some β-Diketones

Acetoacetanilide, benzoylacetanilide and their derivatives have been examined in ultraviolet region in a series of solvents covering a broad polarity range e. e. from chloroform (Z, 63.2) to methanol (Z .83.6). Transition energies and oscillator strengths have been calculated and transition energy (E_T) has been plotted against Z-values, a new empirical measurement of solvent polarity. A linear relationship was observed between the transition energy and Z-values for π → π* and n → π* transitions. These transitions are identified as charge transfer (c-t) transitions and with the solvents having carbonyl oxygen and sulphur atom a c-t complex formation has been suggested. Strong electron-donating substituents on phenyl group of the nitrogen atom also showed a weak to moderate n → π* transitions. These substituents have no influence on the position of the λ_max in the same solvent. Stabilization energy of the excited state of these ligands and hence the dipole moments of the excited states have been calculated in comparison with pyridinium iodide. Solvent sensitivities of these ligands have also been calculated.     

Macroscopic and microscopic authentication of Chinese and North American species of Ephedra

Ephedra sinica Stapf or Ma Huang has been used in traditional Chinese medicine for over 5000 years as a bronchodilating and stimulatory agent. In the West, it is popularly used in dietary supplements for weight loss and to enhance athletic performance. Adverse events have been reported following consumption of dietary supplements containing ephedrine alkaloids. There are about 50 known species of Ephedra. The ratio of ephedrine to other alkaloids varies from species to species; all North American species lack alkaloids. The method commonly used in the dietary supplement industry for botanical authentication is to analyze the product for the presence of chemical markers known to be present in the specific herb. However, this method does not ensure that the product contains authentic herb, especially if it has been spiked with chemical marker compounds. In the trade and raw drug market, Ephedra is available in the form of stem cuttings or powders, without any vouchers, thus making identification of the species difficult. Using light microscopy, we can detect the presence of Ephedra herb, even in powder form, and identify within certain limits its geographical origin. Identification of Chinese and North American species of Ephedra has been made easier by developing a key using leaf and internode length as key identification characters.     

β-(Methoxy-(substitutedphenyl)-methyl)-γ-butyrolactones: A short synthesis from cinnamyl acetate

A simple and short synthesis has been revealed for the preparation of (±) β-(Methoxy-(substitutedphenyl)-methyl)-γ-butyrolactones. The reaction of cinnamyl acetate with Mn(OAc)₃ · 2H₂O in boiling acetic acid containing acetic anhydride gave the products 2 and 3, which further cyclized in 3% H₂SO₄/CH₃OH to afford the butyrolactones (8a–e), which are intermediates of lignin, in good to moderate yields.     

A facile approach to chiral 1,4-benzodioxane toward the syntheses of doxazosin,prosympal, piperoxan,and dibozane

The process describes the concise synthesis of (R/S)-enantiomers of doxazosin, an antidepressant drug and α-adrenergic receptor antagonists like prosympal, piperoxan, and dibozane in practical yields from easily available (R)-2,3-O-cyclohexylidene-d-glyceraldehyde and (S)-3-(benzyloxy)propane-1,2-diol.     

The Role of Hydrogen‐Bonding Interactions in the Ultrafast Relaxation Dynamics of the Excited States of 3‐ and 4‐Aminofluoren‐9‐ones

The dynamics of the excited states of 3‐ and 4‐aminofluoren‐9‐ones (3AF and 4AF, respectively) are investigated in different kinds of solvents by using a subpicosecond time‐resolved absorption spectroscopic technique. They undergo hydrogen‐bonding interaction with protic solvents in both the ground and excited states. However, this interaction is more significant in the lowest excited singlet (S₁) state because of its substantial intramolecular charge‐transfer character. Significant differences in the spectroscopic characteristics and temporal dynamics of the S₁ states of 3AF and 4AF in aprotic and protic solvents reveal that the intermolecular hydrogen‐bonding interaction between the S₁ state and protic solvents plays an important role in its relaxation process. Perfect linear correlation between the relaxation times of the S₁ state and the longitudinal relaxation times (τ_L) of alcoholic solvents confirms the prediction regarding the solvation process via hydrogen‐bond reorganization. In the case of weakly interacting systems, the relaxation process can be well described by a dipolar solvation‐like process involving rotation of the OH groups of the alcoholic solvents, whereas in solvents having a strong hydrogen‐bond‐donating ability, for example, methanol and trifluoroethanol, it involves the conversion of the non‐hydrogen‐bonded form to the hydrogen‐bonded complex of the S₁ state. Efficient radiationless deactivation of the S₁ state of the aminofluorenones by protic solvents is successfully explained by the energy‐gap law, by using the energy of the fully solvated S₁ state determined from the time‐resolved spectroscopic data.     

Growth of Shape‐ and Size‐Selective Zinc Oxide Nanorods by a Microwave‐Assisted Chemical Bath Deposition Method: Effect on Photocatalysis Properties

Herein, we demonstrate the shape‐ and size‐selective growth of ZnO nanostructures on indium tin oxide‐coated glass substrates by using a microwave‐assisted chemical bath deposition method. By systematically controlling the deposition parameters, it is possible to produce shape‐ and size‐selective nanostructures with high alignment and uniformity. Specifically, the pH of the bath can be used to control the shape of rods from bundled structures to tapered and flat tips. Furthermore, the deposition temperature can be used to control the size of the ZnO array from 770 to 125 nm. The prepared rods were active catalysts in the degradation of methylene blue under UV radiation, and exhibited size‐dependent activity.     

Global air quality and climate

Emissions of air pollutants and their precursors determine regional air quality and can alter climate. Climate change can perturb the long-range transport, chemical processing, and local meteorology that influence air pollution. We review the implications of projected changes in methane (CH(4)), ozone precursors (O(3)), and aerosols for climate (expressed in terms of the radiative forcing metric or changes in global surface temperature) and hemispheric-to-continental scale air quality. Reducing the O(3) precursor CH(4) would slow near-term warming by decreasing both CH(4) and tropospheric O(3). Uncertainty remains as to the net climate forcing from anthropogenic nitrogen oxide (NO(x)) emissions, which increase tropospheric O(3) (warming) but also increase aerosols and decrease CH(4) (both cooling). Anthropogenic emissions of carbon monoxide (CO) and non-CH(4) volatile organic compounds (NMVOC) warm by increasing both O(3) and CH(4). Radiative impacts from secondary organic aerosols (SOA) are poorly understood. Black carbon emission controls, by reducing the absorption of sunlight in the atmosphere and on snow and ice, have the potential to slow near-term warming, but uncertainties in coincident emissions of reflective (cooling) aerosols and poorly constrained cloud indirect effects confound robust estimates of net climate impacts. Reducing sulfate and nitrate aerosols would improve air quality and lessen interference with the hydrologic cycle, but lead to warming. A holistic and balanced view is thus needed to assess how air pollution controls influence climate; a first step towards this goal involves estimating net climate impacts from individual emission sectors. Modeling and observational analyses suggest a warming climate degrades air quality (increasing surface O(3) and particulate matter) in many populated regions, including during pollution episodes. Prior Intergovernmental Panel on Climate Change (IPCC) scenarios (SRES) allowed unconstrained growth, whereas the Representative Concentration Pathway (RCP) scenarios assume uniformly an aggressive reduction, of air pollutant emissions. New estimates from the current generation of chemistry-climate models with RCP emissions thus project improved air quality over the next century relative to those using the IPCC SRES scenarios. These two sets of projections likely bracket possible futures. We find that uncertainty in emission-driven changes in air quality is generally greater than uncertainty in climate-driven changes. Confidence in air quality projections is limited by the reliability of anthropogenic emission trajectories and the uncertainties in regional climate responses, feedbacks with the terrestrial biosphere, and oxidation pathways affecting O(3) and SOA.     

Chemical Constituents of <Emphasis Type="Italic">Rhododendron lepidotum</Emphasis>

Two new coumarin glycosides, 7-O-β-D-glucopyranosyl-8-methoxybenzopyranone (1) and 7-hydroxy-8-O-β-glycosylbenzopyranone ((2), are reported along with the isolation of 7,8-dihydroxy coumarin (daphnetin) from Rhododendron lepidotum (aerial part).     

High Temperature Transformation of Iron Minerals in Bauxite

Mössbauer hyperfine and X-ray diffraction studies have been carried on original bauxite sample and thermally treated (between 200 and 1200°C) samples. Mössbauer spectrum of original bauxite shows the dominance of hematite (α-Fe₂O₃) along with Al-substituted hematite and goethite (α-FeOOH) of fine particle size. Mössbauer parameters for thermally treated samples indicate transformation of almost all of iron oxy-hydroxides into hematite up to 350°C. Around 800°C the formation of a new iron phase, assigned as iron substituted mullite (3Al₂O₃ 2SiO₃), occurs and its intensity increases with the rise in temperature and reaches a saturation around 1200°C. Furthermore, our studies confirm that HCl leaching is quite effective for the iron oxide removal.