Crystal Engineering of Stable Temozolomide Cocrystals

The antitumor prodrug temozolomide (TMZ) decomposes in aqueous medium of pH≥7 but is relatively stable under acidic conditions. Pure TMZ is obtained as a white powder but turns pink and then brown, which is indicative of chemical degradation. Pharmaceutical cocrystals of TMZ were engineered with safe coformers such as oxalic acid, succinic acid, salicylic acid, d,l ‐malic acid, and d,l ‐tartaric acid, to stabilize the drug as a cocrystal. All cocrystals were characterized by powder X‐ray diffraction (PXRD), single crystal X‐ray diffraction, and FT‐IR as well as FT‐Raman spectroscopy. Temozolomide cocrystals with organic acids (pK_a 2–6) were found to be more stable than the reference drug under physiological conditions. The half‐life (T_1/2) of TMZ–oxalic and TMZ–salicylic acid measured by UV/Vis spectroscopy in pH 7 buffer is two times longer than that of TMZ (3.5 h and 3.6 h vs. 1.7 h); TMZ–succinic acid, TMZ–tartaric acid, and TMZ–malic acid also exhibited a longer half‐life (2.3, 2.5, and 2.8 h, respectively). Stability studies at 40 °C and 75 % relative humidity (ICH conditions) showed that hydrolytic degradation of temozolomide in the solid state started after one week, as determined by PXRD, whereas its cocrystals with succinic acid and oxalic acid were intact at 28 weeks, thus confirming the greater stability of cocrystals compared to the reference drug. The intrinsic dissolution rate (IDR) profile of TMZ–oxalic acid and TMZ–succinic acid cocrystals in buffer of pH 7 is comparable to that of temozolomide. Among the temozolomide cocrystals examined, those with succinic acid and oxalic acid exhibited both an improved stability and a comparable dissolution rate to the reference drug.     

Determination of cosmological parameters: An introduction for non-specialists

I start by defining the cosmological parameters H ₀, Θ _m and Θ_A. Then I show how the age of the universe depends on them, followed by the evolution of the scale parameter of the universe for various values of the density parameters. Then I define strategies for measuring them, and show the results for the recent determination of these parameters from measurements on supernovas of type 1a. Implications for particle physics is briefly discussed at the end.     

Synthesis of silver nanoparticle in imidazolium and pyrolidium based ionic liquid reverse micelles: A step forward in nanostructure inorganic material in room temperature ionic liquid field

Two silver salts, silver tetrafluoroborate and silver trifluoromethanesulfonate were dissolved in two different room temperature ionic liquids (RTILs), 1-Butyl-3 methyl imidazolium tetrafluoroborate ([Bmim][BF₄]) and 1-Butyl-1 methyl pyrrolidinium trifluoromethanesulfonate ([Bmpy][Tfms]). Triton x-100 (TX-100) surfactant and cyclohexane as nonpolar medium are used to dissolve these RTILs to create reverse micellar system. Pure reverse micellar system is characterized by dynamic light scattering (DLS) measurement. These pure RTIL reverse micellar systems are used to prepare stable silver nanoparticle solution without using any other auxiliary solvent in the whole process.     

Synthesis and characterization of a polymer-anchored palladium(II) Schiff base complex and its catalytic efficiency in phosphine-free Sonogashira coupling reactions

A polymer-anchored Pd(II) Schiff base complex has been synthesized by reacting a polymeric amine with 2-pyridinecarboxaldehyde to get the polymer-anchored Schiff base, which was then reacted with palladium acetate. The catalyst was characterized by physicochemical and spectroscopic methods. It shows excellent catalytic activity in the Sonogashira coupling of phenylacetylene with aryl halides using triethylamine as a base and copper iodide as a co-catalyst in water under open air at 70 °C. We have also studied the effects of base and solvent on the coupling reaction. Sonogashira reactions of phenylacetylene with a variety of functionalized aryl halides were performed under the optimized reaction conditions. This catalyst gives excellent yields without the use of phosphine ligands. Further experiments showed that the catalyst can be used five times without much loss in the catalytic activity.     

DNA-directed artificial light-harvesting antenna

Designing and constructing multichromophoric, artificial light-harvesting antennas with controlled interchromophore distances, orientations, and defined donor-acceptor ratios to facilitate efficient unidirectional energy transfer is extremely challenging. Here, we demonstrate the assembly of a series of structurally well-defined artificial light-harvesting triads based on the principles of structural DNA nanotechnology. DNA nanotechnology offers addressable scaffolds for the organization of various functional molecules with nanometer scale spatial resolution. The triads are organized by a self-assembled seven-helix DNA bundle (7HB) into cyclic arrays of three distinct chromophores, reminiscent of natural photosynthetic systems. The scaffold accommodates a primary donor array (Py), secondary donor array (Cy3) and an acceptor (AF) with defined interchromophore distances. Steady-state fluorescence analyses of the triads revealed an efficient, stepwise funneling of the excitation energy from the primary donor array to the acceptor core through the intermediate donor. The efficiency of excitation energy transfer and the light-harvesting ability (antenna effect) of the triads was greatly affected by the relative ratio of the primary to the intermediate donors, as well as on the interchromophore distance. Time-resolved fluorescence analyses by time-correlated single-photon counting (TCSPC) and streak camera techniques further confirmed the cascading energy transfer processes on the picosecond time scale. Our results clearly show that DNA nanoscaffolds are promising templates for the design of artificial photonic antennas with structural characteristics that are ideal for the efficient harvesting and transport of energy.     

Solvent relaxation of a room-temperature ionic liquid [bmim][PF6] confined in a ternary microemulsion

In this paper we have reported the solvent and rotational relaxation of 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF₆]) confined in tween 20/([bmim][PF₆]/water microemulsion using coumarin 153 (C-153) as probe. The most interesting feature of our experiment was that we observed an increase in solvent relaxation time with increase in R (R = tween 20-to-[bmim][PF₆] molar ratio). This is due to the fact that with increase in [bmim][PF₆] content of the microemulsions, the microviscosity of the pool of the microemulsions increases, and motion of ions of [bmim][PF₆] is hindered in the pool of microemulsions. Since motion of ions is responsible for solvation in room-temperature ionic liquids (RTILs), solvent-relaxation time increases with increase in R.     

ΔB = 2 transitions in supersymmetric theories

We carry out a systematic analysis of ΔB = 2 interactions in supersymmetric theories. The selection rules in ΔB = 2 transition depend on the relative value of M (the mass scale that characterizes the ΔB = 2 interactions) and Λ_s (the super-symmetry-breaking scale). In particular, if M ? 10⁴GeV and Λ_s ～ 10²GeV, the effective ΔB = 2 interactions induce NN annihilation in a nucleus yielding two kaons in the final state while processes with only one or zero kaons are suppressed by mixing angles. On the other hand, if M ? 10⁴GeV, then supersymmetry does not imply any additional selection rules beyond those of ordinary (non-supersymmetric) theories.     

Premicellar and micelle formation behavior of aqueous anionic surfactants in the presence of triphenylmethane dyes: protonation of dye in ion pair micelles

The premicellar and micelle formation behaviors of four cationic triphenylmethane dyes, viz, Pararosaniline (RN), Crystal violet (CV), Ethyl violet (EV), and Malachite green (MG), in aqueous anionic surfactant solutions of sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), and sodium dodecyl sulfonate (SDSN) have been studied by spectral and surface tension measurements. The study was carried out within a pH range where the dyes are stable in their quinoid forms. The dyes have been found to form dye–surfactant ion pairs (DSIPs) with the surfactants, at the surfactant concentrations well below their critical micelle concentration, CMC*. The DSIPs behave like nonionic surfactants and form an air–water interfacial monolayer. The DSIPs have a lower critical micelle concentration (CMC_IP), greater efficiency, and lower effectiveness than the corresponding pure surfactants. As the surfactant concentration is increased below the CMC*, the DSIPs start forming micelles of their own where the dye gets protonated and exists as a protonated dye–surfactant ion pair (PDSIP) in the ion pair micelles. As the concentration of the surfactant exceeds the CMC* of the pure surfactant, the protonation reverses gradually with the dye remaining in the micelles in solubilized form and the DSIPs in the air–water interfacial monolayer are replaced by pure surfactants. The distorted helical isomeric form (isomer B) of the dyes is favored in the PDSIPs. Copyright © 2009 John Wiley & Sons, Ltd.     

Complete tree subset difference broadcast encryption scheme and its analysis

The subset difference (SD) method proposed by Naor, Naor and Lotspiech is the most popular broadcast encryption (BE) scheme. It is suitable for real-time applications like Pay-TV and has been suggested for use by the AACS standard for digital rights management in Blu-Ray and HD-DVD discs. The SD method assumes the number of users to be a power of two. We propose the complete tree subset difference (CTSD) method that allows the system to support an arbitrary number of users. In particular, it subsumes the SD method and all results proved for the CTSD method also hold for the SD method. Recurrences are obtained for the CTSD scheme to count the number, N(n, r, h), of possible ways r users in the system of n users can be revoked to result in a transmission overhead or header length of h. The recurrences lead to a polynomial time dynamic programming algorithm for computing N(n, r, h). Further, they provide bounds on the maximum possible header length. A probabilistic analysis is performed to obtain an O(r log n) time algorithm to compute the expected header length in the CTSD scheme. Further, for the SD scheme we obtain an explicit limiting upper bound on the expected header length.