On the optical properties of the imidazolium ionic liquids

Room-temperature ionic liquids, particularly those based on substituted imidazolium cations, are currently being extensively studied for a variety of applications. Herein, we explore the suitability of several imidazolium salts in optical applications by carefully examining the electronic absorption and fluorescence behavior of these substances, generally believed to be transparent in most of the UV region and fully transparent in the visible region. It is shown that all imidazolium ionic liquids are characterized by significant absorption in the entire UV region and a long absorption tail that extends into the visible region. These absorption characteristics are attributed to the imidazolium moiety and its various associated structures. When excited in the UV or early part of the visible region, these liquids exhibit fluorescence, which covers a large part of the visible region and shows dramatic excitation wavelength dependence. The excitation wavelength dependent shift of the fluorescence maximum has been rationalized taking into consideration the existence of the various associated structures of the ionic liquids and the inefficiency of the excitation energy-transfer process between them. The results imply that these liquids may have serious drawbacks in some of the optical studies.     

Synthesis, characterisation and evaluation of polydithiocarbamate resin supported on macroreticular styrene-divinylbenzene copolymer for the removal of trace and heavy metal ions

A new chelating resin was synthesised by the modification of styrene-divinylbenzene (2%) copolymer and incorporation of dithiocarbamate groups. The polydithiocarbamate resin was characterised by elemental analysis, thermal studies and IR studies. The analytical characteristics of the sorbent were established and optimum sorption conditions for Cu, Ni, Pb, Fe, As and Mn determined. The total sorption capacity of the resin was 37 mg g⁻¹ for Ni(II), 35 mg g⁻¹ for Cu(II), 29 mg g⁻¹ for Fe(III) and 23 mg g⁻¹ for Pb(II). The optimum pH for the removal of metal ions was 3-5 for Ni(II), 5 for Cu(II), 4 for Fe(III) and 4-5 for Pb(II). High sorption capacity was observed when compared with other conventional chelating polymers. The sorption kinetics was fairly rapid, as apparent from the loading half time t_1/2 values, indicating a better accessibility of the chelating sites.     

Link Estimation and Routing in Sensor Network Backbones: Beacon-Based or Data-Driven?

In the context of IEEE 802.11b network testbeds, we examine the differences between unicast and broadcast link properties, and we show the inherent difficulties in precisely estimating unicast link properties via those of broadcast beacons even if we make the length and transmission rate of beacons be the same as those of data packets. To circumvent the difficulties in link estimation, we propose to estimate unicast link properties directly via data traffic itself without using periodic beacons. To this end, we design a data-driven routing protocol Learn-on-the-Fly (LOF). LOF chooses routes based on ETX/ETT-type metrics, but the metrics are estimated via MAC feedback for unicast data transmission instead of broadcast beacons. Using a realistic sensor network traffic trace and an 802.11b testbed of ~195 Stargates, we experimentally compare the performance of LOF with that of beacon-based protocols, represented by the geography-unaware ETX and the geography-based PRD. We find that LOF reduces end-to-end MAC latency by a factor of 3, enhances energy efficiency by a factor up to 2.37, and improves network throughput by a factor up to 7.78, which demonstrate the feasibility and the potential benefits of data-driven link estimation and routing.     

A facile and versatile protocol for the one-pot PhI(OAc)2 mediated divergent synthesis of quinazolines from 2-aminobenzylamine

In this present work iodobenzenediacetate (PIDA) has been found to be the key reagent in absence or presence of catalytic amount of molecular iodine (I₂)/zinc chloride (ZnCl₂) to construct quinazoline scaffold from 2-aminobenzylamine and a variety of easily available aldehydes, aryl and aliphatic amines, aliphatic and aryl alcohols and nitriles. This protocol provides mild and robust conditions along with great versatility to synthesize 2-substituted quinazolines from diverse starting materials in good to excellent yields. The developed protocol is also well applicable to reactants containing ease to oxidation prone functional groups.     

Lanthanide sensitization in II-VI semiconductor materials: a case study with terbium(III) and europium(III) in zinc sulfide nanoparticles

This work explores the sensitization of luminescent lanthanide Tb(3+) and Eu(3+) cations by the electronic structure of zinc sulfide (ZnS) semiconductor nanoparticles. Excitation spectra collected while monitoring the lanthanide emission bands reveal that the ZnS nanoparticles act as an antenna for the sensitization of Tb(3+) and Eu(3+). The mechanism of lanthanide ion luminescence sensitization is rationalized in terms of an energy and charge transfer between trap sites and is based on a semiempirical model, proposed by Dorenbos and co-workers (Dorenbos, P. J. Phys.: Condens. Matter 2003, 15, 8417-8434; J. Lumin. 2004, 108, 301-305; J. Lumin. 2005, 111, 89-104. Dorenbos, P.; van der Kolk, E. Appl. Phys. Lett. 2006, 89, 061122-1-061122-3; Opt. Mater. 2008, 30, 1052-1057. Dorenbos, P. J. Alloys Compd. 2009, 488, 568-573; references 1-6.) to describe the energy level scheme. This model implies that the mechanisms of luminescence sensitization of Tb(3+) and Eu(3+) in ZnS nanoparticles are different; namely, Tb(3+) acts as a hole trap, whereas Eu(3+) acts as an electron trap. Further testing of this model is made by extending the studies from ZnS nanoparticles to other II-VI semiconductor materials; namely, CdSe, CdS, and ZnSe.     

Mechanistic pathway for controlled extraction of guest molecule bound to herring sperm DNA using α-cyclodextrin

trans-2-[4-(Dimethylamino)styryl]benzothiazole (DMASBT) is known to have dual emitting states where the locally excited (LE) state is responsible for fluorescence in less polar environment and in polar milieu fluorescence is from the twisted intramolecular charge transfer (TICT) state. This compound also undergoes minor groove binding to herring sperm DNA (hsDNA) evidenced by the absorption spectra before and after the binding process and an effect on DMASBT fluorescence by an anionic quencher. The binding occurs efficiently in a 1:1 manner, i.e. one guest molecule binds to one site on the hsDNA. Instead of following the DNA twist, the aromatic part seems to project outward. Thus, the bound molecule can be successfully extracted out from the DNA in a controlled way by the hydrophobic cavity of α-cyclodextrin (α-CD). The extraction starts even with a low concentration of α-CD and increases as the concentration is increased. Absorption, steady-state and time resolved fluorescence spectroscopic methods have been employed to explore the mechanistic pathway of binding of DMASBT to hsDNA. The mechanistic approach toward controlled extraction of the guest molecules from hsDNA by α-CD is reported and is expected to serve a significant purpose in treatment of drug overdose.     

Dynamic Forwarding over Tree-on-DAG for Scalable Data Aggregation in Sensor Networks

Computing and maintaining network structures for efficient data aggregation incurs high overhead for dynamic events where the set of nodes sensing an event changes with time. Moreover, structured approaches are sensitive to the waiting-time which is used by nodes to wait for packets from their children before forwarding the packet to the sink. Although structure-less approaches can address these issues, the performance does not scale well with the network size. We propose ToD, a semi-structured approach that uses Dynamic Forwarding on an implicitly constructed structure composed of multiple shortest path trees to support network scalability. The key principle behind ToD is that adjacent nodes in a graph will have low stretch in one of these trees in ToD, thus resulting in early aggregation of packets. Based on simulations on a $2000$ nodes network and real experiments on a $105$ nodes Mica2-based network, we conclude that efficient aggregation in large scale networks can be achieved by our semi-structured approach.     

Physicochemical perspective of cyclodextrin nano and microaggregates

'Chemistry beyond the molecule' is the nickname for supramolecular chemistry. This branch of study is based on molecular recognition that is host-guest chemistry. A number of potential hosts have been defined and applied in scores of studies. Among all potential hosts, cyclodextrins occupy a high position due to their characteristic solubilisation capability and biocompatibility. In the present article we are revisiting the host-guest aspects of cyclodextrins from a physicochemical perspective. We present details of formation and applications of cyclodextrin nanoaggregates induced by guest molecules, the concerned thermodynamics behind the process and also the effect of concentration of the guest molecules on the morphology of the aggregates. This article reviews the topic mainly from the spectroscopic point of view.