Copper(II) Complexes of l-Arginine as Netropsin Mimics Showing DNA Cleavage Activity in Red Light

Copper(II) complexes [Cu(L-arg)(2)](NO3)(2) (1) and [Cu(L-arg)(B)Cl]Cl (2-5), where B is a heterocyclic base, namely, 2,2'-bipyridine (bpy, 2), 1,10-phenanthroline (phen, 3), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 4), and dipyrido[3,2-a:2',3'-c)phenazine (dppz, 5), are prepared and their DNA binding and photoinduced DNA cleavage activity studied. Ternary complex 3, structurally characterized using X-ray crystallography, shows a square-pyramidal (4 + 1) coordination geometry in which the N,O-donor L-arginine and N,N-donor 1,10-phenanthroline form the basal plane with one chloride at the elongated axial site. The complex has a pendant cationic guanidinium moiety. The one-electron paramagnetic complexes display a metal-centered d-d band in the range of 590-690 nm in aqueous DMF They show quasireversible cyclic voltammetric response due to the Cu(II)/Cu(I) couple in the range of -0.1 to -0.3 V versus a saturated calomel electrode in a DMF-Tris HCl buffer (pH 7.2). The DNA binding propensity of the complexes is studied using various techniques. Copper(II) bis-arginate 1 mimics the minor groove binder netropsin by showing preferential binding to the AT-rich sequence of double-strand (ds) DNA. DNA binding study using calf thymus DNA gives an order: 5 (L-arg-dppz) >= 1 (biS-L-arg) > 4 (L-arg-dpq) > 3 (L-arg-phen) >> 2 (L-arg-bpy). Molecular docking calculations reveal that the complexes bind through extensive hydrogen bonding and electrostatic interactions with ds-DNA. The complexes cleave supercoiled pUC19 DNA in the presence of 3-mercaptopropionic acid as a reducing agent forming hydroxyl ((OH)-O-center dot) radicals. The complexes show oxidative photoinduced DNA cleavage activity in UV-A light of 365 nm and red light of 647.1 nm (Ar-Kr mixed-gas-ion laser) in a metal-assisted photoexcitation process forming singlet oxygen (O-1(2)) species in a type-II pathway. All of the complexes, barring complex 2, show efficient DNA photocleavage activity. Complexes 4 and 5 exhibit significant double-strand breaks of DNA in red light of 647.1 nm due to the presence of two photosensitizers, namely, L-arginine and dpq or dppz in the molecules.

Perception of ultraviolet light by crab spiders and its role in selection of hunting sites

The perception of ultraviolet (UV) light by spiders has so far been only demonstrated in salticids. Crab spiders (Thomisidae) hunt mostly on flowers and need to find appropriate hunting sites. Previous studies have shown that some crab spiders that reflect UV light use UV contrast to enhance prey capture. The high UV contrast can be obtained either by modulation of body colouration or active selection of appropriate backgrounds for foraging. We show that crab spiders (Thomisus sp.)hunting on Spathiphyllum plants use chromatic contrast, especially UV contrast, to make themselves attractive to hymenopteran prey. Apart from that, they are able to achieve high UV contrast by active selection of non-UV reflecting surfaces when given a choice of UV-reflecting and non-UV reflecting surfaces in the absence of odour cues. Honeybees (Apis cerana) approached Spathiphyllum plants bearing crab spiders on which the spiders were high UV-contrast targets with greater frequency than those plants on which the UV-contrast of the spiders was low. Thus, crab spiders can perceive UV and may use it to choose appropriate backgrounds to enhance prey capture, by exploiting the attraction of prey such as honeybees to UV.

Enhancing field emission from a carbon nanotube array by lateral control of electrodynamic force field

Fluctuation of field emission current from carbon nanotubes (CNTs) poses certain difficulties for their use in nanobiomedical X-ray devices and imaging probes. This problem arises due to deformation of the CNTs due to electrodynamic force field and electron-phonon interaction. It is of great importance to have precise control of emitted electron beams very near the CNT tips. In this paper, a new array configuration with stacked array of CNTs is analysed and it is shown that the current density distribution is greatly localised at the middle of the array, that the scatter due to electrodynamic force field is minimised and that the temperature transients are much smaller compared to those in an array with random height distribution.

Disulfide luminescence. Emission characteristics of cyclic tetrapeptide disulfides

Luminescence has been detected in cyclic tetrapeptide disulfides containing only nonaromatic residues. Excitation of the S-S- n-cr transition between 280 and 290 nm leads to.ernission in the region 300-340 nm. The position and intensity of the emission band depends on the stereochemistry of the peptide and polarity of the solvent. Quantum yields ranging from 0.002 to 0.026 have been determined. Disulfide luminescence is quenched by oxygen and enhanced in solutions saturated with nitrogen. Contributions from disulfide linkages should be considered, when analysing the emission spectra of proteins, lacking tryptophan but having a high cystine content.

Singlet emission studies on porphyrins appended with heterocyclic bases

Porphyrins appended in the meso positions with 1,2-diazole, indole and quinoline are shown to exhibit enhanced fluorescence quantum yields relative to meso tetraphenyl porphyrin. The singlet emission yields decrease with the number of appended heterocyclic bases. An intramolecular charge transfer resonance mechanism has been advanced to interpret these results.

Light scattering studies on solutions of chlorinated rubber

Measurements have been made of the depolarisation factors \sigma u ,\sigma v ,\sigma h, and the intensity of scattering in the horizontal transverse direction, in the case of solutions of four different samples of chlorinated rubber in carbon tetrachloride. The size, shape and molecular weight of the micelles have been deduced by the application of the light scattering theories of Gans, Vrklajan and Katalinic and Debye. The extent to which the degradation of the rubber molecule occurs on chlorination has also been assessed.

Catalytic transformation of aliphatic alcohols to corresponding esters in O2 under neutral conditions using visible-light irradiation

Selective oxidation of aliphatic alcohols under mild and base-free conditions is a challenging process for organic synthesis. Herein, we report a one-pot process for the direct oxidative esterification of aliphatic alcohols that is significantly enhanced by visible-light irradiation at ambient temperatures. The new methodology uses heterogenerous photocatalysts of gold–palladium alloy nanoparticles on a phosphate-modified hydrotalcite support and molecular oxygen as a benign oxidant. The alloy photocatalysts can absorb incident light, and the light-excited metal electrons on the surface of metal nanoparticles can activate the adsorbed reactant molecules. Tuning the light intensity and wavelength of the irradiation can remarkably change the reaction activity. Shorter wavelength light (<550 nm) drives the reaction more efficiently than light of longer wavelength (e.g., 620 nm), especially at low temperatures. The phosphate-exchanged hydrotalcite support provides sufficient basicity (and buffer) for the catalytic reactions; thus, the addition of base is not required. The photocatalysts are efficient and readily recyclable. The findings reveal the first example of using “green” oxidants and light energy to drive direct oxidative esterification of aliphatic alcohols under base-free, mild conditions.

Single-Symbol ML Decodable Distributed STBCs for Partially-Coherent Cooperative Networks

A relay network with N relays and a single source-destination pair is called a partially-coherent relay channel (PCRC) if the destination has perfect channel state information (CSI) of all the channels and the relays have only the phase information of the source-to-relay channels. In this paper, first, a new set of necessary and sufficient conditions for a space-time block code (STBC) to be single-symbol decodable (SSD) for colocated multiple antenna communication is obtained. Then, this is extended to a set of necessary and sufficient conditions for a distributed STBC (DSTBC) to be SSD for. a PCRC. Using this, several SSD DSTBCs for PCRC are identified. It is proved that even if a SSD STBC for a co-located MIMO channel does not satisfy the additional conditions for the code to be SSD for a PCRC, single-symbol decoding of it in a PCRC gives full-diversity and only coding gain is lost. It is shown that when a DSTBC is SSD for a PCRC, then arbitrary coordinate interleaving of the in-phase and quadrature-phase components of the variables does not disturb its SSD property for PCRC. Finally, it is shown that the possibility of channel phase compensation operation at the relay nodes using partial CSI at the relays increases the possible rate of SSD DSTBCs from (2)/(N) when the relays do not have CSI to(1)/(2), which is independent of N.

Evidence for peroxide and Cul+ species in La1.8Sro.2Cu04 from photo-emission studies

Employing photo-emission and Auger electron spectroscopy, it is shown that La, ,Sr&uO,contains 0:- -typespeciesandCu'+ ions, proportionsof these speciesincrease with decreasing temperature. These species may play an important role in the high-temperature superconductivity of this oxide.

The Reorganisation of Provincial Territories in Light of the Imperial Decision-Making Process : Later Roman Arabia and Tres Palaestinae as Case Studies

The dissertation examines Roman provincial administration and the phenomenon of territorial reorganisations of provinces during the Imperial period with special emphasis on the provinces of Arabia and Palaestina during the Later Roman period, i.e., from Diocletian (r. 284 305) to the accession of Phocas (602), in the light of imperial decision-making. Provinces were the basic unit of Roman rule, for centuries the only level of administration that existed between the emperor and the cities of the Empire. The significance of the territorial reorganisations that the provinces were subjected to during the Imperial period is thus of special interest. The approach to the phenomenon is threefold: firstly, attention is paid to the nature and constraints of the Roman system of provincial administration. Secondly, the phenomenon of territorial reorganisations is analysed on the macro-scale, and thirdly, a case study concerning the reorganisations of the provinces of Arabia and Palaestina is conducted. The study of the mechanisms of decision-making provides a foundation through which the collected data of all known major territorial reorganisations is interpreted. The data concerning reorganisations is also subjected to qualitative comparative analysis that provides a new perspective to the data in the form of statistical analysis that is sensitive to the complexities of individual cases. This analysis of imperial decision-making is based on a timeframe stretching from Augustus (r. 30 BC AD 14) to the accession of Phocas (602). The study identifies five distinct phases in the use of territorial reorganisations of the provinces. From Diocletian s reign there is a clear normative change that made territorial reorganisations a regular tool of administration for the decision-making elite for addressing a wide variety of qualitatively different concerns. From the beginning of the fifth century the use of territorial reorganisations rapidly diminishes. The two primary reasons for the decline in the use of reorganisations were the solidification of ecclesiastical power and interests connected to the extent of provinces, and the decline of the dioceses. The case study of Palaestina and Arabia identifies seven different territorial reorganisations from Diocletian to Phocas. Their existence not only testifies to wider imperial policies, but also shows sensitivity to local conditions and corresponds with the general picture of provincial reorganisations. The territorial reorganisations of the provinces reflect the proactive control of the Roman decision-making elite. The importance of reorganisations should be recognised more clearly as part of the normal imperial administration of the provinces and especially reflecting the functioning of dioceses.

Simultaneous display of spectrum and image in a single plane, and the realization of a lensless coherent optical processor

A novel method, designated the holographic spectrum reconstruction (HSR) method, is proposed for achieving simultaneous display of the spectrum and image of an object in a single plane. A study of the scaling behaviour of both the spectrum and the image has been carried out and based on this study, it is demonstrated that a lensless coherent optical processor can be realized.

Photosynthetic responses of subtidal seagrasses to a daily light cycle in Torres Strait: A comparative study

In this study, we examined the photosynthetic responses of five common seagrass species from a typical mixed meadow in Torres Strait at a depth of 5–7 m using pulse amplitude modulated (PAM) fluorometry. The photosynthetic response of each species was measured every 2 h throughout a single daily light cycle from dawn (6 am) to dusk (6 pm). PAM fluorometry was used to generate rapid light curves from which measures of electron transport rate (ETRmax), photosynthetic efficiency (α), saturating irradiance (Ek) and light-adapted quantum yield (ΔF/F′m) were derived for each species. The amount of light absorbed by leaves (absorption factor) was also determined for each species. Similar diurnal patterns were recorded among species with 3–4 fold increases in maximal electron rate from dawn to midday and a maintenance of ETRmax in the afternoon that would allow an optimal use of low light by all species. Differences in photosynthetic responses to changes in the daily light regime were also evident with Syringodium isoetifolium showing the highest photosynthetic rates and saturating irradiances suggesting a competitive advantage over other species under conditions of high light. In contrast Halophila ovalis, Halophila decipiens and Halophila spinulosa were characterised by comparatively low photosynthetic rates and minimum light requirements (i.e. low Ek) typical of shade adaptation. The structural makeup of each species may explain the observed differences with large, structurally complex species such as Syringodium isoetifolium and Cymodocea serrulata showing high photosynthetic effciciencies (α) and therefore high-light-adapted traits (e.g. high ETRmax and Ek) compared with the smaller Halophila species positioned lower in the canopy. For the smaller Halophila species these shade-adapted traits are features that optimise their survival during low-light conditions. Knowledge of these characteristics and responses improves our understanding of the underlying causes of changes in seagrass biomass, growth and survival that occur when modifications in light quantity and quality arise from anthropogenic and climatic disturbances that commonly occur in Torres Strait.

Patterns in tropical seagrass photosynthesis in relation to light, depth and habitat

Seagrass meadows across north-eastern Australia, survive a range of environmental conditions in coastal bays, reefs, estuarine and deepwater habitats through adaptation of a range of structural, morphological and physiological features. The aim of this study was to investigate the influence of spatial features (habitat type, site and depth) and photon flux on the photosynthetic performance of 11 tropical seagrass species. Pulse amplitude modulated (PAM) fluorometry was used to generate rapid light curves from which measures of maximal electron transport rate (ETRmax), photosynthetic efficiency (?), saturating irradiance (Ek) and effective quantum yield (?F/Fm?) were derived. The amount of light absorbed by leaves (absorption factor) was also determined for each population. In intertidal habitats many seagrass species exhibited typical sun-type responses with a close coupling of both ETRmax and Ek with photon flux. Photosynthetic performance ranged from minima in Thalassodendron ciliatum to maxima in Syringodium isoetifolium. The absence of a coupling between photosynthetic performance and photon flux in subtidal populations was most likely due to highly variable light climates and possible light attenuation, and hence the photo-biology of estuarine and deepwater seagrasses exhibited photosynthetic responses indicative of light limitation. In contrast seagrass species from shallow reef and coastal habitats for the most part exhibited light saturation characteristics. Of all the variables examined ETRmax, Ek and ?F/Fm? were most responsive to changing light climates and provide reliable physiological indicators of real-time photosynthetic performance of tropical seagrasses under different light conditions.