Deep eutectic solvents (DESs) have shown potential as novel media to support molecular aggregation. The self-aggregation behavior of two common and popular carbocyanine dyes, 5,5',6,6'-tetrachloro-1,1'-diethyl-3,3'-di(4-sulfobutyl)-benzimidazole carbocyanine (TDBC) and 5,5'-dichloro-3,3'-di(3-sulfopropyl)-9-methyl-benzothiacarbo cyanine (DMTC), is investigated within DES-based systems under ambient conditions. Although TDBC is known to form J-aggregates in basic aqueous solution, DMTC forms H-aggregates under similar conditions. The DESs used, glyceline and reline, are composed of salt choline chloride and two vastly different H-bond donors, glycerol and urea, respectively, in 1:2 mol ratios. Both DESs in the presence of base are found to support J-aggregates of TDBC. These fluorescent J-aggregates are characterized by small Stokes' shifts and subnanosecond fluorescence lifetimes. Under similar conditions, DMTC forms fluorescent H-aggregates along with J-aggregates within the two DES-based systems. The addition of cationic surfactant cetyltrimethylammonium bromide (CTAB) below its critical micelle concentration (cmc) to a TDBC solution of aqueous base-added glyceline shows the prominent presence of J-aggregates, and increasing the CTAB concentration to above cmc results in the disruption of J-aggregates and the formation of unprecedented H-aggregates. DMTC exclusively forms H-aggregates within a CTAB solution of aqueous base-added glyceline irrespective of the surfactant concentration. Anionic surfactant, sodium dodecylsulfate (SDS), present below its cmc within aqueous base-added DESs supports J-aggregation by TDBC; for similar SDS addition, DMTC forms H-aggregates within the glyceline-based system whereas both H- and J-aggregates exist within the reline-based system. A comparison of the carbocyanine dye behavior in various aqueous base-added DES systems to that in aqueous basic media reveals contrasting aggregation tendencies and/or efficiencies. Surfactants as additives are demonstrated to control and modulate carbocyanine dye self-aggregation within DES-based media. The unique nature of DESs as alternate media toward affecting cyanine dye aggregation is highlighted.
august 16, 2008 EPW Economic & Political Weekly 20 panchayats, which alone enjoy substantial revenue raising powers. This cannot be done by more revenue assignments alone. It is as much a function of tax efforts, functional devolution as of making the size of panchayats viable in terms of convergence of services, technical and administrative capability and availability of revenue – raising potential. There is a great need to make the majority of panchayats viable units, at least in terms of population and revenue. While this is primarily the task of the SFCs and depends a great deal on the political will of the concerned state government, the UFC cannot stay away from the task of building local democracy in Indian fiscal federal system. Special Claim Octroi, which was a substantial source of revenue for local governments is being phased out. The entertainment tax, an important revenue source of local governments, is treated as a service tax. My plea is that general sales tax should be made a shareable tax with a special share assigned to local governments to compensate for the losses they suffer. In brief, the task of building a viable local government system, which is made an integral part of Indian federal polity is a challenging task and a continuing legacy of the 73rd/74th constitutional amendments. The UFC has an important role in this. This note seeks to underscore the issues in the context of the THFC, which should work towards a new public finance architecture in the country.
Thirty one genotypes of rice were evaluated for high grain yield. The results indicated that high estimates of genotypic and phenotypic coefficient of variation were recorded for plant height, number of reproductive tillers per plant, panicle length, biological yield per plant, harvest index, test weight, number of grain per panicle and grain yield per plant. High heritability coupled with high genetic advance were revealed for plant height, number of reproductive tillers per plant, panicle length, biological yield per plant, harvest index, test weight, number of grain per panicle and grain yield per plant. Improvement in grain yield can be made by selecting these yield contributed characters having high heritability coupled with high genetic advance. Grain yield per plant showed significant and positive association with number of reproductive tillers per plant, panicle length, days to maturity, number of grain per panicle biological yield per plant and harvest index at both genotypic and phenotypic level. Thus, it can be inferred that selection based on any one of these traits either alone or in combination, will result in identifying high yielding strains. Path coefficient analysis of genotypic and phenotypic exhibited high positive and direct effect of harvest index, number of grains per panicle, test weight, biological yield per plant and plant height on grain yield per plant.
Abstract Based on fluorescence probe, electrical conductivity, surface tension, small‐angle X‐ray/dynamic light scattering, and transmission electron microscopy experiments, we present the first clear lines of evidence for self‐aggregation of cationic surfactants of the n ‐alkyltrimethylammonium family within an archetypical deep eutectic solvent comprised of a 1:2 molar mixture of choline chloride and glycerol. Estimated thermodynamic parameters suggest this self‐aggregation process to be less entropically driven than that in water. These novel water‐free self‐assemblies might serve as dynamic soft templates to direct the growth of size‐ or shape‐tailored nanoparticles within water‐restricted media.
Developing and characterizing green solvents with low toxicity and cost is one of the most important issues in chemistry. Deep Eutectic Solvents (DESs), in this regard, have shown tremendous promise. Compared to popular organic solvents, DESs possess negligible VOCs and are non-flammable. Compared to ionic liquids, which share many characteristics but are ionic compounds and not ionic mixtures, DESs are cheaper to make, much less toxic and mostly biodegradable. An estimate of the polarity associated with DESs is essential if they are to be used as green alternatives to common organic solvents in industries and academia. As no one physical parameter can satisfactorily represent solute-solvent interactions within a medium, polarity of DESs is assessed through solvatochromic optical spectroscopic responses of several UV-vis absorbance and molecular fluorescence probes. Information on the local microenvironment (i.e., the cybotactic region) that surrounds several solvatochromic probes [betaine dye, pyrene, pyrene-1-carboxaldehyde, 1-anilino-8-naphthalene sulfonate (ANS), p-toluidinyl-6-naphthalene sulfonate (TNS), 6-propionyl-2-(dimethylaminonaphthalene) (PRODAN), coumarin-153, and Nile Red] for four common and popular DESs formed from choline chloride combined with 1,2-ethanediol, glycerol, urea, and malonic acid, respectively, in 1 : 2 molar ratios termed ethaline, glyceline, reline, and maline is obtained and used to assess the effective polarity afforded by each of these DESs. The four DESs as indicated by these probe responses are found to be fairly dipolar in nature. Absorbance probe betaine dye and fluorescence probes ANS, TNS, PRODAN, coumarin-153, and Nile Red, whose solvatochromic responses are based on photoinduced charge-transfer, imply ethaline and glyceline, DESs formed using alcohol-based H-bond donors, to be relatively more dipolar in nature as compared to reline and maline. The pyrene polarity scale, which is based on polarity-induced changes in vibronic bands, indicates reline, the DES composed of urea as the hydrogen bond donor, to be significantly more dipolar than the other three DESs. Response of pyrene-1-carboxaldehyde, a polarity probe based on inversion of n-π* and π-π* states, hints at maline to be the most dipolar of the four DESs. The molecular structure of the H-bond donor in a DES clearly controls the dipolarity afforded by the DES. H-bonding and other specific solute-solvent interactions are found to play an important role in solvatochromic probe behavior for the four DESs. The cybotactic region of a probe dissolved in a DES affords information on the polarity of the DES towards solutes of similar nature and functionality.
Fabrication of complex molecular films of organic materials is one of the most important issues in modern nanoscience and nanotechnology. Soft materials with flexible properties have been given much attention and can be obtained through bottom up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and technologies. In this short communication, we report the successful incorporation of cationic laser dye Rhodamine 6G abbreviated as R6G into the pre-assembled polyelectrolyte/Surfactant complex film onto quartz substrate by electrostatic adsorption technique. Poly(allylamine hydrochloride) (PAH) was used as polycation and Sodium dodecyl sulphate(SDS) was used as anionic surfactant. UV-Vis absorption spectroscopic characterization reveals the formation of only H-type aggregates of R6G in their aqueous solution and both H and J-type aggregates in PAH/SDS/R6G complex LbL films as well as the kinetics of adsorption of R6G onto the complex films. The ratio of the absorbance intensity of two aggregated bands in PAH/SDS/R6G complex films is merely independent of the concentration range of the SDS solution used to fabricate PAH/SDS complex self-assembled films. Atomic Force Microscopy reveals the formation of R6G aggregates in PAH/SDS/R6G complex films.
Deep eutectic solvents (DESs) have shown tremendous promise as green solvents with low toxicity and cost. Understanding molecular aggregation processes within DESs will not only enhance the application potential of these solvents but also help alleviate some of the limitations associated with them. Among DESs, those comprising choline chloride and appropriate hydrogen-bond donors are inexpensive and easy to prepare. On the basis of fluorescence probe, electrical conductivity, and surface tension experiments, we present the first clear lines of evidence for self-aggregation of an anionic surfactant within a DES containing a small fraction of water. Namely, well-defined assemblies of sodium dodecyl sulfate (SDS) apparently form in the archetype DES Reline comprising a 1:2 molar mixture of choline chloride and urea. Significant enhancement in the solubility of organic solvents that are otherwise not miscible in choline chloride-based DESs is achieved within Reline in the presence of SDS. The remarkably improved solubility of cyclohexane within SDS-added Reline is attributed to the presence of spontaneously formed cyclohexane-in-Reline microemulsions by SDS under ambient conditions. Surface tension, dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), density, and dynamic viscosity measurements along with responses from the fluorescence dipolarity and microfluidity probes of pyrene and 1,3-bis(1-pyrenyl)propane are employed to characterize these aggregates. Such water-free oil-in-DES microemulsions are appropriately sized to be considered as a new type of nanoreactor.
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