Far-Field Optical Microscopy with a Nanometer-Scale Resolution Based on the In-Plane Image Magnification by Surface Plasmon Polaritons

A new far-field optical microscopy capable of reaching nanometer-scale resolution is developed using the in-plane image magnification by surface plasmon polaritons. This approach is based on the optical properties of a metal-dielectric interface that may provide extremely large values of the effective refractive index neff up to 103 as seen by surface polaritons, and thus the diffraction limited resolution can reach nanometer-scale values of lambda/2neff. The experimental realization of the microscope has demonstrated the optical resolution better than 60 nm at 515 nm illumination wavelength.

Compact operators without extended eigenvalues

A complex number lambda is called an extended eigenvalue of a bounded linear operator T on a Banach space B if there exists a non-zero bounded linear operator X acting on B such that XT = lambda TX. We show that there are compact quasinilpotent operators on a separable Hilbert space, for which the set of extended eigenvalues is the one-point set {1}.

Three constructive examples of separable pre-Hilbert spaces nonisomorphic to their closed hyperplanes

An example of a sigma -compact infinite-dimensional pre-Hilbert space H is constructed such that any continuous linear operator T: H --> H is of the form T = lambdaI + F for some lambda is an element of R and for a finite-dimensional continuous linear operator F. A class of simple examples of pre-Hilbert spaces nonisomorphic to their closed hyperplanes is given. A sigma -compact pre-Hilbert space H isomorphic to H x R x R and nonisomorphic to H x R is also constructed.

Mechanically tunable multiband compact quadrifilar helix antenna with dual mode operation

We show that by introducing a gap at the center of the helical sections (where the current is minimum) of a lambda/2 quadrifilar helix antenna (QHA) and varying the axial length and radial gap between the overlapping volutes, the antenna gives a 28% impedance bandwidth which is nine times the bandwidth of a conventional QHA. A 16% bandwidth with a front to back ratio of >= 14 dB is achievable with 5-14% reduction in the size of the QHA. The structure can yield a monopole radiation pattern suitable for terrestrial applications or a hemispherical pattern suitable for satellite use. The simulation results are validated by measurements at L-band.

Dual-mode compact structure comprising of side-fed bifilar and quadrifilar helix antenna

A side-fed bifilar helix antenna can be integrated with a quadrifilar helix antenna in a piggy back configuration in order to achieve a dual-mode radiating structure. The overall length of the structure is 0.44 lambda at the resonant frequency (1.54 GHz) of the space mode antenna and 0.39 lambda at the resonant frequency (1.34 GHz) of the terrestrial mode antenna. The computed results are validated by experimental data.

Effect of helix turn angle on the performance of a half wavelength quadrifilar antenna

The impedance and radiation pattern parameters of a lambda/2 quadrifilar helix antenna (QHA) with turn angles in the range 0 degrees to 235 degrees are analyzed. It is shown that by selecting the helix turn angle to satisfy the minimum bandwidth and beamwidth requirements, an improved electrical performance and a reduction in the physical size of the antenna is obtained. This is demonstrated by comparing the performance of a conventional half turn QHA with structures having a smaller pitch length. The computed results are validated by experimental data at L-band.

Lewis acid platinum complexes of conformationally flexible NUPHOS diphosphines: Highly efficient catalysts for the carbonyl-ene reaction

Enantiopure Lewis acid complexes of conformationally flexible acyclic and monocyclic NUPHOS diphosphines, delta- and lambda-[(NUPHOS)Pt(OTf)(2)], are efficient catalysts for the carbonyl-ene reaction between various unsymmetrical 1,1'-disubstituted alkenes and phenylglyoxal or ethyl glyoxylate. While catalyst performance was substrate dependent, ee values as high as 95% and yields up to 90% have been obtained. In a number of cases catalysts generated from delta- and lambda-[(NUPHOS)Pt{(S)-BINOL}] showed marked enhancements in enantioselectivity in ionic liquids compared with organic media. Although an enhancement in enantioselectivity was not obtained for all substrate combinations in such cases, the enantioselectivities were comparable to those obtained in dichloromethane. Furthermore, although the ee's are initially comparable in both the ionic liquid and dichloromethane, a gradual erosion of ee with time was found in the organic solvent, whereas the ee remained constant in the ionic liquid. Preliminary kinetic investigations suggest that the decrease in ee may be due to a faster racemization of the catalyst in dichloromethane compared with the ionic liquid.

Comparative study of diastereoisomer interconversion in chiral BINOL-ate and diamine platinum complexes of conformationally flexible NUPHOS diphosphines

A thorough and detailed study of diastereointerconversion in the chiral platinum complexes [(NUPHOS)Pt{(S)-BINOL}] (3a-e) has been undertaken and compared with the results of a similar study with [(BIPHEP)Pt{(S)-BINOL}]. Rate data revealed that this process obeys first-order relaxation kinetics, and rate constants for conversion of the minor to the major diastereoisomer have been obtained. Eyring analysis of the data gave DeltaH(double dagger) and DeltaS(double dagger) values of 22-25 kcal mol(-1) and -1 to -16 eu, respectively. In combination with computational analysis, these studies indicate that atropinversion most likely occurs via an on-metal pathway involving a planar seven-membered transition state. Substitution of (S)-BINOL for (S,S)-DPEN results in a marked reduction in the barrier to atropinversion; a DeltaH(double dagger) value of 17 kcal mol(-1) has been determined for the conversion of delta-[(Ph-4-NUPHOS)Pt{(S,S)-DPEN}]Cl-2 to lambda-[(Ph-4-NUPHOS)Pt{(S,S)-DPEN}]Cl-2, which could indicate that an alternative mechanism operates.

Highly efficient asymmetric hetero-Diels-Alder reactions of carbonyl compounds catalyzed by Lewis acid platinum complexes of conformationally flexible NUPHOS-type diphosphines

Conformationally flexible NUPHOS-type diphosphines have been resolved as their diastereopure platinum BINOLate complexes delta- and lambda-[(NUPHOS)Pt{(S)-BINOL}] and the corresponding enantiopure Lewis acids delta- and lambda-[(NUPHOS)Pt(OTf)(2)], being generated by protonation with trifluoromethanesulfonic acid, act as highly efficient catalysts for the hetero-Diels-Alder reaction of nonactivated conjugated dienes with aryl glyoxals and glyoxylate esters, giving ee's as high as 99%.

Resonance Raman and DFT studies of tetra-tert-butyl porphine: Assignment of strongly enhanced distortion modes in a ruffled porphyrin

The free-base form of tetra-tert-butyl porphine (TtBP), which has extremely bulky meso substituents, is severely distorted from planarity, with a ruffling angle of 65.5degrees. The resonance Raman spectrum of TtBP (lambda(ex) = 457.9 nm) and its d(2), d(8), and d(10) isotopomers have been recorded, and while the spectra show high-frequency bands similar to those observed for planar meso-substituted porphyrins, there are several additional intense bands in the low-frequency region. Density functional calculations at the B3-LYP/6-31G(d) level were carried out for all four isotopomers, and calculated frequencies were scaled using a single factor of 0.98. The single factor scaling approach was validated on free base porphine where the RMS error was found to be 14.9 cm(-1). All the assigned bands in the high-frequency (> 1000 cm(-1)) region of TtBP were found to be due to vibrations similar in character to the in-plane skeletal modes of conventional planar porphyrins. In the low-frequency region, two of the bands, assigned as nu(8) (ca. 330 cm(-1)) and nu(16) (ca. 540 cm(-1)), are also found in planar porphyrins such as tetra-phenyl porphine (TPP) and tetra-iso-propyl porphine (IPP). Of the remaining three very strong bands, the lowest frequency band was assigned as gamma(12) (pyr swivel, obsd 415 cm(-1), calcd 407 cm(-1) in do). The next band, observed at 589 cm-1 in the do compound (calcd 583 cm(-1)), was assigned as a mode whose composition is a mixture of modes that were previously labeled gamma(13) (gamma(CmCaHmCa)) andy gamma(11) (pyr fold(asym)) in NiOEP. The final strong band, observed at 744 cm(-1) (calcd 746 cm(-1)), was assigned to a mode whose composition is again a mixture of gamma(11) and gamma(13), although here it is gamma(11) rather than gamma(13) which predominates. These bands have characters and positions similar to those of three of the four porphyrin ring-based, weak bands that have previously been observed for NiTPP. In addition there are several weaker bands in the TtBP spectra that are also

The dichotomy in the DNA-binding behaviour of ruthenium(II) complexes bearing benzoxazole and benzothiazole groups

The substituted tris(bipyridine)ruthenium(II) complexes {[Ru(bpy)(2)(4,4'-bbob)](2+) and [Ru(bpy)(2)(5,5'-bbob)](2+) [where bpy = 2,2'-bipyridine and bbob = bis(benzoxazol-2-yl)-2,2'-bipyridine] have been prepared and compared to the previously studied complex [Ru(bpy)(2)(4,4'-bbtb)](2+) [where bbtb = bis(benzothiazol-2-yl)-2,2'-bipyridine]. From the UV/VIS titration studies, Delta-[Ru(bpy)(2)(4,4'bbob)](2+) displays a stronger association than the Lambda-isomer with calf-thymus DNA (ct-DNA). For [Ru(bpy)(2)(5,5'-bbob)](2+), there appears to be minimal interaction with ct-DNA. The results of fluorescence titration studies suggest that [Ru(bpy)(2)(4,4'-bbob)](2+) gives an increase in emission intensity with increasing ct-DNA concentrations, with an enantiopreference for the A isomer, confirmed by membrane dialysis studies. The fluorescent intercalation displacement studies revealed that [Ru(bpy)(2)(4,4'-bbob)](2+) and [Ru.(bpy)(2)(5,5'bbob)](2+) display a preference for more open DNA structures such as bulge and hairpin sequences. While Delta-[Ru(bpy)(2)(4,4'-bbtb)](2+) has shown the most significant affinity for all the oligonucleotides sequences screened in previous studies, it is the A isomer of the comparable benzoxazole ruthenium(II) complex (Delta-[Ru(bpy)(2)(4,4'-bbob)](2+)) that preferentially binds to DNA.

Benzothiazole bipyridine complexes of ruthenium(II) with cytotoxic activity

A series of benzothiazole-substituted trisbipyridine ruthenium(II) analogues {[Ru(bpy)(2)(4,5'-bbtb)](2+), [Ru(bpy)(2)(5,5'-bbtb)](2+) and [Ru(bpy)(2)(5-mbtb)](2+) [bpy is 2,2'-bipyridine, bbtb is bis(benzothiazol-2-yl)-2,2'-bipyridine, 5-mbtb is 5-(benzothiazol-2-yl),5'-methyl-2,2'-bipyridine]} have been prepared and compared with the complex [Ru(bpy)(2)(4,4'-bbtb)](2+) reported previously. From the UV-vis spectral studies, substitution at the 5-position of the bpy causes the ligand-centred transitions to occur at considerably lower energy than for those with the functionality at the 4-position, while at the same time causing the emission to be effectively quenched. However, substitution at the 4-position causes the metal-to-ligand charge transfer to occur at lower energies. Fluorescent intercalator displacement studies indicate that the doubly substituted complexes displace ethidium bromide from a range of oligonucleotides, with the greater preference shown for bulge and hairpin sequences by the Lambda enantiomer. Since the complexes only show small variation in the UV-vis spectra on the introduction of calf thymus DNA and a small increase in fluorescence they do not appear to be intercalators, but appear to associate within one of the grooves. All of the reported bisbenzothiazole complexes show reasonable cytotoxicity against a range of human cancer cell lines.

Enantiomeric programming in tripodal transition metal scaffolds

A new route to the isolation of the enantiopure tris- chelate complex (Delta/Lambda)- fac-[Ru( L-1)(3)] 21 (where L-1 is 2,2'-bipyridine-5-carboxylic acid) is demonstrated, where the transition metal centre retains the memory of the chirality present in a simple tripodal tether used to control the metal centred geometry.

Stereoselective coordination chemistry of the tetradentate chelating ligand (2R,3R)-bis(2,2 '-dipyridyl-5-methoxyl) butane

The enantiomerically pure ligand L-3RR (2R, 3R)-bis(2,2'-dipyridyl-5-methoxyl) butane has been synthesised by linking two 2,2'-bipyridine units with (2R, 3R)-butandiol. The reaction of L-3RR with Zn(II) afforded a mononuclear species and the H-1 NMR spectroscopy points to a C-1 symmetry, expected for a distorted trigonal bipyramidal coordination environment. These observations were confirmed by MM2 calculations and electrospray mass spectrometry. The reaction of L-3RR with iron(II) indicated the formation of a dinuclear species by mass spectrometry. Solution state CD spectroscopy indicates that both complexes adopt a Lambda-configuration, implying a single stranded dinuclear iron(II) complex is present rather than the anticipated triple helical architecture.

Dynamic resonances and tunnelling in the multiphoton ionization of argon

We present results of wavepacket simulations for multiphoton ionization in argon. A single active electron model is applied to estimate the single-electron ionization rates and photoelectron energy distributions for lambda = 390 nm light with intensities up to I = 2 x 10(14) W cm(-2). The multiphoton ionization rates are compared with R-matrix Floquet calculations and found to be in very good agreement. The photoelectron energy distribution is used to study the nature of ionization at the higher intensities. Our results are consistent with recent calculations and experiments which show the imprint of the tunnelling process in the multiphoton regime. For few-cycle intense pulses, we find that the strong modulation of intensity and increased bandwidth leads to dynamic mixing of the 3d and 5s resonances.