A CORM loaded nanoplatform for single NIR light-activated bioimaging, gas therapy, and photothermal therapy in vitro.

Carbon monoxide (CO) can cause mitochondrial dysfunction, inducing apoptosis of cancer cells, which sheds light on a potential alternative for cancer treatment. However, the existing CO-based compounds are inherently limited by their chemical nature, such as high biological toxicity and uncontrolled CO release. Therefore, a nanoplatform - UmPF - that addresses such pain points is urgently in demand. In this study, we have proposed a nanoplatform irradiated by near-infrared (NIR) light to release CO. Iron pentacarbonyl (Fe(CO)5) was loaded in the mesoporous polydopamine layer that was coated on rare-earth upconverting nanoparticles (UCNPs). The absorption wavelength of Fe(CO)5 overlaps with the emission bands of the UCNPs in the UV-visible light range, and therefore the emissions from the UCNPs can be used to incite Fe(CO)5 to control the release of CO. Besides, the catechol groups, which are abundant in the polydopamine structure, serve as an ideal locating spot to chelate with Fe(CO)5; in the meantime, the mesoporous structure of the polydopamine layer improves the loading efficiency of Fe(CO)5 and reduces its biological toxicity. The photothermal effect (PTT) of the polydopamine layer is highly controllable by adjusting the external laser intensity, irradiation time and the thickness of the polydopamine layer. The results illustrate that the combination of CO gas therapy (GT) and polydopamine PTT brought by the final nanoplatform can be synergistic in killing cancer cells in vitro. More importantly, the possible toxic side effects can be effectively prevented from affecting the organism, since CO will not be released in this system without near-infrared light radiation.

High selectivity and effectiveness for removal of tetracycline and its related drug resistance in food wastewater through schwertmannite/graphene oxide catalyzed photo-Fenton-like oxidation.

Selectively and effectively for removal of tetracycline (TC) and its related antibiotic resistance gene from food wastewater matrix with high-salt and high COD characteristics is highly desirable. In this work, novel schwertmannite/graphene oxide (SCH/GO) nanocomposites were synthesized through a facile oxidation-coprecipitation method. The SCH/GO nanocomposites were characterized by TEM, XRD, BET, PL, DRS, XPS and FTIR. In the presence of 1 mM H2O2, the SCH/GO catalyzed Fenton-like oxidation can thoroughly degrade TC under visible light irradiation, even under nature sunlight, whose second-order kinetic rate constant was about 15 times higher than that of pure SCH. SCH/GO was capable of highly selectively capturing and effectively degrading TC in the presence of similar concentration of Cl-, NO3-, SO42- and PO43- with that of food wastewater, even at organic matters concentration of 12.5 times than that of TC. At the same time, the removal of total organic carbon (TOC) and chemical oxygen demand (COD) in aforementioned food wastewater in SCH/GO+H2O2+Vis system reached 27.3 % and 34.5 % after 60 min, respectively. The inhibition zone experiments authenticated that the removal of drug resistance of bacteria by TC degradation intermediates can be achieved very well without producing secondary contamination in this system.

Potent anticancer activity of photo-activated oxo-bridged diiron(III) complexes.

Cancer-specific anticancer drugs are still an elusive goal. Using light as the temporal control to generate cytotoxic species from photo-activated prodrug in the presence or absence of molecular oxygen has shown potential application targeted chemotherapy as in photodynamic therapy (PDT). In the present work we explored the chemistry of several photo-active (µ-oxo)diiron(III) complexes of the following formulation [{Fe(µ-O) (L-his)(B)}2](ClO4)2 (1a-1c), [Fe2(µ-O)(H2O)2B4](ClO4)4 (2b, 2c) and [Fe2(µ-O)(µ-O2CMe)B4](ClO4)3 (3b, 3c), L-his = l-histidine, B is 2,2'-bipyridine, 1,10-phenanthroline (phen) and dipyrido[3,2-d:2',3'-f]quinoxaline (dpq) complexes for tumor-specific anticancer activity. Facile redox chemistry and photochemical aspects of the complexes prompted us to investigate the cytotoxic as well as the photo-activated cytotoxic properties of the complexes to the cancer cells. In the present investigation we explored the cancer-specific condition of excess concentration of H2O2 for our approach to targeted chemotherapy. Cytotoxic effect of the complexes to the cancer cells was found to be significantly higher than in normal cells indicating tumor-specific anticancer activity of the complexes. Cytotoxic effect was even more pronounced when the cancer cells treated with the complexes were exposed to the visible light (400-700 nm). There was >12 fold increase in cytotoxicity of the photoactivated complexes in cancer cells (MCF-7) in comparison to the normal cells (MCF-10a). We have defined a factor viz. cancer cell specificity factor (f) describing the targeted photochemotherapeutic effect of the complexes at their specific concentration. The factor (f) > 1 indicated the cancer cell specificity of the complexes, while f > 2.5 for the complexes under the visible light exposure suggested photodynamic effect. DCFDA assay indicated the presence of excess of ROS in the treated HeLa cells. ROS concentration was found to increase even more on visible light exposure. Increased ROS in the cancer cells disturb the cellular redox mechanism inducing oxidative stress to lethality. Decarboxylation of photo-activated diiron(III) complexes generate OH radical responsible for cell death. Overall, the high efficacy and selectivity of the (µ-oxo)diiron(III) complexes potentially make them suitable for in vivo applications and extensive testing toward transfer into the clinical arena.

A simple chemical route toward monodisperse iron carbide nanoparticles displaying tunable magnetic and unprecedented hyperthermia properties.

We report a tunable organometallic synthesis of monodisperse iron carbide and core/shell iron/iron carbide nanoparticles displaying a high magnetization and good air-stability. This process based on the decomposition of Fe(CO)(5) on Fe(0) seeds allows the control of the amount of carbon diffused and therefore the tuning of nanoparticles magnetic anisotropy. This results in unprecedented hyperthermia properties at moderate magnetic fields, in the range of medical treatments.

Magnetic nanochains of FeNi3 prepared by a template-free microwave-hydrothermal method.

Magnetic FeNi3 nanochains were synthesized by reducing iron(III) acetylacetonate and nickel(II) acetylacetonate with hydrazine in ethylene glycol solution without any template under a rapid and economical microwave irradiation. The morphology and composition of the as-prepared products were characterized by field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and elemental mapping. The size of the aligned nanospheres in the magnetic FeNi3 chains could be adjusted from 150 to 550 nm by increasing the amounts of the precursors. The length of the nanochain is about several tens of micrometers. The ratio of the precursors plays an important role in the formation of FeNi3 nanostructures. Magnetic measurement reveals that the FeNi3 nanochains show enhanced coercivity and saturation magnetization. The formation mechanism of the product is discussed. Toxicity tests of FeNi3 nanochains show that the as-prepared nanochains are nontoxic to zebrafish larvae. In vitro magnetic resonance imaging (MRI) confirms the effectiveness of the FeNi3 nanochains as sensitive MRI probes.

Solid-phase photocatalytic degradation of polyethylene-goethite composite film under UV-light irradiation.

A novel photodegradable polyethylene-goethite (PE-goethite) composite film was prepared by embedding the goethite into the commercial polyethylene. The degradation of PE-goethite composite films was investigated under ultraviolet light irradiation. The photodegradation activity of the PE plastic was determined by monitoring its weight loss, scanning electron microscopic (SEM) analysis and FT-IR spectroscopy. The weight of PE-goethite (1 wt%) sample steadily decreased and led to the total 16% reduction in 300 h under UV-light intensity for 1 mW/cm(2). Through SEM observation there were some cavities around the goethite powder in the composite films, but there were few changes except some surface chalking phenomenon in pure PE film. The degradation rate could be controlled by changing the concentration of goethite particles in PE plastic. The degradation of composite plastic initiated on PE-goethite interface and then extended into polymer matrix induced by the diffusion of the reactive oxygen species generated on goethite particle surface. The photocatalytic degradation mechanism of the composite films was briefly discussed.

Electrically assisted magnetic recording in multiferroic nanostructures.

We demonstrate the room-temperature control of magnetization reversal with an electric field in an epitaxial nanostructure consisting of ferrimagnetic nanopillars embedded in a ferroelectric matrix. This was achieved by combining a weak, uniform magnetic field with the switching electric field to selectively switch pillars with only one magnetic configuration. On the basis of these experimental results, we propose to use an electric field to assist magnetic recording in multiferroic systems with high perpendicular magnetic anisotropy.

Photochemistry of the [Fe4(mu3-S)3(NO)7]- complex in the presence of S-nucleophiles: a spectroscopic study.

Biological systems usually contain cysteine, glutathione or other sulfur-containing biomolecules. These S-nucleophiles were found to affect drastically the [Fe(4)(mu(3)-S)(3)(NO)(7)](-) photolysis pathway generating products completely different from that of the neat cluster, which produces Fe(II) and NO and S(2-). The effect is interpreted in terms of formation of a pseudo-cubane adduct, [Fe(4)(mu(3)-S)(3)(mu(3)-SR)(NO)(7)](2-), whose existence in equilibrium with the parent complex has no detectable influence on the spectral properties, whereas shifts the redox potential and induces photoconversion leading to the Fe(III) species and N(2)O. Characteristic bond lengths, bond angles and atomic Mulliken charges were calculated using semi-empirical quantum chemical methods for the RBS anion and a series of pseudo-cubane complexes with S-donor or N-donor ligands. The results justify the hypothesis of the adduct formation and show that only in case of S-ligands the higher contribution of the Fe(III)-NO(-) components in adduct than in RBS is observed, which on excitation can undergo heterolytic cleavage yielding Fe(III) and NO(-), converted rapidly into N(2)O. These results are crucial in understanding the physiological activity of RBS. Fe(III) formation can be detected only when the S-ligand enables formation of a stable Fe(III) compound; the effect was recorded in the presence of sulfide, thioglycolate, 2-mercaptopropionate, mercaptosuccinate, penicillamine, 2,3-dimercaptosuccinate, 2,3-dimercaptopropanol, and thiocyanate. For all these S-ligands the Fe(III) photoproducts were identified and characterised. In the case of other thiolates, their excess results in fast reduction of Fe(III) to Fe(II), whereas N(2)O can be still detected. Quantum yields of Fe(III) formation in the presence of the S-ligands are considerably higher than that of the Fe(II) photoproduction from neat [Fe(4)(mu(3)-S)(3)(NO)(7)](-).

NO-dependent phototoxicity of Roussin's black salt against cancer cells.

A metal-nitrosyl complex, Roussin's black salt (RBS), releases nitric oxide after illumination. Approximately 3.7 NO molecules were released from one RBS molecule. Both short- and long-term effects of photogenerated NO on the two neoplastic cell lines: human (SK-MEL188) and mouse (S91) have been investigated. Exogenous NO from RBS was toxic to cells in a dose-dependent manner. Apoptotic damage predominates in the response to the injury, as shown by TUNEL assay. NO and its short-lived metabolites, but not other RBS photoproducts, are responsible for cellular death. RBS in dark was toxic to cells at concentrations above 1 microM. This relatively high cytotoxicity of RBS in the dark prevents its application as a systemic anticancer agent in vivo, unless it is applied locally.

In situ nitric oxide (NO) measurement by modified electrodes: NO labilized by photolysis of metal nitrosyl complexes.

Described are studies directed at refining quantitative analysis of nitric oxide in solution using electrochemical techniques. The fabrication and behavior of several sensors based on modified carbon-based electrodes are reported. This technique has been used to resolve the vexing problem of determining the stoichiometry of the photochemical decomposition of the known antihypertension agent sodium nitroprusside, Na2[Fe(CN)5NO], as well as of two other metal nitrosyl complexes of biological interest, Roussin's black salt, NH4[Fe4S3(NO)7], and Roussin's red salt, Na2[Fe2S2(NO)4], in aqueous solutions. In this manner it was shown that the molar ratios of nitric oxide produced per starting complex photochemically decomposed were 0.95 +/- 0.03, 5.9 +/- 0.2, and 0.50 +/- 0.02 for Na2[Fe(C-N)5NO], NH4[Fe4S3(NO)7], and Na2[Fe2S2(NO)4], respectively.