Quantization of the electromagnetic field outside static black holes and its application to low-energy phenomena

We discuss the Gupta-Bleuler quantization of the free electromagnetic field outside static black holes in the Boulware vacuum. We use a gauge which reduces to the Feynman gauge in Minkowski spacetime. We also discuss its relation with gauges used previously. Then we apply the low-energy sector of this field theory to investigate some low-energy phenomena. First, we discuss the response rate of a static charge outside the Schwarzschild black hole in four dimensions. Next, motivated by string physics, we compute the absorption cross sections of low-energy plane waves for the Schwarzschild and extreme Reissner-Nordstr\"om black holes in arbitrary dimensions higher than three.Comment: 26 pages (revtex), no figures, misprints in some conditions correcte

Recent Advances in Ru Catalyzed Transfer Hydrogenation and Its Future Perspectives

Over the past few decades, Ru catalyzed transfer hydrogenation (TH) and asymmetric transfer hydrogenation (ATH) reactions of unsaturated hydrocarbons, imine, nitro and carbonyl compounds have emerged as economic and powerful tools in organic synthesis. These reactions are most preferred processes having applications in the synthesis of fine chemicals to pharmaceuticals due to safe handling as these do not require hazardous pressurized H2 gas. The catalytic activity and selectivity of Ru complexes were investigated with a variety of ligands based on pincer NHC, cyclophane, half-sandwich, organophosphine etc. These ligands coordinate to Ru center in a proper orientation with a labile group replaced by H-source (like methanol, isopropanol, formic acid, dioxane, THF), which facilitate the β-hydrogen transfer to generate metal hydride species (Ru-H) and produce desired reduced product. This chapter describes the recent advances in TH and ATH reactions with homogeneous and heterogeneous Ru catalysts having different ligand environments and mechanistic details leading to their sustainable industrial applications

Selective interactions of a few acridinium derivatives with single strand DNA: study of photophysical and DNA binding interactions

Novel acridinium derivatives 1-3, wherein steric factors have been varied systematically through substitution at the ninth position of the acridinium ring, were synthesized and their interactions with single strand and double strand DNA have been investigated through photophysical, biophysical, and microscopic techniques. The acridinium derivative 1 exhibited quantitative fluorescence yields (φ<SUB>f</SUB>≅ 1) and high lifetime of 35 ns, while significantly lower fluorescence yields of 0.11 and 0.02 and lifetimes of 3.5 and 1.2 ns were observed for 2 and 3, respectively. The derivatives 1 and 2 having 2-methylphenyl and 2,4-dimethylphenyl substituents at the ninth position of the acridinium ring showed selective interactions with single strand DNA (ssDNA) with association constants of K<SUB>ssDNA</SUB> = 6.3-6.6 × 10<SUP>4</SUP> M<SUP>−1</SUP>, while negligible interactions were observed with double strand DNA (dsDNA). In contrast, the derivative 3 with 2,6-dimethylphenyl substitution showed negligible interactions with both ssDNA and dsDNA. Studies with a series of 19-mer oligonucleotides indicate that these derivatives exhibit significant selectivity for the sequences rich in guanosine (ca. 3-fold) as compared to the cytosine-rich sequences. These derivatives with high water solubility and the ability to distinguish between ssDNA and dsDNA through changes in fluorescence emission can be used as fluorescent probes for understanding the role of ssDNA in various biological processes and to study various DNA-ligand interactions

Dansyl - naphthalimide dyads as molecular probes: effect of spacer group on metal ion binding properties

Interaction of a few dansyl-naphthalimide conjugates 1a-e linked through polymethylene spacer groups with various metal ions was investigated through absorption, fluorescence, NMR, isothermal calorimetric (ITC), and laser flash photolysis techniques. The characteristic feature of these dyads is that they exhibit competing singlet-singlet energy transfer (SSET) and photoinduced electron transfer (PET) processes, both of which decrease with the increase in spacer length. Depending on the spacer group, these dyads interact selectively with divalent Cu2+ and Zn2+ ions, as compared to other mono- and divalent metal ions. Jobs plot analysis showed that these dyads form 2:3 complexes with Cu2+ ions, while 1:1 complexes were observed with Zn2+ ions. The association constants for the Zn2+ and Cu2+ complexes were determined and are found to be in the order 103-105 M-1. Irrespective of the length of the spacer group, these dyads interestingly act as fluorescence ratiometric molecular probes for Cu2+ ions by altering the emission intensity of both dansyl and naphthalimide chromophores. In contrast, only the fluorescence intensity of the naphthalimide chromophore of the lower homologues (n = 1-3) was altered by Zn2+ ions. 1H NMR and ITC measurements confirmed the involvement of both sulfonamide and dimethylamine groups in the complexation with Cu2+ ions, while only the latter group was involved with Zn2+ ions. Laser excitation of the dyads 1a-e showed formation of a transient absorption which can be attributed to the radical cation of the naphthalimide chromophore, whereas only the triplet excited state of the dyads 1a-e was observed in the presence of Cu2+ ions. Uniquely, the complexation of 1a-e with Cu2+ ions affects both PET and SSET processes, while only the PET process was partially inhibited by Zn2+ ions in the lower homologues (n = 1-3) and the higher homologues exhibited negligible changes in their emission properties. Our results demonstrate that the spacer length dependent variations of the photophysical properties of these novel conjugates not only enable the selective detection of Cu2+ and Zn2+ ions but also aid in discriminating these two biologically important metal ions

DNA-assisted long-lived excimer formation in a cyclophane

A color-changed sandwich: A novel water-soluble cyclophane containing anthracene and imidazolium moieties (see structure) exhibits dual emission in aqueous medium and undergoes sequence-selective interactions with DNA but not with proteins and micelles. In the presence of DNA, it forms a sandwich-type excimer, which exhibits an unusually long lifetime (T) and red-shifted emission. This cyclophane can be used for DNA recognition through "turned on" excimer emission

Development of new photosensitizers for photodynamic therapy

In the photo-dynamic therapy (PDT) uses it, that certain compounds, called photosensitizers, for cells only in the light toxicity. Thus, for example, tumor cells are killed in the organism targeted. This could be particularly successful if it succeeds, with the photosensitizers before light exposure selectively transport into tumor cells and then be killed to enrich

Direct Evidence on the external stimuli induced dissembly of DNA through microscopic techniques

Calf thymus DNA exhibited a regular network-like structure on mica and copper surfaces, respectively, under atomic force (AFM) and scanning electron (SEM) microscopic techniques while oily streak cholesteric birefringent texture was observed on the glass surface under optical polarizing microscopy (OPM). In the presence of an external stimuli such as temperature, intercalating compounds such as the viologen-linked pyrene 1 and para-tolylacridinium iodide (2) and the minor groove binding spermine (4) prevented the DNA-DNA interactions and thereby perturbed the self-assembly of DNA. In contrast, the major groove binding bovine serum albumin (BSA) and the noninteracting ligand ortho-tolylacridinium iodide (3) did not affect the overall morphology of DNA, as characterized through the AFM, SEM, OPM, and circular dichroism (CD) techniques. As far as we know, this is the first report that presents direct evidence for the perturbation of supramolecular assembly of DNA under various conditions and that can be visualized through different microscopic techniques

Chiral supramolecular assemblies of a squaraine dye in solution and thin films: concentration-, temperature-, and solvent-induced chirality inversion

We prepared novel cholesterol-appended squaraine dye 1 and model squaraine dye 2 and investigated their aggregation behavior in solution and thin films using photophysical, chiroptical, and microscopic techniques. Investigations on the dependence of aggregation on solvent composition (good/poor, CHCl3/CH3CN) demonstrated that squaraine dye 1 forms two novel H-type chiral supramolecular assemblies with opposite chirality at different good/poor solvent compositions. Model compound 2 formed J-type achiral assemblies under similar conditions. The supramolecular assembly of 1 observed at lower fractions of the poor solvent could be assigned to the thermodynamically stable form, while a kinetically controlled assembly is formed at higher fractions of the poor solvent. This assignment is evidenced by temperature- and concentration-dependent experiments. With increasing temperature, the chirality of the kinetically controlled aggregate was lost and, on cooling, the aggregate with the opposite chirality was formed. On further heating and cooling the aggregates thus formed resulted in no significant changes in chirality, that is they are thermodynamically stable. Similarly, at lower concentrations, the thermodynamically stable form exists, but at higher concentration aggregation was found to proceed with kinetic control. Based on these observations it can be assumed that formation of the kinetically controlled assembly might be largely dependent on the presence of the nonpolar cholesterol moiety as well as the amount of poor solvent present. However, under solvent-free conditions, structurally different aggregates were observed when drop cast from solutions containing monomer, whereas a left-handed CD signal corresponding to the thermodynamically controlled assemblies was observed from pre-aggregated solutions

Novel bifunctional acridine-acridinium conjugates: synthesis and study of their chromophore-selective electron-transfer and DNA-binding properties

Novel bifunctional conjugates 1-3, with varying polymethylene spacer groups, were synthesized, and their DNA interactions have been investigated by various biophysical techniques. The absorption spectra of these systems showed bands in the regions of 300-375 and 375-475 nm, corresponding to acridine and acridinium chromophores, respectively. When compared to 1 (φf = 0.25), bifunctional derivatives 2 and 3 exhibited quantitative fluorescence yields (φf = 0.91 and 0.98) and long lifetimes (τ = 38.9 and 33.2 ns). The significant quenching of fluorescence and lifetimes observed in the case of 1 is attributed to intramolecular electron transfer from the excited state of the acridine chromophore to the acridinium moiety. DNA-binding studies through spectroscopic investigations, viscosity, and thermal denaturation temperature measurements indicate that these systems interact with DNA preferentially through intercalation of the acridinium chromophore and exhibit significant DNA association constants (KDNA = 105-107 M−1). Compound 1 exhibits chromophore-selective electron-transfer reactions and DNA binding, wherein only the acridinium moiety of 1 interacts with DNA, whereas optical properties of the acridine chromophore remain unperturbed. Among bifunctional derivatives 2 and 3, the former undergoes DNA mono-intercalation, whereas the latter exhibits bis-intercalation; however both of them interact through mono-intercalation at higher ionic strength. Results of these investigations demonstrate that these novel water-soluble systems, which exhibit quantitative fluorescence yields, chromophore-selective electron transfer, and DNA intercalation, can have potential use as probes in biological applications

A supramolecular ON-OFF-ON fluorescence assay for selective recognition of GTP

With the objective of developing small molecule based receptors for nucleosides and nucleotides, interactions of a cyclic donor-acceptor conjugate 1 with adenosine, AMP, ADP, CTP, UTP, ITP, ATP, and GTP have been investigated by absorption, steady-state, and time-resolved fluorescence, cyclic voltammetry (CV), NMR, and fluorescence indicator displacement techniques. Titration of 1 with the fluorescent indicator, 8-hydroxy-1,3,6-pyrene trisulfonate (HPTS), resulted in nearly complete fluorescence quenching of HPTS, along with 25% hypochromicity in its absorption spectrum. Benesi-Hildebrand analysis gave a 1:1 stoichiometry for the complex between the receptor 1 and HPTS with an association constant (Kass) of 4.66 × 104 M−1 in buffer. The driving force for such a complexation was evaluated to be the synergistic effects of π-stacking and electrostatic interactions inside the cavity as confirmed by the effect of ionic strength, temperature, and the negative results obtained with the model compound 2. Titration of the nonfluorescent complex [1.HPTS] with various nucleosides and nucleotides resulted in revival of fluorescence of the indicator, HPTS. It was observed that GTP induces maximum displacement of HPTS from the complex [1.HPTS] with an overall fluorescence enhancement of ca. 150-fold. The addition of adenosine, AMP, ADP, CTP, and UTP showed negligible changes, whereas ca. 45- and 50-fold enhancement was observed with ATP and ITP, respectively. The competitive displacement of the indicator by various analytes is found to be in the order GTP (buffer) ≈ GTP (biofluid) » ITP ≈ ATP &gt; UTP &gt; CTP ≈ ADP ≈ AMP ≈ Ade. By virtue of having a better π-electron cloud, GTP undergoes effective electronic, π-stacking, and electrostatic interactions inside the cavity and forms a stable complex with the receptor 1. The uniqueness of this assay is that it differentiates GTP from ATP and other nucleotides and signals the event through a visual "turn on" fluorescence mechanism in buffer as well as in biological fluids