Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines

A combined spectroscopic and TD-DFT case study was performed, to identify a robust method to calculate the complex near UV/Vis absorption spectra of various amino- vs. nitro-substituted 2,4-diphenylquinolines, which vary strongly under neutral and successively acidic conditions. For this, different DFT functionals were tested for geometry optimization and the TD part to calculate the neutral and different protonated species in a fast screening approach, i. e. using single point calculations in an implicit solvent. Offset-corrected M06HF, hitherto only applied to polymers, was identified as a suitable method to reproduce the absorption spectra in a reasonable fashion for all different substitution pattern and all different protonated species at different pH values; moreover, the method properly predicts the energetic ordering of low-lying n-π* and ππ* transitions, which is decisive for the non-/emissive nature of the different compounds. In all, this might provide a valuable tool for computer-aided design of related classes of compounds.     

Hybrid sol–gel silica adsorbent materials synthesized by molecular imprinting for tannin removal

Journal of Sol-Gel Science and Technology - This study reports the development of a functional adsorbent synthesized by the molecular imprinting method in a sol–gel matrix. The adsorption...     

Effect of 300 and 500 MPa pressure treatments on starch–water adsorption/desorption isotherms and hysteresis

Pressure treatments of 300 and 500?MPa during 15?min were found to change starch–water sorption (adsorption and desorption) isotherms and the hysteresis effect, particularly the 500?MPa. This last treatment shifted the adsorption/desorption isotherms downward, compared with non-treated starch and starch treated at 300?MPa. The observed hysteresis effect decreased with the increase in pressure level in the whole a_w range, indicating that adsorption and desorption isotherms became closer. Guggenheim–Anderson–De Boer and Brunauer–Emmett–Teller model parameters Cb, Cg, K and Mm also showed changes caused by pressure, the latter being lower in the pressure-processed samples, thus indicating possible changes on microbial and (bio)chemical stabilities of pressure-processed food products containing starch.     

Assessing the effect of a barrier between two rooms subjected to low frequency sound using the boundary element method

The boundary element method (BEM) has been used to compute the acoustic wave propagation through a single vertical panel, which separates two rooms, made of concrete, when one of the rooms is excited by a steady-state, spatially sinusoidal, harmonic line load pressure at low frequencies. This work focuses on how the connection of the panel to the ceiling affects the acoustic insulation provided by the wall. Perfect double-fixed partitions and acoustic barrier-type structures with differently-sized gaps between the ceiling and the barrier are studied. The BEM model is formulated in the frequency domain and takes the air-solid interaction fully into account. Insulation dips are localised in the frequency domain and identified with dips associated with both the wall's natural dynamic vibration modes and with those associated with the air in the rooms. The influence of the wall's thickness on acoustic insulation is also analysed. The computed results obtained with the acoustic barrier type structure are compared with those obtained by a rigid model. The importance of the rooms' surface conditions is assessed, modelling the rooms with cork.     

Uniqueness of H-surfaces in {\mathbb{H}}^2 \times \mathbb{R},{{\vert H\vert \leq 1/2}} , with boundary one or two parallel horizontal circles

We prove that a H-surface M in ${\mathbb{H}}^2 \times {\mathbb{R}} ,\vert H\vert \leq 1/2$ , inherits the symmetries of its boundary $\partial M,$ when $\partial M$ is either a horizontal curve with curvature greater than one or two parallel horizontal curves with curvature greater than one, whose distance is greater or equal to π. Furthermore we prove that the asymptotic boundary of a surface with mean curvature bounded away from zero consists of parts of straight lines, provided it is sufficiently regular.     

Radium equivalent and annual effective dose from geological samples from Pedra – Pernambuco – Brazil

The natural radioactivity of an uranium-anomalous area utilized for agricultural activities in Pedra, Brazil, was monitored. For this, samples from the granite and calcium-silicate amphibole rocks underlying this area and also from samples of the soil derived from these rocks were collected and analyzed by high-resolution gamma spectrometry. The equivalent radium (Ra_eq) was used as a reference for estimating the rate of the effective equivalent dose. The average, minimum and maximum values for the samples were of 319.2 Bq kg^?1 (91.1–758.5 Bq kg^?1) for soil; 327.5 Bq kg^?1 (36.3–1624.0 Bq kg^?1) for granitic rocks and 70,124.5 Bq kg^?1 (16,979.6–147,159.0 Bq kg^?1) for the calcium-silicate amphibole rocks. An estimation of the external exposition was carried out based on the calculation of the parameters obtained.     

Synthesis and characterization of some heterocyclic derivatives by cyclization of carbohydrate thiosemicarbazone — part II

The syntheses of 2,3‐dihydro‐1,3,4‐thiadiazoles and 1,3,4‐thiadiazoles from 1,2‐O‐isopropylidene‐α‐D‐xylo‐1,5‐pentadialdo‐1,4‐furanose thiosemicarbazone are described. The new compounds as well as the intermediate products are physically and spectroscopically characterized. We discuss a possible mechanistic pathway for heterocyclization in this particular substrate, using computational calculation.