Remote‐Controlled Release of Singlet Oxygen by the Plasmonic Heating of Endoperoxide‐Modified Gold Nanorods: Towards a Paradigm Change in Photodynamic Therapy

The photodynamic therapy of cancer is contingent upon the sustained generation of singlet oxygen in the tumor region. However, tumors of the most metastatic cancer types develop a region of severe hypoxia, which puts them beyond the reach of most therapeutic protocols. More troublesome, photodynamic action generates acute hypoxia as the process itself diminishes cellular oxygen reserves, which makes it a self‐limiting method. Herein, we describe a new concept that could eventually lead to a change in the 100 year old paradigm of photodynamic therapy and potentially offer solutions to some of the lingering problems. When gold nanorods with tethered endoperoxides are irradiated at 808 nm, the endoperoxides undergo thermal cycloreversion, resulting in the generation of singlet oxygen. We demonstrate that the amount of singlet oxygen produced in this way is sufficient for triggering apoptosis in cell cultures.     

Probing mixed valence in a new tppz-bridged diruthenium(III,II) complex {(mu-tppz)[Ru(bik)Cl]2}3+ (tppz=2,3,5,6-tetrakis(2-pyridyl)pyrazine, bik=2,2'-bis(1-methylimidazolyl)ketone): EPR silence, intervalence absorption, and nu(CO) line broadening

The complex dication of the diruthenium(II) compound {(mu-tppz)[Ru(bik)Cl]2}(ClO4)2 can be oxidized and reduced in two one-electron steps each. In CH3CN/0.1 M Bu4NPF6, the odd-electron intermediates{(mu-tppz)[Ru(bik)Cl]2}n+, n=1 and 3, have comproportionation constants of 7x10(8) and 1x10(5), respectively. Both exhibit near-infrared absorptions, in the case of n=3 the 1640 nm band (epsilon=1200 M-1 cm-1, Deltanu1/2=1560 cm-1) is attributed to an intervalence charge-transfer transition. While the mixed-valent intermediate (n=3) is EPR silent even at 4 K, the n=1 form shows g(parallel) 2.005 and g( perpendicular) 1.994 at that temperature, signifying a diruthenium(II) complex of the tppz*- radical anion. The variation of energy and intensity of nuCO and of the ring vibration band around 1590 cm-1 has been monitored not only for {(mu-tppz)[Ru(bik)Cl]2}n+, n=0-4, but also for the mononuclear {(tppz)Ru(bik)Cl}n+, n=0-2. In the dinuclear complex the carbonyl stretching bands of the spectator ligand bik are shifted by about 15 cm-1 on each one-electron-transfer step, increasing with the positive charge. The mixed-valent {(mu-tppz)[Ru(bik)Cl]2}3+ shows a perceptibly broader nuCO band, suggesting incomplete valence averaging (partial localization).     

Heavy metal contamination in street dusts of Istanbul (Pendik to Levent) E-5 highway

Street dust composition is an important environmental parameter that should be considered in investigations of environmental pollution originating from traffic. In this study, fifty-six samples of street dusts were collected during the period December 2003-April 2004 from Pendik to Levent on E-5 highway in Istanbul, Turkey. Analyses were determined by graphite furnace atomic absorption spectrometry after digestion using USEPA, 1996 (Method 3050B). The mean concentration levels of Pb, Mn, Zn, Ni, Cd and Cu were found to be 368.3, 747.8, 431.2, 27.1, 0.3 and 191.1 microg/g respectively. Pb, Cu, Zn and Mn mean concentrations in studied areas were higher than levels of these heavy metals according to USEPA (1992) and Republic of Turkey Ministry of Environment and Foresty (2003). Highly significant correlations except for Mn were found between the number of vehicles and heavy metal concentrations.     

IR, Raman and SERS spectra of 2-phenoxymethylbenzothiazole

The FT-IR and FT-Raman spectra of 2-phenoxymethylbenzothiazole were recorded and analyzed. The surface enhanced Raman scattering (SERS) spectrum was recorded in a silver colloid. The vibrational wavenumbers of the compound have been computed using the Hartree–Fock/6-31G* basis and compared with the experimental values. The appearance of the Ag–O stretching mode at 237 cm⁻¹ in the SERS spectrum along with theoretically calculated atomic charge density, leads us to suggest that the molecule is adsorbed through the oxygen atom with the molecular plane tilted on the colloidal silver surface. The direction of charge transfer contribution to SERS has been discussed from the frontier orbital theory.     

Quartic B-spline Galerkin approach to the numerical solution of the KdVB equation

The nonlinear Korteweg-de Vries–Burgers’ equation is solved numerically by method of Galerkin using quartic B-splines as both shape and weight functions over the finite intervals. Five test problems are studied to demonstrate the accuracy and efficiency of the proposed method. A comparison of numerical results of both algorithm and some published articles is done in computational section. The numerical results are found in good agreement with exact solutions.     

New type of tetrazine‐substituted metallophthalocyanines by microwave irradiation: Synthesis and characterization

5,6‐bis(4‐methylphenyl)‐2,3‐dihydro‐1,2,3,4‐tetrazine 2 was synthesized by the dimerization of ethyl p‐methylbenzoateformylhydrazone 1 in hydrazinehydrate solution. 2,3‐bis(4‐methylphenyl)‐6,7,14,15‐tetrahydro[1,2,3,4]tetrazino [2,3d][1,8, 4,5]benzodithia‐diazecine‐10,11‐dicarbonitrile 4 was sythesized by cyclization reaction of tetrazine monomer 2 onto 1,2‐bis‐(2‐iodoethylmercapto)‐4,5‐dicyanobenzene 3 . Co(II) and Cu(II) phthalocyanine complexes were prepared by reaction of the dinitrile compound ( 4 ) with the chlorides of Co(II), Cu(II), and DMAE at 175°C, 350 W in a microwave oven for 10 min. Zn(II)‐phthalocyanine complex was prepared by reaction of the dinitrile compound 4 with the acetate of Zn(II) and DMAE at 175°C, 350 W in a microwave oven for 10 min. The new compounds were characterized by a combination of IR, ¹H‐NMR, ¹³C NMR, UV‐vis, elemental analysis, and MS spectral data. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:456–461, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20623     

Phthalocyanine-based fluorescent chemosensor for the sensing of Zn (II) in dimethyl sulfoxide-acetonitrile

A tetra-substituted phthalocyanine based on 4-[2-(4-nitrophenoxy)ethoxy]phthalonitrile carrying nitrophenyl group for the sensing of Zn²⁺ has been prepared and characterized by elemental analysis, FT-IR, ¹H and ¹³C NMR, and MS spectral data. The sensing of Zn²⁺ is based on the fluorescence quenching of Pc. Both absorbance and fluorescence spectra of ZnPc exhibit distinct changes in visible region in response to treatment with Zn²⁺ ion in dimethyl sulfoxide. The fluorescence spectrum of the ligand showed quenching in the intensity of the signal at 688?nm for Zn²⁺. The complex composition of ZnPc was found 1:1 by means of spectrophotometric and spectrofluorimetric titration data. The spectrofluorimetric method showed good sensitivity for Zn²⁺ with linear range and detection limit of 4.0?×?10^?6–4.4?×?10^?5 and 2.4×10^?7?M, respectively.     

Transformation of 2,4-dichlorophenol by H2O2/UV-C, Fenton and photo-Fenton processes: Oxidation products and toxicity evolution

In the present study, H₂O₂/UV-C, Fenton and photo-Fenton treatment of 2,4-dichlorophenol was compared in terms of oxidation products and acute toxicity. The oxidation products were identified by gas chromatography-mass spectroscopy, high performance liquid chromatography and ion chromatography, whereas changes in acute toxicity were evaluated by the Vibrio fischeri luminescence inhibition assay. H₂O₂/UV-C and photo-Fenton processes ensured complete 2,4-dichlorophenolremoval, detoxification and significant mineralization. Hydroquinone and formic acid were identified as the common oxidation products of the studied advanced oxidation processes investigated. 3,5-dichloro-2-hydroxybenzaldehyde, phenol, 4-chlorophenol and 2,5-dichlorohydroquinone were identified as the additional H₂O₂/UV-C oxidation products of 2,4-dichlorophenol. Acute toxicity decreased with decreasing 2,4-dichlorophenol and increasing chloride release.     

Adversarial Machine Learning for NextG Covert Communications Using Multiple Antennas

This paper studies the privacy of wireless communications from an eavesdropper that employs a deep learning (DL) classifier to detect transmissions of interest. There exists one transmitter that transmits to its receiver in the presence of an eavesdropper. In the meantime, a cooperative jammer (CJ) with multiple antennas transmits carefully crafted adversarial perturbations over the air to fool the eavesdropper into classifying the received superposition of signals as noise. While generating the adversarial perturbation at the CJ, multiple antennas are utilized to improve the attack performance in terms of fooling the eavesdropper. Two main points are considered while exploiting the multiple antennas at the adversary, namely the power allocation among antennas and the utilization of channel diversity. To limit the impact on the bit error rate (BER) at the receiver, the CJ puts an upper bound on the strength of the perturbation signal. Performance results show that this adversarial perturbation causes the eavesdropper to misclassify the received signals as noise with a high probability while increasing the BER at the legitimate receiver only slightly. Furthermore, the adversarial perturbation is shown to become more effective when multiple antennas are utilized.     

Spectrofluorimetric Determination of Aflatoxin B1 in Winter Herbal Teas via Magnetic Solid Phase Extraction Method by using Metal–Organic Framework (MOF) Hybrid Structures Anchored with Magnetic Nanoparticles

MIL53(Al)-SiO₂@Fe₃O₄ composite was prepared by co-precipitation route with a typical Stöber synthetic process and ultrasonic-agitation, then subsequently utilized as a multi-component novel sorbent in solid-phase microextraction (SPME) of aflatoxin B1 in winter herbal teas. Microstructural properties of MIL53(Al)-SiO₂@Fe₃O₄ composite was characterized by using Fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) methods, and Brunauer–Emmett–Teller (BET) surface area measurement. The MIL53(Al)-SiO₂@Fe₃O₄ composite was found to be a very effective sorbent in spectrofluorimetric determination of aflatoxin B1 (AFB1) in winter herbal teas via magnetic solid-phase extraction (SPE) route. The proposed method showed a wide linear range from 0.5 to 150 ng/ml, low limit of detection (LOD = 0.5 ng/ml), and an acceptable recovery values (70.7–96.5%) in real samples analysis. This study shows that the suggested method possesses an important potential to use for detecting AFB1 in quality control laboratories.