UV–Vis and NMR spectroscopic investigations on effective and selective non-covalent interactions between fullerenes and calix[6]arene

Ground state non-covalent interactions between a macro cyclic calixarene receptor, namely, 4-tert-butylcalix[6]arene (1), and fullerenes (C₆₀ and C₇₀) were studied in toluene medium by absorption spectrophotometric method. Absorption band due to the charge transfer (CT) transition have been observed in the visible region between fullerenes and 1. Utilizing the CT absorption bands, various important physicochemical parameters like oscillator strength, resonance energy, transition dipole strength of the fullerene-1 complexes and ionization potential of 1 is determined in present investigations. From Jobs method of continuous variation, it is observed that both C₆₀ and C₇₀ form stable 1:1 complexes with 1. The most fascinating feature of the present study is that 1 binds selectively C₇₀ compared to C₆₀ as obtained from binding constant (K) data of C₆₀–1 (K_C60–1) and C₇₀–1 (K_C70–1) complexes, i.e., K_C60–1 = 32,400 dm³·mol^? 1 and K_C70–1 = 110,000 dm³.mol^? 1 and selectivity (K_C70–1/K_C60–1) = 3.4. ¹H NMR analysis provides very good support in favor of strong binding between C₇₀ and 1.     

Development and validation of a sensitive ELISA for quantitation of Grastim (rhG-CSF) in rat plasma: Application to a pharmacokinetic study

Grastim is bacterially produced recombinant counterpart of human granulocyte colony stimulating factor (G-CSF). It has biological activity similar to that of endogenous G-CSF. In the present work a sensitive, accurate, precise and enzyme-linked immunosorbent assay (ELISA) for the quantitation of G-CSF in rat plasma was developed and validated. The ELISA method employed a technique in which anti-human-G-CSF was adsorbed onto 96-well maxisorp plates and used to capture the G-CSF in rat plasma samples. The captured G-CSF was then detected using streptavidin-HRP amplification system. Absolute recovery was >90% from rat plasma. The validation includes assessments of method accuracy and precision, range of reliable response, lower limit of quantitation (LLOQ), storage stability (30 days) in rat plasma and assay specificity. The standard curve for G-CSF was linear (R2 > 0.996) in the concentration range 4.88-625 pg/mL. The LLOQ was established at 4.88 pg/mL. The inter- and intra-day precisions in the measurement of quality control (QC) samples, 15, 250 and 500 pg/mL, were in the range 3.00-8.66% relative standard deviation (RSD) and 1.03-4.69% RSD, respectively. Accuracy in the measurement of QC samples was in the range 87.28-110.79% of the nominal values. The assay shows dilutional linearity and specificity. Stability of G-CSF was established for 30 days at -80 degrees C and through three freeze-thaw cycles. The validated assay was successfully employed for the assessment of pharmacokinetic disposition of G-CSF in rats.     

The transient dynamics leading to spin turbulence in high-field solution magnetic resonance: a numerical study

The dynamics under the joint action of radiation damping and the distant dipolar field in high-field solution magnetic resonance are investigated. Different dynamical regimes during the evolution are identified and their individual features are discussed. In the steady state, the dynamics can be associated with a strange attractor in phase space on which the motion is chaotic. The possibility of the observed chaotic motion being spatiotemporal is examined.     

Absorption spectrophotometric study of supramolecular complexation of [60]- and [70]fullerenes with 24,26-dimethoxy-25,27-dihydroxy calix[4]arene

Supramolecular interactions of 24,26-dimethoxy-25,27-dihydroxy calix[4]arene (1) with [60]- and [70]fullerenes have been studied in only chloroform and in a ternary solvent mixture comprising of chloroform, ethyl alcohol and toluene by UV-vis absorption spectrophotometric method. The experimental results are explained using the model that takes into account the interaction between electronic subsystems of 1 and fullerene. The most interesting feature is the preference of [60]fullerene over [70]fullerene for 1 in ternary solvent mixture as revealed by higher value of formation constant of [60]fullerene/1 complex. The selectivity towards [60]fullerene opens up the way toward self-assembling systems and new separation and purification methods for fullerenes.     

A study on oriented relative clique number

An oriented graph is a directed graph with no directed cycle of length one or two. The relative clique number of an oriented graph is the cardinality of a largest subset $X$ of vertices such that each pair of vertices is either adjacent or connected by a directed 2-path. It is known that the oriented relative clique number of a planar graph is at most 80. Here we improve the upper bound to 32. We also prove an upper bound of 14 for oriented relative clique number of triangle-free planar graphs. Furthermore, we determine the exact values of oriented relative clique number for the families of outerplanar graphs with girth at least $g$ and planar graphs with girth at least $g+2$ for all $g\ge 3$. Moreover, we study the relation of oriented relative clique number with oriented chromatic number, oriented absolute clique number and maximum degree of a graph. We also show that oriented relative clique number of a connected subcubic graph is at most seven which weakly supports a conjecture by Sopena (JGT 1997).     

Chiral bis-Acetal Porphyrazines as Near-infrared Optical Agents for Detection and Treatment of Cancer

We report the preparation of chiral oxygen atom-appended porphyrazines (pzs) as biomedical optical agents that absorb and emit in the near-IR wavelength range. These pzs take the form M[pz(A_4-nB_n)], where “A” and “B” represent moieties appended to the pz’s pyrrole entities, A = (2R,3R) 2,3-dimethyl-2,3-dimethoxy-1,4-diox-2-ene, B = β,β′-di-isopropoxybenzo, M is the incorporated metal ion (M = H₂, Zn), and n = 0, 1, 2 (-cis/-trans) and 3 ( Scheme 1 ). When dissolved in polar media, H₂[pz(trans-A₂B₂)] 5a does not fluoresce and has a negligible quantum yield for singlet oxygen generation (Ф_Δ = 0.074 ± 0.001, methanol), as measured by the photo-oxidation of DMA. However, when sequestered in the nonpolar environment of a liposome, it displays strong NIR emission (λ _max = 705 nm, Ф _f = 0.087) and an extremely high singlet oxygen quantum yield (Ф_Δ→1). Of this series, H₂[pz(trans-A₂B₂)] 5a is attractive as a potential optical probe, showing strongly fluorescent uptake by cells in culture, while 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide measurements of cell viability show no evidence of dark toxicity. This agent does show significant photoinduced toxicity suggesting that pzs such as 5a have promise as “theranostic” optical agents that can be visualized with fluorescence imaging while acting as a sensitizer for photodynamic therapy.

Figure Scheme 1. Open in figure viewer PowerPoint Synthesis of Porphyrazines 3a – 7a , 3b – 7b .     

A self-assembled, luminescent europium cholate hydrogel: a novel approach towards lanthanide sensitization

We propose a new self-assembly based strategy for the design of novel lanthanide based luminescent materials. In this approach a europium hydrogel is prepared and sensitization is achieved by doping the gel with pyrene in a non-coordinated fashion.     

Magnetic properties of the mixed spinel NiAlxCrxFe2-2xO4

The crystal structure and magnetic properties of the Al and Cr cosubstituted disordered spinel series NiAl_xCr_xFe_2-2xO₄ are investigated by means of Xray diffraction, magnetization, a.c. susceptibility and Mössbauer effect measurements. The lattice constants are determined and the applicability of Vegard's law has been tested. The variation of the saturation magnetic moment per formula unit measured at 77 K and 300 K with Al–Cr content is satisfactorily explained on the basis of Neel's collinear spin ordering model for =0.1–0.5. The Mössbauer spectra at 300 K have been fitted with two sextets in the ferrimagnetic state corresponding to Fe³⁺ at tetrahedral (A) and octahedral (B) sites for 0.5. Mössbauer results confirm a collinear ferrimagnetic structure for =0.1–0.5. The Curie temperature obtained from a.c. susceptibility decreases nearly linear with increase of Al–Cr concentration from =0.1 to 0.5.