Excitation wavelength dependence of solvation dynamics in a supramolecular assembly: PEO-PPO-PEO triblock copolymer and SDS

The triblock copolymer (PEO)20-(PPO)70-(PEO)20 (P123) forms a supramolecular aggregate with sodium dodecyl sulfate (SDS). The solvation dynamics and anisotropy decay of coumarin 480 (C480) in different regions of a P123-SDS aggregate are studied through variation of the excitation wavelength (lambdaex) using femtosecond upconversion. In a P123 micelle, because of the drastic differences in polarity between the hydrophilic corona region (PEO block) and the hydrophobic PPO core, C480 exhibits a pronounced red edge excitation shift (REES) of emission maximum by 24 nm. In the P123-SDS aggregate, SDS penetrates the core of the P123 micelle. This increases the polarity of the core and reduces the difference in the polarity between the core and the corona region. In a P123-SDS aggregate, the REES is much smaller (5 nm) which suggests a reduced difference between the core and the corona. Solvation dynamics in a P123 micelle displays a bulklike ultrafast component (<0.3 and 1 ps) in the PEO corona region, a 200 ps component arising from dynamics of polymer segments, and a very long component (5000 or 3000 ps) due to the highly restricted PPO core. In a P123-SDS aggregate, at lambdaex = 375 and 405 nm, the solvation dynamics is found to be faster than that in P123 micelle. In this case, the component (3000 ps) arising from the core region is faster than that (5000 ps) in P123 micelle. In both P123 micelle and P123-SDS aggregate, the relative contribution of the core region decreases and that of the corona region increases with an increase in lambdaex. At lambdaex = 435 nm, which probes the hydrophilic corona, the solvation dynamics for both P123 micelle and P123-SDS aggregate are almost similar.     

Room temperature synthesis of crystalline CeO2 nanopowder: advantage of sonochemical method over conventional method

In the present study, nano-sized ceria (CeO(2)) powders were prepared using conventional and sonochemically assisted precipitation method, without any stabilizers, using cerium nitrate as a starting material and sodium hydroxide as a precipitating agent. The synthesized ceria powders were characterized by XRD, TGA and SEM to determine crystallite size, % crystallinity, thermal weight loss and shape respectively. It was found that the crystallite size obtained in both the synthesis methods were below 30 nm. It was also found that sonochemical synthesis method is energy efficient method saving more than 92% of energy as compared to that utilized by the conventional synthesis method. There was also a significant reduction in the reaction duration.     

Investigation of chemical bath deposition of CdO thin films using three different complexing agents

Chemical bath deposition of CdO thin films using three different complexing agents, namely ammonia, ethanolamine, and methylamine is investigated. CdSO₄ is used as Cd precursor, while H₂O₂ is used as an oxidation agent. As-grown films are mainly cubic CdO₂, with some Cd(OH)₂ as well as CdO phases being detected. Annealing at 400 °C in air for 1 h transforms films into cubic CdO. The calculated optical band gap of as-grown films is in the range of 3.37-4.64 eV. Annealed films have a band gap of about 2.53 eV. Rutherford backscattering spectroscopy of as-grown films reveals cadmium to oxygen ratio of 1.00:1.74 ± 0.01 while much better stoichiometry is obtained after annealing, in accordance with the X-ray diffraction results. A carrier density as high as 1.89 × 10²⁰ cm⁻³ and a resistivity as low as 1.04 × 10⁻² Ω-cm are obtained.     

A review of biphasic hydroformylation for long chain substrates

The regioselective hydroformylation reactions of long chain olefins catalyzed by different unmodified and modified Co-based, Rh-based catalysts are summarized. The mechanism of homogeneous hydroformylation reactions using Co-based/Rh-based catalysts (unmodified) showed inhibition of reaction rate due to higher partial pressure of CO and also caused difficulty in separating catalysts from the product mixture. Hydroformylation reactions in biphasic medium using water soluble catalysts (Rh, Co, Ru/TPPTS) with an effective surfactant, cetyltrimethylammonium bromide (CTAB), are discussed. The homogeneous biphasic systems are not applicable for long chain olefins due to their low solubility in aqueous phase.     

Femtosecond solvation dynamics in different regions of a bile salt aggregate: excitation wavelength dependence

Solvation dynamics of coumarin 480 (C480) in the secondary aggregate of a bile salt (sodium deoxycholate, NaDC) is studied using femtosecond up-conversion. The secondary aggregate resembles a long (approximately 40 A) hollow cylinder with a central water-filled tunnel. Different regions of the aggregate are probed by variation of the excitation wavelength (lambdaex) from 375 to 435 nm. The emission maximum of C480 displays an 8 nm red shift as the lambdaex increases from 345 to 435 nm. The 8 nm red edge excitation shift (REES) suggests that the probe (C480) is distributed over regions of varied polarity. Excitation at a short wavelength (375 nm) preferentially selects the probe molecule in the buried locations and exhibits slow dynamics with a major (84%) slow component (3500 ps) and a small (16%) contribution of the ultrafast component (2.5 ps). Excitation at lambdaex=435 nm (red end) corresponds to the exposed sites where solvation dynamics is very fast with a major (73%) ultrafast component (相似文献   

Sonochemical reactors: scale up aspects

The present work deals with the discussion on the engineering aspects of the design of large-scale sonochemical reactors using the solutions of the bubble dynamics equations as well as experimentation with different reactor types and reactions. Design correlations for the collapse pressure and its relation to the cavitational yield have also been given which should assist the designers in the choice of the operating parameters for a desired cavitational effect. Some techniques for the intensification of cavitational activity (with the use of additives) with an aim of reducing the cost of operation have also been discussed. The guidelines for the future work to be carried out to remove the lacunae in the design information with an aim of developing industrial scale efficient sonochemical reactors have also been mentioned.     

Ultrasonic atomization: effect of liquid phase properties

Experiments have been conducted to understand the mechanism by which the ultrasonic vibration at the gas liquid interface causes the atomization of liquid. For this purpose, aqueous solutions having different viscosities and liquids showing Newtonian (aqueous solution of glycerin) and non-Newtonian behavior (aqueous solution of sodium salt of carboxy methyl cellulose) were employed. It has been found that the average droplet size produced by the pseudo-plastic liquid is less than that produced by the viscous Newtonian liquid having viscosity equal to zero-shear rate viscosity of the shear thinning liquid. The droplet size was found to increase initially with an increase in the viscosity up to a certain threshold viscosity after which the droplet size was found to decrease again. Also droplet size distribution is found to be more compact (uniform sizes) with an increasing viscosity of the atomizing liquid. The presence of the cavitation and its effect on the atomization has been semi quantitatively confirmed using energy balance and by the measurement of the droplet ejection velocities and validated on the basis of the decomposition of the aqueous KI solution. A correlation has been proposed for the prediction of droplet size for aqueous Newtonian fluids and fluids showing non-Newtonian behavior based on the dimensionless numbers incorporating the operating parameters of the ultrasonic atomizer and the liquid phase physico-chemical properties.     

Fe-catalyzed Selective N-Formylation Protocol for Amines Using Glycolic Acid as C1 Bio-Building Block

Due to current global issues involving climate change and energy crises, it requires several complete overhauls in process developments sectors of energy and chemical manufacturing industries towards more sustainable and readily applicable protocols. As a contribution to this goal with an example of iron-based catalysis, this work presents a synthetic protocol for synthesis of N-formamides with glycolic acid as a C1 bio-building block, which is catalyzed through earth abundant and magnetically active Fe powder as catalyst. The protocol was applied to a wide variety of substrates affording yields in the range of 68–94 % and also performed well at 1 gram and 5 gram scale with yields of up to 86 % and 83 %, respectively. The catalyst was shown to be reusable up to 4 runs and the spent catalyst has been studied using PXRD and XPS analyses to determine catalyst deactivation and its remediation. Plausible reaction pathway has been suggested based on control experiments and GC-MS results for the process.     

Using statistical data for reliable mobile communications

We examine the extent to which statistical mobility information can increase the reliability of the service experienced by users in mobile networks. Interrupted or dropped calls are an aspect of reliability that stems from the mobility of users. An existing user can move to a cell where there are no resources available to support their call. A natural solution is the reservation of resources in multiple cells that the user is likely to move to. This scheme is called selective reservations and it relies on predicting the next move of the user. Recently, there has been some work on estimating the movement probabilities (also known as the mobility profile) of the user. In this paper, we quantify the usefulness of the mobility profile to improve the reliability of the service perceived by the mobile users. We identify two parameters which characterize the profile: Accuracy and Focus. Accuracy expresses the probability that the host will move as we expect it to. Focus describes how well we can identify patterns in the movement of the users. In our simulations, we examine the effect of the quality of the predictions on the performance of the system. We show that Accuracy and Focus have great impact on the performance of selective reservations. We also show how flexibility in hand‐offs can help in decreasing the dropping probability, and how this can be facilitated by letting the users make a second try at moving in case it fails the first time. Copyright © 2001 John Wiley & Sons, Ltd.