Carbohydrate-Appended Tumor Targeting Iron(III) Complexes Showing Photocytotoxicity in Red Light

Glucose-appended photocytotoxic iron(III) complexes of a tridentate Schiff base phenolate ligand Fe(bpyag) (L)] (NO3) (1-3), where bpyag is N,N-bis(2- pyridylmethyl)-2-aminoethyl-beta-D-glucopyranoside and H2L is 3-(2-hydroxyphenylimino)-1-phenylbutan-1-one (H(2)phap) in 1, 3-(2-hydroxyphenylimino)-9-anthrylbutan-1-one (H(2)anap) 2, and 3- (2-hydroxyphenylimino)-1-pyrenylbutan-1-one (H(2)pyap) in 3, were synthesized and characterized. The complex Fe(dpma)(anapn(NO3) (4), having bis-(2-pyridylmethyl)benzylamine (dpma), in which the glucose moiety of bpyag is substituted by a phenyl group, was used as a control, and the complex Fe(dpma)(anap)](PF6) (4a) was structurally characterized by X-ray crystallography. The structure shows a FeN4O2 core in a distorted octahedral geometry. The high-spin iron(III) complexes with magnetic moment value of similar to 5.9 mu(B) showed a low-energy phenolate-to-Fe(III) charge-transfer (CT) absorption band as a shoulder near 500 nm with a tail extending to 700 nm and an irreversible Fe(III)-Fe(II) redox couple near -0.6 V versus saturated calomel electrode. The complexes are avid binders to calf thymus DNA and showed photocleavage of supercoiled pUC19 DNA in red (647 nm) and green (532 nm) light. Complexes 2 and 3 displayed significant photocytotoxicity in red light, with an IC50 value of similar to 20 mu M in HeLa and HaCaT cells, and no significant toxicity in dark. The cell death is via an apoptotic pathway, by generation of reactive oxygen species. Preferential internalization of the carbohydrate-appended complexes 2 and 3 was evidenced in HeLa cells as compared to the control complex 4. A 5-fold increase in the cellular uptake was observed for the active complexes in HeLa cells. The photophysical properties of the complexes are rationalized from the density functional theory calculations.

Going beyond Red with a Tri- and Tetracoordinate Boron Conjugate: Intriguing Near-IR Optical Properties and Applications in Anion Sensing

The design and synthesis of a new tri- and tetracoordinate boron conjugate is reported. The conjugate shows broad near-IR emission (similar to 625-850 nm) and is found to be a selective colorimetric and ratiometric sensor for fluoride ions.

Protamine-Capped Mesoporous Silica Nanoparticles for Biologically Triggered Drug Release

The fabrication of a mesoporous silica nanoparticle (MSN)-protamine hybrid system (MSN-PRM) is reported that selectively releases drugs in the presence of specific enzyme triggers present in the proximity of cancer cells. The enzyme trigger involved is a protease called trypsin, which is overexpressed in certain specific pathological conditions, such as inflammation and cancer. Overexpression of trypsin is known to be associated with invasion, metastasis, and growth in several cancers, such as leukemia, colon cancer, and colorectal cancer. The current system (MSN-PRM) consists of an MSN support in which mesopores are capped with an FDA-approved peptide drug protamine, which effectively blocks the outward diffusion of the drug molecules from the mesopores of the MSNs. On exposure to the enzyme trigger, the protamine cap disintegrates, opening up the molecular gates and releasing the entrapped drug molecules. The system exhibits minimal premature release in the absence of the trigger and selectively releases the encapsulated drugs in the presence of the proteases secreted by colorectal cancer cells. The ability of the MSN-PRM particles to deliver anticancer drugs to colorectal cancer cells has also been demonstrated. The hydrophobic drug is released into cancer cells subsequent to disintegration of the protamine cap, resulting in cell death. Drug-induced cell death in colorectal cancer cells is significantly enhanced when the hydrophobic drug that is known to degrade in aqueous environments is encapsulated in the MSN-PRM system in comparison to the free drug (P < 0.05). The system, which shows good biocompatibility and selective drug release, is a promising platform for cancer specific drug delivery.

Iron(III) benzhydroxamates of dipicolylamines for photocytotoxicity in red light and cellular imaging

Benzhydroxamate (BHA) iron(III) complexes Fe(BHA)(L)ClICI (I, 2)], where L is (phenyl)dipicolylamine (phdpa in I) and (pyrenyl)dipicolylamine (pydpa in 2), were prepared and their photocytotoxicity in visible (400-700 nm) and red (600-720 nm) light was studied. Complex 1 was structurally characterized by X-ray crystallography. The complexes have high-spin iron(III) centers. Complex 2, with a pyrenyl fluorophore, was used for cellular imaging, showing both mitochondrial and nuclear localization in the fluorescence microscopic study. The complex exhibited photocytotoxicity in red light in HeLa cancer cells, giving IC50 value of 24.4(+/- 0.4) pM, but remained essentially non-toxic in the dark. The involvement of reactive oxygen species and an apoptotic nature of cell death were observed from the cellular studies. (C) 2014 Elsevier Ltd. All rights reserved.

GdAlO3:Eu3+:Bi3+ nanophosphor: Synthesis and enhancement of red emission for WLEDs

GdAlO3, GdAlO3:Eu3+ and GdAlO3:Eu3+:Bi3+ nanophosphors were synthesised by solution combustion technique. Pure orthorhombic phase was obtained from powder X-ray diffraction (PXRD) studies. Scanning electron microscopy (SEM) micrographs showed the porous, agglomerated and irregular shaped particles. The particle size obtained by transmission electron microscopy (TEM) measurement was in good agreement with the values obtained by Debye Scherrer's and W-H plots. The selected area electron diffraction (SAED) pattern show single crystalline nature of the sample. Photoluminescence (PL) measurements were carried out for GdAlO3:Eu3+ and GdAlO3:Eu3+:Bi3+ phosphors excited at a wavelength of 274 nm. The characteristic emission peaks of Eu3+ ions were recorded at 590, 614, 655 and 695 nm corresponding to D-5(0) -> F-7(J) (J = 1, 2, 3, 4) transitions respectively. However, with addition of Bi3+ ions in GdAlO3:Eu3+, PL intensity drastically enhanced. Orange red color was tuned to deep red color with the addition of Bi3+ ions in GdAlO3:Eu3+ phosphor. Therefore, the phosphor was highly useful as red component in WLEDs. A single well resoled glow peak at 225 degrees C was recorded in GdAlO3 and GdAlO3:Eu3+. Further, with addition of Bi3+ ions, an additional peak at 300 degrees C was recorded. TL glow curves of different UV-exposed GdAlO3:Eu3+:Bi3+ show two TL peaks at 207 and 300 degrees C respectively. The 207 degrees C peak show simple glow peak structure and its intensity increases linearly up to 25 mm and after that it decrease. (C) 2014 Elsevier B.V. All rights reserved.

Oxovanadium(IV) catecholates of terpyridine bases for cellular imaging and photocytotoxicity in red light

Oxovanadium(IV) catecholates of terpyridyl bases, viz. VO(cat)(L)] (L - phtpy, 1; stpy, 2) and VO(dopa-NBD)(L)] (L = phtpy, 3; stpy, 4), where cat is benzene-1,2-diolate, dopa-NBD is 4-(2-(4-nitrobenzoc]1,2,5]oxadiazol-7-ylamino)ethyl)benzene-1,2-di olate, phtpy is (4'-phenyl)-2,2':6',2 `'-terpyridine and stpy is (2,2':6',2 `'-terpyridin-4'-oxy)ethyl-beta-D-glucopyranoside, were prepared and characterized, and their DNA binding, DNA photo-cleavage activity, photocytotoxicity in red light (600-720 nm), cellular uptake and intracellular localization behaviour were studied. The complexes showed an intense ligand-to-metal charge transfer (LMCT) band at similar to 500 nm. The sugar appended complexes 2 and 4 showed significant uptake into the cancer cells. The dopa-NBD complexes 3 and 4 showing green emission were used for cellular imaging. The complexes showed diffused cellular localization mainly in the cytosol and to a lesser extent into the nucleus as evidenced from the confocal microscopy study. Complexes 1-4 showed significant photocytotoxicity in the PDT spectral window giving low IC50 values, while remaining relatively non-toxic in dark.

Iron(III) Catecholates for Cellular Imaging and Photocytotoxicity in Red Light

Iron(III) complexes Fe(L)(L') (NO3)]-in which L is phenyl-N, N-bis(pyridin-2-yl) methyl]methanamine (1), (anthracen-9-yl)N, N-bis(pyridin-2-yl) methyl] methanamine (2), (pyreny-1-yl)-N, N-bis(pyridin- 2-yl) methyl] methanamine (3-5), and L' is catecholate (1-3), 4-tert-butyl catecholate (4), and 4-(2-aminoethyl)benzene- 1,2-diolate (5)-were synthesized and their photocytotoxic proper-ties examined. The five electron-paramagnetic complexes displayed a FeIII/ Fe-II redox couple near similar to 0.4 V versus a saturated calomel electrode (SCE) in DMF/0.1m tetrabutylammonium perchlorate (TBAP). They showed unpre-cedented photocytotoxicity in red light (600-720 nm) to give IC50-15 mm in various cell lines by means of apoptosis to generate reactive oxygen species. They were ingested in the nucleus of HeLa and HaCaT cells in 4 h, thereby interacting favorably with calf thymus (ct)-DNA and photocleaving pUC19 DNA in red light of 785 nm to form hydroxyl radicals.

A Comparative Assessment of Hand Preference in Captive Red Howler Monkeys, Alouatta seniculus and Yellow-Breasted Capuchin Monkeys, Sapajus xanthosternos

There are two major theories that attempt to explain hand preference in non-human primates-the `task complexity' theory and the `postural origins' theory. In the present study, we proposed a third hypothesis to explain the evolutionary origin of hand preference in non-human primates, stating that it could have evolved owing to structural and functional adaptations to feeding, which we refer to as the `niche structure' hypothesis. We attempted to explore this hypothesis by comparing hand preference across species that differ in the feeding ecology and niche structure: red howler monkeys, Alouatta seniculus and yellow-breasted capuchin monkeys, Sapajus xanthosternos. The red howler monkeys used the mouth to obtain food more frequently than the yellow-breasted capuchin monkeys. The red howler monkeys almost never reached for food presented on the opposite side of a wire mesh or inside a portable container, whereas the yellow-breasted capuchin monkeys reached for food presented in all four spatial arrangements (scattered, on the opposite side of a wire mesh, inside a suspended container, and inside a portable container). In contrast to the red howler monkeys that almost never acquired bipedal and clinging posture, the yellow-breasted capuchin monkeys acquired all five body postures (sitting, bipedal, tripedal, clinging, and hanging). Although there was no difference between the proportion of the red howler monkeys and the yellow-breasted capuchin monkeys that preferentially used one hand, the yellow-breasted capuchin monkeys exhibited an overall weaker hand preference than the red howler monkeys. Differences in hand preference diminished with the increasing complexity of the reaching-for-food tasks, i.e., the relatively more complex tasks were perceived as equally complex by both the red howler monkeys and the yellow-breasted capuchin monkeys. These findings suggest that species-specific differences in feeding ecology and niche structure can influence the perception of the complexity of the task and, consequently, hand preference.

A quinazoline derivative as quick-response red-shifted reporter for nanomolar Al3+ and applicable to living cell staining

A newly synthesized and structurally characterized quinazoline derivative (L) has been shown to act as a quick-response chemosensor for Al3+ with a high selectivity over other metal ions in water-DMSO. In the presence of Al3+, L shows a red-shifted ratiometric enhancement in fluorescence as a result of internal charge transfer and chelation-enhanced fluorescence through the inhibition of a photo-induced electron transfer mechanism. This probe detects Al3+ at concentrations as low as 1.48 nM in 100 mM HEPES buffer (DMSO-water, 1 : 9 v/v) at biological pH with a very short response time (15-20 s). L was applied to biological imaging to validate its utility as a fluorescent probe for monitoring Al3+ ions in living cells, illustrating its value in practical environmental and biological systems.

Colorimetric detection of melamine based on the size effect of AuNPs

A simple colorimetric detection of melamine was studied using 15 nm (AuNPs-I), 30 nm (AuNPs-II), and 40 nm (AuNPs-III) citrate-capped gold nanoparticles (AuNPs). The AuNPs aggregated in aqueous solution in the presence of melamine, showing a visual color change from red to blue. This color change led to a shift in the absorption peak from 527 nm, 526 nm, and 525 nm to 638 nm, 626 nm, and 680 nm for AuNPs-I, AuNPs-II, and AuNPs-III, respectively. For all the three AuNPs, linearity was observed between the melamine concentration in aqueous solution and the absorbance ratios, A(638/527), A(626/525), and A(680/526), respectively. The limit of detection (LOD) for melamine for the AuNPs-II was found to be 2.37 x 10(-8) M (correlation coefficient R-2 = 0.9745), which showed better sensitivity as compared to the LOD of the AuNPs-I and AuNPs-III, which were 3.3 x 10(-8) M and 8.9 x 10(-8) M, respectively. The synthesis of AuNPs-II also involved a lower HAuCl4 concentration compared with the other two types of AuNPs, which may reduce the process cost. The AuNPs-II was selected to analyze melamine in pre-treated milk samples, and the recovery percentage was in the range of 91-106%. Thus, the efficient detection of melamine was possible using AuNPs-II for the on-site detection without the aid of expensive instruments.

Negative hyperconjugation and red-, blue- or zero-shift in X-Z center dot center dot center dot Y complexes

A generalized explanation is provided for the existence of the red-and blue-shifting nature of X-Z bonds (Z = H, halogens, chalcogens, pnicogens, etc.) in X-Z center dot center dot center dot Y complexes based on computational studies on a selected set of weakly bonded complexes and analysis of existing literature data. The additional electrons and orbitals available on Z in comparison to H make for dramatic differences between the H-bond and the rest of the Z-bonds. The nature of the X-group and its influence on the X-Z bond length in the parent X-Z molecule largely controls the change in the X-Z bond length on X-Z center dot center dot center dot Y bond formation; the Y-group usually influences only the magnitude of the effects controlled by X. The major factors which control the X-Z bond length change are: (a) negative hyperconjugative donation of electron density from X-group to X-Z sigma* antibonding molecular orbital (ABMO) in the parent X-Z, (b) induced negative hyperconjugation from the lone pair of electrons on Z to the antibonding orbitals of the X-group, and (c) charge transfer (CT) from the Y-group to the X-Z sigma* orbital. The exchange repulsion from the Y-group that shifts partial electron density at the X-Z sigma* ABMO back to X leads to blue-shifting and the CT from the Y-group to the sigma* ABMO of X-Z leads to red-shifting. The balance between these two opposing forces decides red-, zero- or blue-shifting. A continuum of behaviour of X-Z bond length variation is inevitable in X-Z center dot center dot center dot Y complexes.

Li2MnO3: a rare red-coloured manganese(IV) oxide exhibiting tunable red-yellow-green emission

An experimental assessment of Li2MnO3 has been conducted, in conjunction with related Mn(IV) oxides, to investigate its red colour and photoluminescence. Optical absorption spectra revealed strong band gap absorption, with a sharp edge at similar to 610 nm and a transparent region between similar to 610 and similar to 650 nm, giving rise to the red colour of this compound. Octahedral Mn(IV) ligand field transitions have been observed in the excitation spectra of Li2MnO3, corresponding both to Mn(IV) at ideal sites and displaced in Li sites in the rock salt-based layered structure of Li2MnO3. Optical excitation at ligand field transition energies produces tunable emission in the red-yellow-green region, rendering Li2MnO3 a unique Mn(IV) oxide. The honeycomb-ordered LiMn6] units in its structure are probably the origin of both the absorption and the photoluminescent properties of Li2MnO3.

Biodiesel Exhaust Treatment with HFAC Plasma supported by Red Mud: Study on DeNOx and power consumption

The concentration of Nitrogen Oxides (NOx) in engines which use biodiesel as fuel is higher compared to conventional diesel engine exhaust. In this paper, an attempt has been made to treat this exhaust using a combination of High frequency AC (HFAC) plasma and an industrial waste, Red Mud which shows proclivity towards Nitrogen dioxide (NO2) adsorption. The high frequency AC source in combination with the proposed compact double dielectric plasma reactors is relatively more efficient in converting Nitric Oxide (NO) to NO2. It has been shown that the plasma treated gas enhances the activity of red mud as an adsorbent/catalyst and about 60-72% NOx removal efficiency was observed at a specific energy of 250 J/L. The advantage in this method is the cost effectiveness and abundant availability of the waste red mud in the industry. Further, power estimation studies were carried out using Manley's equation for the two reactors employed in the experiment and a close agreement between experimental and predicted powers was observed. (C) 2015 The Authors. Published by Elsevier Ltd.

Ag-doped hydroxyapatite as efficient adsorbent for removal of Congo red dye from aqueous solution: Synthesis, kinetic and equilibrium adsorption isotherm analysis

In the present study a versatile and efficient adsorbent with high adsorption capacity for adsorption of Congo red dye in aqueous solution at ambient temperature without adjusting any pH is presented over the Ag modified calcium hydroxyapatite (CaHAp). CaHAp and Ag-doped CaHAp materials were synthesized using facile aqueous precipitation method. The physico-chemical properties of the materials were determined by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, Transmission electron microscopy (TEM), UV-Visible spectroscopy, N-2 physisorption and acidity was determined by n-butylamine titration and pyridine adsorption methods. XRD analysis confirmed all adsorbents exhibit hexagonal CaHAp structure with P6(3)/m space group. TEM analysis confirms the rod like morphology of the adsorbents and the average length of the rods were in the range of 40-45 nm. Pyridine adsorption results indicate increase in number of Lewis acid sites with Ag doping in CaHAp. Adsorption capacity of CaHAp was found increased with Ag content in the adsorbents. Ag (10): CaHAp adsorbent showed superior adsorption performance among all the adsorbents for various concentrations of Congo red (CR) dye in aqueous solutions. The amount of CR dye adsorbed on Ag (10): CaHAp was found to be 49.89-267.81 mg g(-1) for 50-300 ppm in aqueous solution. A good correlation between adsorption capacity and acidity of the adsorbents was observed. The adsorption kinetic data of adsorbents fitted well with pseudo second-order kinetic model with correlation coefficients ranged from 0.998 to 0.999. The equilibrium adsorption data was found to best fit to the Langmuir adsorption isotherm model. (C) 2015 Elsevier Inc. All rights reserved.