Water-Soluble Organic Nanoparticles with Programable Intermolecular Charge Transfer for NIR-II Photothermal Anti-Bacterial Therapy.

Extensive recent efforts have been put on the design of high-performance organic near-infrared (NIR) photothermal agents (PTAs), especially over NIR-II bio-window (1000-1350 nm). So far, the development is mainly limited by the rarity of molecules with good NIR-II response. Here, we report organic nanoparticles of intermolecular charge-transfer complexes (CTCs) with easily programmable optical absorption. By employing different common donor and acceptor molecules to form CTC nanoparticles (CT NPs), absorption peaks of CT NPs can be controllably tuned from the NIR-I to NIR-II region. Notably, CT NPs formed with perylene and TCNQ have a considerably red-shifted absorption peak at 1040 nm and achieves a good photothermal conversion efficiency of 42 % under 1064 nm excitation. These nanoparticles were used for antibacterial application with effective activity towards both Gram-negative and Gram-positive bacteria. This work opens a new avenue into the development of efficient PTAs.

Photooxidation products of polycyclic aromatic compounds containing sulfur.

Photooxidation of crude oil components is an important process that removes pollutants from the environment. Polycyclic aromatic compounds (PACs) are known to be toxic to many life forms, but little is known about their photooxidation products in the aqueous phase. We here identify a large number of photoproducts from 11 benzothiophenes, a polycyclic aromatic sulfur heterocycle that is a major representative of PACs in crude oil. The investigated compounds contain two to four methyl groups and an ethyl or an n-octyl group. In water, the products arise through oxidation of alkyl side chains to aldehydes and carboxylic acids or through an opening in one of the aromatic rings. The product analysis was performed using gas chromatography with mass spectrometric or atomic emission detection. The main product is always a sulfobenzoic acid, which strongly lowers the pH of the solution. With long alkyl substituents, surfactants are formed, which may possess solubilizing properties in water. The larger the number of alkyl groups, the faster is the photooxidation. Several of the identified acidic compounds were also found when whole crude oil was photooxidized, showing that simulation with individual compounds reflects the situation in whole crude.

Stable photoinduced charge separation in heptacene.

Heptacene, generated in inert gas matrices by photobisdecarbonylation of a bridged alpha-diketone precursor, undergoes ionization into radical anion and radical cation upon UV irradiation.

Photochemical tuning of light emission in a conjugated polymer containing norbornadiene units in the main chain.

A conjugated alternating copolymer containing norbornadiene and bis(ethynylene)phenylene units was prepared by the Cassar-Heck-Sonogashira cross-coupling reaction. Its electroluminescence was tested in a device, and its fluorescence colour could be tuned by light-induced norbornadiene-quadricyclane isomerization.

Laser flash photolysis of 1,2-diketopyracene and a theoretical study of the phenolic hydrogen abstraction by the triplet state of cyclic alpha-diketones.

Laser flash photolysis (LFP) studies, atoms in molecules (AIM) studies, and density functional theory (DFT) calculations have been performed in order to study the mechanism of the hydrogen abstraction by alpha-diketones in the presence of phenols. Laser irradiation of a degassed solution of 1,2-diketopyracene in acetonitrile resulted in the formation of a readily detectable transient with absorption at 610 nm, but with very low absorptivity. This transient decays with a lifetime of around 2 micros. The quenching rate constant for substituted phenols, kq, ranged from 1.10x10(8) L mol-1 s-1 (4-cyanophenol) to 3.87x10(9) L mol-1 s-1 (4-hydroxyphenol). The Hammett plot for the reaction of the triplet of 1,2-diketopyracene with phenols gave a reaction constant rho=-0.9. DFT calculations (UB3LYP/6-311++G**//UB3LYP/6-31G*) of the triplet complex ketone-phenol revealed that hydrogen transfer has predominantly occurred and that the reaction with alpha-diketones are generally 7 kcal/mol less endothermic than the respective reactions of the monoketones. These results together with the geometries obtained from the DFT calculations, natural bond order (NBO) analysis, and AIM results indicate that hydrogen abstraction for alpha-diketones is facilitated by the electrophilicity of the ketone, instead of neighboring group participation by the second carbonyl group.

Radiation damage in coronene, rubrene and p-terphenyl, measured for incident electrons of kinetic energy between 100 and 200 kev.

We have measured the sensitivity of three highly conjugated organic compounds to electron irradiation. Using a 200 keV TEM, loss of crystallinity was determined from quantitative electron-diffraction measurements. Degradation of the molecular ring structure was monitored from fading of the 6 eV pi-excitation peak in the energy-loss spectrum. Measurements at incident energies between 30 keV and 100 eV were made using a scanning electron microscope (SEM), by recording gradual decay of the cathodoluminescence (CL) signal. Expressed in Grays, the energy dose required for CL decay in coronene is a factor of 30 lower than for destruction of crystallinity and a factor of 300 lower than for destruction of the molecular structure. Below 1 keV, the CL-decay cross section shows no evidence of a threshold effect, indicating that the damage involved is caused by valence-electron (rather than K-shell) excitation. Therefore even relatively radiation-resistant organic materials may undergo some form of damage when examined in a low-energy electron microscope or a low-voltage SEM.

Photoisomerization of a rotaxane hydrogen bonding template: light-induced acceleration of a large amplitude rotational motion.

Establishing methods for controlling aspects of large amplitude submolecular movements is a prerequisite for the development of artificial devices that function through rotary motion at the molecular level. Here we demonstrate that the rate of rotation of the interlocked components of fumaramide-derived [2]rotaxanes can be accelerated, by >6 orders of magnitude, by isomerizing them to the corresponding maleamide [2]rotaxanes by using light.

Photophysical studies on melatonin and its receptor agonists.

Previous work has demonstrated that melatonin inhibits the growth of both dermal and uveal melanoma cells. Recent clinical trials have found that melatonin is an efficacious treatment for metastatic dermal melanoma. The goal of this study was to provide further insight into the oncostatic mechanism(s) of melatonin. The inhibition of the growth of uveal melanoma cells is dose-dependent (0.1-10 nM) within the range of endogenous melatonin concentrations (2 nM) found in the human aqueous humor. We know that this inhibition of growth is receptor-mediated, at least in part, because uveal melanoma cell growth was also blocked by the agonists of melatonin receptors. There are two known membrane receptors for melatonin (Mel(1a) and Mel(1b)) and one known nuclear receptor (Mel2). To determine if singlet oxygen production and/or quenching contributed to the growth inhibition of melatonin, we examined the photophysical properties of melatonin and its agonists. Using flash photolysis, we determined that melatonin and its membrane receptor agonist 6-chloromelatonin (Mel(1a-b), Lilly, Indianapolis, IN) produced very little singlet oxygen (psidelta = 0.073 and psidelta = 0.01, respectively). There was no detectable singlet oxygen phosphorescence at 1,270 nm for the nuclear receptor agonist CG-52608 (Mel2, Novartis, Basel, Switzerland). In contrast, the agonist of the Mel(1b) receptor, S-20098 (Servier, Paris, France), produced singlet oxygen with a quantum efficiency of psidelta = 0.34. Singlet oxygen was quenched by melatonin and 6-chloromelatonin at approximately the same rate (6.1 x 10(7) M(-1)s(-1) and 6.0 x 10(7) M(-1)s(-1) in CD3OD), while the rate of quenching for the nuclear receptor agonist CG-52608 and membrane receptor agonist S-20098 was less (2.2 x 10(7) M(-1)s(-1) and 1.5 x 10(7) M(-1) s(-1), respectively). It appears that the production of singlet oxygen by melatonin would not be sufficient to directly block the proliferation of melanoma cells, but may activate gene products that could contribute to the oncostatic effect.

Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices.

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

Single photon infrared emission spectroscopy: a study of IR emission from UV laser excited PAHs between 3 and 15 micrometers.

Single-photon infrared emission spectroscopy (SPIRES) has been used to measure emission spectra from polycyclic aromatic hydrocarbons (PAHs). A supersonic free-jet expansion has been used to provide emission spectra of rotationally cold and vibrationally excited naphthalene and benzene. Under these conditions, the observed width of the 3.3-micrometers (C-H stretch) band resembles the bandwidths observed in experiments in which emission is observed from naphthalene with higher rotational energy. To obtain complete coverage of IR wavelengths relevant to the unidentified infrared bands (UIRs), UV laser-induced desorption was used to generate gas-phase highly excited PAHs. Lorentzian band shapes were convoluted with the monochromator-slit function in order to determine the widths of PAH emission bands under astrophysically relevant conditions. Bandwidths were also extracted from bands consisting of multiple normal modes blended together. These parameters are grouped according to the functional groups mostly involved in the vibration, and mean bandwidths are obtained. These bandwidths are larger than the widths of the corresponding UIR bands. However, when the comparison is limited to the largest PAHs studied, the bandwidths are slightly smaller than the corresponding UIR bands. These parameters can be used to model emission spectra from PAH cations and cations of larger PAHs, which are better candidate carriers of the UIRs.

Photosensitization with anticancer agents. 20--EPR studies on the photodynamic action of phleichrome: formation of semiquinone radical and activated oxygen species on illumination with visible light.

When phleichrome was illuminated with visible light, the semiquinone radical, singlet oxygen, and superoxide anion radical were detected. The formation of the semiquinone radical and activated oxygen species and the transformations and competitions between them depend on quinone and oxygen concentration, duration and intensity of illumination, and the nature of the substrate. In anaerobic solution, the semiquinone radical was predominantly photoproduced via the self-electron transfer between the excited and ground species. In contrast, in aerobic solution, singlet oxygen is the principal product in the photosensitization of phleichrome. In addition to singlet oxygen, superoxide anion radical is also generated by the quinones upon illumination in aerobic solution, but to a lesser extent. The generation of the superoxide anion is significantly enhanced by the presence of electron donors.

Irreversible oxidative inactivation of protein kinase C by photosensitive inhibitor calphostin C.

Isolated protein kinase C (PKC) was irreversibly inactivated by a brief (min) incubation with calphostin C in the presence of light. This inactivation required Ca2+ either in a millimolar range in the absence of lipid activators or in a submicromolar range in the presence of lipid activators. In addition, an oxygen atmosphere was required suggesting the involvement of oxidation(s) in this inactivation process. Furthermore, PKC inactivation might involve a site-specific oxidative modification of the enzyme at the Ca(2+)-induced hydrophobic region. Physical quenchers of singlet oxygen such as lycopene, beta-carotene, and alpha-tocopherol all reduced the calphostin C-induced inactivation of PKC. In intact cells treated with calphostin C, the inactivation of PKC was rapid in the membrane fraction compared to cytosol. This intracellular PKC inactivation was also found to be irreversible. Therefore, calphostin C can bring prolonged effects for several hours in cells treated for a short time. Taken together these results suggest that the calphostin C-mediated inactivation of PKC involves a site-specific and a 'cage' type oxidative modification of PKC.

[Distribution, formation, carcinogenic and mutagenic activities of nitro derivatives of polycyclic aromatic hydrocarbons]. / Raspredelenie, obrazovanie, kantserogennaia i mutagennaia aktivnost' nitroproizvodnykh politsiklicheskikh aromaticheskikh uglevodorodov.

Nitro-PAHs (nitro-substituted derivatives of polycyclic aromatic hydrocarbons) are a class of chemical compounds with high biologic activity. They have been detected in samples of air pollutants, diesel and gasoline engine exhausts, in airplane exhaust emissions, cigarette smoke condensate, emissions of coke ovens, wood-burning fireplaces, coal-fired plants, in food and tea. Concentrations of nitro-PAHs have been compared with those of PAHs present in air pollutant samples and emissions from different sources. Information on the environmental occurrence, formation, and decomposition of nitro-PAHs in the atmosphere is given. Biologic effects (carcinogenic and mutagenic) of pure nitro-PAHs and nitro-PAHs-containing complex mixtures are discussed.

A preliminary study of the changes in the direct-acting mutagenicities of several nitropolycyclic aromatic hydrocarbons after exposure under sunlight.

Five commercially available nitropolyclyclic aromatic hydrocarbons (nitro-PAH), namely, 4-nitrobiphenyl, 2-nitrofluorene, 9-nitroanthracene, 1-nitropyrene, and 2,7-dinitrofluorene, were exposed under restricted sunlight in the open air. The direct-acting mutagenicities of the samples after an exposure of 45 days were measured in order to compare them with those of the original samples in the Ames Salmonella typhimurium bioassay. It was found that the mutagenicities of some nitro-PAH do not change significantly while the mutagenicities of others increase or decrease after exposure. A preliminary study of nitro-PAH reaction products after exposure using GC, GC/MS, and FT-IR is also reported.

Solvent-induced photodegradation as a source of error in the analysis of polycyclic aromatic hydrocarbons.

The photodegradation of seven common polycyclic aromatic hydrocarbons (PAHs) has been examined in a range of organic solvents. Reactions followed a first order equation with benzo[a]pyrene and benzo[a]anthracene being the most rapidly photodegraded. Generally, the more polar the solvent the faster is the degradation process. A number of photodegradation products were identified by gas chromatography-mass spectrometry. The identification of compounds such as 4-amino-1-naphthalenecarbonitrile and 1H,3H-naphtho[1,8-cd]pyran-1-one clearly indicated that the solvent molecules have taken part in the formation of these compounds. Solvent-induced photodegradation is shown to be an important consideration in choosing the optimum solvent for the best analytical recoveries of PAHs from various matrices.

Photochemical degradation of polycyclic aromatic hydrocarbons (PAH) in real and laboratory conditions.

Studies were carried out on the effects induced by the main components of airborne particulate matter (APM) as soot, inorganic and cyclohexane soluble substances and by glass fiber filters on photodegradation of pyrene, benz(a)anthracene and benzo(a)pyrene exposed to UV and solar radiation. In both experimental models tested hydrocarbons showed a higher photochemical stability when absorbed on APM. Inorganic components of APM slightly enhance UV photodegradation. In real condition (outdoor exposure to solar radiation) PAH half lives generally showed a good linear correlation with mean solar radiation intensity; only degradation rate of benzo(a)pyrene on APM, exposed to sunlight was practically constant. Pyrene, in particular, showed a higher degradation rate when high ozone concentrations (0.2 ppm) occurred.

Determination of 23 polycyclic aromatic hydrocarbons in atmospheric particulate matter of the Paris area and photolysis by sunlight.

Twenty-three polycyclic aromatic hydrocarbons (PAH) were determined in atmospheric particulate matter in 4 places of the Paris area at several times of the year. Fractionation was performed by reversed-phase high-pressure liquid chromatography. Determination was done by recording emission or excitation fluorescence spectra via a stopped-flow technique. Triphenylene was also extemporaneously determined by its phosphorescence spectrum at low temperature. Among the PAH determined dibenz(e,ghi)perylene has not been detected before in atmospheric particulate matter. The 10 more abundant PAH ranged from 0.1 to 40 ng/m3 of filtered air. Concentrations in August are from 14 to 250 times less than in January depending on the PAH. The reasons for this difference of behaviour among the PAH were investigated with regard to their photochemical and non-photochemical reactivity.