Photoreactive Compounds Research Articles

Hydrocarbons in the atmospheric gas phase of a coastal city in Tunisia: Levels, gas–particle partitioning, and health risk assessment

Many studies have focused on aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (AHs and PAHs) in different environmental compartments, especially atmospheric particles (aerosols), due to their adverse effects on the environment and human health. However, much less information is currently available on the content of AHs and PAHs in the atmospheric gas phase, which is a major reservoir of volatile and photoreactive compounds. Here, for the first time, we assessed the levels, gas–particle partitioning, human health risks and seasonal variations of AHs and PAHs in the atmospheric gas-phase of Bizerte city (Tunisia, North Africa) over a one-year period (March 2015–January 2016). Σ34PAH concentration in the gas phase over the period ranged from 6.7 to 90.6 ng m−3 and on average was 2.5 times higher in the cold season than in the warm season. Σ28AH concentration in the gas phase over the period ranged from 14.0 to 35.9 ng m−3, with no clear seasonal variations. In the gas phase, hydrocarbons were dominated by low-molecular-weight (LMW) compounds, i.e. 3- and 4-ring for PAHs and < n-C24 for AHs. Gas-phase concentrations of PAHs and AHs accounted for up to 80 % of the total (gas + particle phases) atmospheric concentrations of PAHs and AHs. Further analysis of gas–particle partitioning showed that LMW hydrocarbons preferential accumulated in the gas phase, and that gas–particle partitioning was not in equilibrium but dominated by absorption processes into the aerosol organic matter. Benzo[a]pyrene toxic equivalency quotient (BaP-TEQ) in the gas phase represented on average 37 % of the total atmospheric BaP-TEQ concentration, which was always higher in the cold season. Atmospheric gas is a significant factor in the risks of cancer associated with inhalation of ambient air. The Monte Carlo simulation-based exposure assessment model predicted that outdoor air exposure to PAHs does not pose a cancer risk to infants, but the children, adolescent, and adult populations may face a lower cancer risk during the warm season and a higher risk in the cold season.

Synthesis and Photoreactivity of 7-Nitroindoline-S-thiocarbamates.

The photolytic properties of N-acyl-7-nitroindolines make these compounds attractive as photocleavable protecting groups and "caged" compounds for the light-induced release ("uncaging") of biologically active compounds and as acylating reagents under neutral conditions. However, the synthesis of N-acyl-7-nitroindolines usually requires multiple steps, and the direct acylation of 7-nitroindolines can be quite challenging. 7-Nitroindolines with other types of N-carbonyl-containing groups may also be photoreactive and could potentially be better accessible. Here we demonstrate the short and efficient synthesis of 5-bromo-7-nitroindoline-S-thiocarbamates, a new class of photoreactive compounds, and the study of some of their photochemical and photophysical properties. Using 5-bromo-7-nitroindoline-S-ethylthiocarbamate as a model compound, we show that it can undergo one-photon and two-photon photolysis at 350 and 710 nm, respectively. Our experimental data and quantum chemistry calculations support a photolysis pathway that differs from photolysis pathways previously reported for N-acyl-7-nitroindolines. The photolysis with 350 nm light results in 5-bromo-7-nitrosoindoline, which is in equilibrium with its dimeric form(s), as supported by experiment and theory. This study expands the scope of photoreactive 7-nitroindoline derivatives and informs the development of novel photocleavable compounds.

Improved Understanding of Dissolved Organic Matter Processing in Freshwater Using Complementary Experimental and Machine Learning Approaches.

Dissolved organic matter plays an important role in aquatic ecosystems and poses a major problem for drinking water production. However, our understanding of DOM reactivity in natural systems is hampered by its complex molecular composition. Here, we used Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and data from two independent studies to disentangle DOM reactivity based on photochemical and microbial-induced transformations. Robust correlations of FT-ICR-MS peak intensities with chlorophyll a and solar irradiation were used to define 9 reactivity classes for 1277 common molecular formulas. Germany's largest drinking water reservoir was sampled for 1 year, and DOM processing in stratified surface waters could be attributed to photochemical transformations during summer months. Microbial DOM alterations could be distinguished based on correlation coefficients with chlorophyll a and often shared molecular features (elemental ratios and mass) with photoreactive compounds. In particular, many photoproducts and some microbial products were identified as potential precursors of disinfection byproducts. Molecular DOM features were used to further predict molecular reactivity for the remaining compounds in the data set based on a random forest model. Our method offers an expandable classification approach to integrate the reactivity of DOM from specific environments and link it to molecular properties and chemistry.

Photomechanical materials driven by photoisomerization or photodimerization

Light is an adjustable, multiparameter stimulus that can be used for fine, noncontact manipulation or as an energy supply. Recently, deformable light-controlled macroscopic materials have gained attention both from a fundamental research perspective and for various actuator applications. The main challenge in developing these materials is converting the photoinduced effects at the molecular level to macroscopic movements in the working pieces; a variety of mechanisms have been proposed for this. Both crystals and polymers containing photoreactive compounds have been intensively studied and have exhibited different advantages. Crosslinked liquid crystalline polymers have also attracted attention because they combine the advantages of macroscopically deformable polymers and crystals. In most circumstances, photodeformable materials contain photoreactive molecules that absorb light of a specific wavelength and thus undergo structural changes. This is followed by concomitant changes in their physical and chemical properties, resulting in macroscopic mechanical movements. Therefore, various photoreactions have been studied to induce macroscopic deformations using light. The purpose of this review is to highlight key examples in the design of photodeformable materials using various photoreactions and to introduce some new and evolving trends by highlighting recent research. Macroscopic deformable materials controlled by light have been the subject of growing research interest in the last few decades due to both their fundamental properties and their wide applicability. In this review, examples of photomechanical effects in crystals, polymers, and CLCPs based on photoisomerization and photodimerization are reviewed.

Intermolecular crosslinking of abnormal prion protein is efficiently induced by a primuline-sensitized photoreaction

In prion diseases, infectious pathogenic particles that are composed of abnormal prion proteins (PrPSc) accumulate in the brain. PrPSc is biochemically characterized by its protease-resistance core (PrPres), but its structural features have not been fully elucidated. Here, we report that primuline, a fluorescent dye with photosensitization activity, dramatically enhances UV-irradiation-induced SDS-resistant PrPSc/res oligomer formation that can be detected by immunoblot analysis of prion-infected materials. This oligomer formation occurs specifically with PrPSc/res but not with normal prion protein, and it was demonstrated using purified PrPSc/res as well as unpurified materials. The oligomer formation proceeded in both primuline-dose- and UV irradiation time-dependent manners. Treatment with urea or formic acid did not break oligomers into monomers. Neither did the presence of aromatic amino acids modify oligomer formation. Analysis with a panel of anti-prion protein antibodies showed that the antibodies against the N-terminal region of PrPres were less reactive in the dimer than the monomer. These findings suggest that the primuline-sensitized photoreaction enhances intermolecular crosslinking of PrPSc/res molecules at a hydrophobic area of the N-terminal region of PrPres. In the screening of other compounds, photoreactive compounds such as luciferin exhibited a similar but lower activity with respect to oligomer formation than primuline. The enhanced photoreaction with these compounds will be useful for evaluating the structural features of PrPSc/res, especially the interactions between PrPSc/res molecules.

Development of an in vitro photosafety evaluation method utilizing intracellular ROS production in THP-1 cells.

Photoreactive compounds that may experience exposure to ultraviolet (UV) radiation can lead to the intracellular production of reactive oxygen species (ROS), which may cause phototoxic and photoallergenic responses. Here, we developed a novel in vitro photosafety assay and investigated whether it could be used to predict phototoxicity and photosensitivity by measuring changes in intracellular ROS production. THP-1 cells that had previously taken up 5-(and-6)-carboxy-2',7'-difluorodihydrofluorescein diacetate (carboxy-H2DFFDA), a ROS-sensitive fluorescent reagent, were exposed to photoreactive substances such as phototoxic and photoallergenic materials and then subjected to with UV-A irradiation (5 J/cm2). The fluorescence intensity was subsequently measured using a flow cytometer, and the intracellular ROS production was calculated. A statistically significant increase in ROS following treatment with photoreactive substances was observed in cells irradiated with UV-A. In contrast, no significant increase was observed for non-photoreactive substances in comparison to the control solution. Next, to confirm the impact of intracellular ROS on the photosensitive response, changes in CD86 and CD54 expression were measured following quencher addition during the photo human cell line activation test (photo h-CLAT). The results confirmed the reduction of CD86 and CD54 expression in response to photoallergenic substances following quencher addition. Together, these findings suggest that intracellular ROS production is involved in photosensitizing reactions. Therefore, we suggest that the developed method utilizing intracellular ROS production as an index may be useful as a novel in vitro evaluation tool for photoreactive substances.

Molecular Insights on Dissolved Organic Matter Transformation by Supraglacial Microbial Communities.

Snow overlays the majority of Antarctica and is an important repository of dissolved organic matter (DOM). DOM transformations by supraglacial microbes are not well understood. We use ultrahigh resolution mass spectrometry to elucidate molecular changes in snowpack DOM by in situ microbial processes (up to 55 days) in a coastal Antarctic site. Both autochthonous and allochthonous DOM is highly bioavailable and is transformed by resident microbial communities through parallel processes of degradation and synthesis. DOM thought to be of a more refractory nature, such as dissolved black carbon and carboxylic-rich alicyclic molecules, was also rapidly and extensively reworked. Microbially reworked DOM exhibits an increase in the number and magnitude of N-, S-, and P-containing formulas, is less oxygenated, and more aromatic when compared to the initial DOM. Shifts in the heteroatom composition suggest that microbial processes may be important in the cycling of not only C, but other elements such as N, S, and P. Microbial reworking also produces photoreactive compounds, with potential implications for DOM photochemistry. Refined measurements of supraglacial DOM and their cycling by microbes is critical for improving our understanding of supraglacial DOM cycling and the biogeochemical and ecological impacts of DOM export to downstream environments.

Pulsed xenon flash treatment inactivates bacteria in apheresis platelet concentrates while preserving in vitro quality and functionality.

Pulsed xenon (Xe) flash without any photoreactive compounds has been shown to inactivate a type of bacteria spiked into platelet (PLT) suspension in plasma, but enhanced the PLT storage lesion (PSL). Predicting reduction of PSL with increasing bactericidal ability, pulsed Xe flash was filtered through a band-stop filter, which excluded ultraviolet (UV)A, UVB, and visible light. Apheresis PLT concentrates (PCs) inoculated with bacteria were irradiated with filtered Xe flash (fXe treatment). For in vitro functional quality assessment, PLT aggregation and thrombin generation together with other assays that monitor the PSL were investigated. Staphylococcus aureus and Streptococcus dysgalactiae could be inactivated without regrowth during 6 days of storage. PC variables, such as PLT count, concentrations of soluble CD40 ligand, and ratio of aggregated PLTs, were not significantly different between fXe-treated and untreated PCs after 6 days of storage, while PAC-1 binding increased in the fXe-treated PLTs. Responsiveness of fXe-treated PLTs to ADP was maintained over a 6-day storage period as shown by the up regulation of P-selectin expression and induction of both integrin αIIbβ3 conformational change and PLT aggregation. The fXe-treated PLTs showed a sustained aggregation curve in response to ADP, whereas untreated PLTs transiently aggregated and then subsequently dissociated. Thrombin-generating kinetics of fXe-treated PLTs via PLT membrane surface were equivalent to those of untreated PLTs. The fXe treatment inactivated bacteria in apheresis PCs in plasma without additional chemical compounds. The fXe-treated PCs retained acceptable in vitro properties of PC quality and PLT functionality.

Femtochemistry of selected di-substituted benzenes

Ortho-di-substitution of benzenes provides the opportunity to study interactions between diverse functional groups in a defined environment. The substituents are forced to distances which allow chemical reactions to occur. In this feature article, we focus on photoreactive compounds containing nitro and carbonyl groups. The complex electronic structure of these molecules results in a rich photochemistry on the femto- and picosecond timescale. A combination of femtosecond spectroscopic techniques and quantum chemical calculations shows that all compounds studied undergo hydrogen transfers via both, singlet and triplet channels. In several cases these transfers are the starting point for further rearrangements. The experiments enabled us to elucidate the mechanisms of prominent photoreactions as the ones of ortho-nitrobenzaldehyde or of nitrobenzene derived photolabile protecting groups.

Influence of pressure on molecular packing and photochemical properties in three chalcone analogs

Abstract The structures of 1-(4-methylphenyl)-3-(2-thienyl)prop-2-en-1-one, (I), 1-(5-bromo-2-hydroxyphenyl)-3-(2-furyl)prop-2-en-1-one, (II), and 1-(3-furyl)-3-[3-(trifluoromethyl)phenyl]prop-2-en-1-one, (III), were determined in ambient and high pressure conditions. The values of the intermolecular geometrical parameters describing possibilities of execution of [2+2] photodimerization were calculated and analysed. In the case of ambient pressure, for (I) they are close to the border valid for photoreactive compounds and for (II) and (III) they exclude the photochemical reaction in crystals. High pressure hardly changed the mutual orientation of adjacent molecules and largely the distance between them: in the case of (I), the distance was far below limits for compounds undergoing [2+2] photodimerization. The volume of free space was calculated for the studied compounds for different values of pressure and analysed in the context of possibilities of the [2+2] photodimerization.

High Photoreactivity of o-Nitrobenzyl Ligands on Gold

We have studied the photopatterning of a gold surface functionalized with a self-assembled monolayer of an o-nitrobenzyl-based photouncaging ligand bound to the gold surface with a dual thiol anchor. We find that the dose of UV light required to induce the photoreaction on gold is very similar to the dose in an alcohol solution, even though many optical phenomena are strongly suppressed on metal surfaces. We attribute this finding to a combination of the large skin depth in gold at UV wavelengths, the high speed of the photoreaction, and the spatially indirect nature of the lowest excited singlet. Any photoreactive compounds where the quantum efficiency of fluorescence is sufficiently low, preferably no larger than about 10–5 in the case of gold surfaces, will show a similarly high photoreactivity in metal-surface monolayers.

Azidoblebbistatin, a photoreactive myosin inhibitor

Photoreactive compounds are important tools in life sciences that allow precisely timed covalent crosslinking of ligands and targets. Using a unique technique we have synthesized azidoblebbistatin, which is a derivative of blebbistatin, the most widely used myosin inhibitor. Without UV irradiation azidoblebbistatin exhibits identical inhibitory properties to those of blebbistatin. Using UV irradiation, azidoblebbistatin can be covalently crosslinked to myosin, which greatly enhances its in vitro and in vivo effectiveness. Photo-crosslinking also eliminates limitations associated with the relatively low myosin affinity and water solubility of blebbistatin. The wavelength used for photo-crosslinking is not toxic for cells and tissues, which confers a great advantage in in vivo tests. Because the crosslink results in an irreversible association of the inhibitor to myosin and the irradiation eliminates the residual activity of unbound inhibitor molecules, azidoblebbistatin has a great potential to become a highly effective tool in both structural studies of actomyosin contractility and the investigation of cellular and physiological functions of myosin II. We used azidoblebbistatin to identify previously unknown low-affinity targets of the inhibitor (EC(50) ≥ 50 μM) in Dictyostelium discoideum, while the strongest interactant was found to be myosin II (EC(50) = 5 μM). Our results demonstrate that azidoblebbistatin, and potentially other azidated drugs, can become highly useful tools for the identification of strong- and weak-binding cellular targets and the determination of the apparent binding affinities in in vivo conditions.

An Instrument for In Situ Measuring the Volume Scattering Function of Water: Design, Calibration and Primary Experiments

The optical volume scattering function (VSF) of seawater is a fundamental property used in the calculation of radiative transfer for applications in the study of the upper-ocean heat balance, the photosynthetic productivity of the ocean, and the chemical transformation of photoreactive compounds. A new instrument to simultaneously measure the VSF in seven directions between 20° to 160°, the attenuation coefficient, and the depth of water is presented. The instrument is self-contained and can be automatically controlled by the depth under water. The self-contained data can be easily downloaded by an ultra-short-wave communication system. A calibration test was performed in the laboratory based on precise estimation of the scattering volume and optical radiometric calibration of the detectors. The measurement error of the VSF measurement instrument has been estimated in the laboratory based on the Mie theory, and the average error is less than 12%. The instrument was used to measure and analyze the variation characteristics of the VSF with angle, depth and water quality in Daya Bay for the first time. From these in situ data, we have found that the phase functions proposed by Fournier-Forand, measured by Petzold in San Diego Harbor and Sokolov in Black Sea do not fit with our measurements in Daya. These discrepancies could manly due to high proportion of suspended calcium carbonate mineral-like particles with high refractive index in Daya Bay.

Quantitative analysis of aqueous phase composition of model dentin adhesives experiencing phase separation

There have been reports of the sensitivity of our current dentin adhesives to excess moisture, for example, water-blisters in adhesives placed on over-wet surfaces, and phase separation with concomitant limited infiltration of the critical dimethacrylate component into the demineralized dentin matrix. To determine quantitatively the hydrophobic/hydrophilic components in the aqueous phase when exposed to over-wet environments, model adhesives were mixed with 16, 33, and 50 wt % water to yield well-separated phases. Based upon high-performance liquid chromatography coupled with photodiode array detection, it was found that the amounts of hydrophobic BisGMA and hydrophobic initiators are less than 0.1 wt % in the aqueous phase. The amount of these compounds decreased with an increase in the initial water content. The major components of the aqueous phase were hydroxyethyl methacrylate (HEMA) and water, and the HEMA content ranged from 18.3 to 14.7 wt %. Different BisGMA homologues and the relative content of these homologues in the aqueous phase have been identified; however, the amount of crosslinkable BisGMA was minimal and, thus, could not help in the formation of a crosslinked polymer network in the aqueous phase. Without the protection afforded by a strong crosslinked network, the poorly photoreactive compounds of this aqueous phase could be leached easily. These results suggest that adhesive formulations should be designed to include hydrophilic multimethacrylate monomers and water compatible initiators.

Photomobile polymers from commercially available compounds: photoinduced deformation of side-chain polymers containing hydrogen-bonded photoreactive compounds

A photomobile polymer fiber containing anthracene carboxylic acid was prepared from a mixture of commercially available compounds and the photomechanical effects of the fiber were investigated. Upon exposure to UV light, the fiber bent toward the actinic light source owing to [4+4] photodimerization of the anthracene unit, which is similar to that for anthracene side-chain polymers. In addition, the photomechanical properties of the fiber were significantly enhanced by the introduction of liquid-crystalline (LC) properties through the addition of low molecular weight LC acids. Photomobile polymer fiber was prepared from a mixture of commercially available compounds. The fiber was bent toward the light source upon exposure to UV light. Addition of a low-molecular weight liquid-crystalline compound enhanced the photomechanical properties and photoreactivity.

Synthesis and Functional Characterization of Azido-Blebbistatin, a Photoreactive Myosin Inhibitor

Photoreactive compounds are important tools in life sciences that allow precisely timed covalent crosslinking of ligands and targets. Using a novel large-scale technique we have synthesized azidoblebbistatin, which is a new derivative of blebbistatin, the most widely used myosin inhibitor. Without UV irradiation azidoblebbistatin exhibits identical inhibitory properties to those of blebbistatin. Using UV irradiation azidoblebbistatin can be covalently crosslinked to myosin, which greatly enhances its in vitro and in vivo effectiveness. Photocrosslinking also eliminates limitations associated with the relatively low myosin affinity and water solubility of blebbistatin. Irradiating light used for photocrosslinking is not toxic for cells and tissues, which confers a great advantage in in vivo tests. As the crosslink results in an irreversible association of the inhibitor to myosin and the irradiation eliminates the residual activity of unbound inhibitor molecules, azidoblebbistatin has a great potential to become a highly effective tool in both structural studies of actomyosin contractility and the investigation of cellular and physiological functions of myosin II.

Immunogenicity and protective efficacy of a psoralen-inactivated dengue-1 virus vaccine candidate in Aotus nancymaae monkeys

Psoralens are photoreactive compounds that cross-link pyrimidines after exposure to UVA radiation. In this experiment, we tested the protective efficacy of a psoralen-inactivated dengue vaccine candidate in non-human primates. Two groups of 7 Aotus nancymaae monkeys received either 10 ng per dose of inactivated DENV1 plus alum adjuvant or alum alone (controls). Doses were injected intradermally on days 0, 14, and 28. Monkeys then received a challenge inoculation of 1.1 × 10 4 PFUs of WestPac 74 DENV-1 on day 132. At 62 days, only 1/7 vaccinated monkeys had detectable IgM, but IgG and neutralizing antibody remained detectable in 7/7. No IgM, IgG, or neutralizing antibody was detectable in control monkeys. DENV-1 viremia was detected after challenge in 3/7 vaccinated monkeys and 5/6 control monkeys (with one removed due to pregnancy) ( p = 0.27), but days of viremia were reduced from 3.67 days/animal among controls to 0.71 days/animal among vaccinated monkeys ( p = 0.051). Psoralen-inactivated DENV1 is immunogenic in Aotus nancymaae with a trend towards a reduction in days of viremia following experimental challenge.

Spectral properties and photobehaviour of 2,5-distyrylfuran derivatives

Four novel trans, trans-2,5-distyrylfuran derivatives ( E, E-X-DStFs, X = Cl, OCH 3, N(CH 3) 2, NO 2) have been synthesized and characterized by 1H and 13C NMR and UV–vis spectroscopy. The photophysical properties of the excited states of these poorly photoreactive compounds have been studied in two solvents of different polarities by stationary and pulsed techniques and also by the help of semiempirical quantum-mechanical calculations. The high fluorescence efficiency of these systems was accompanied by a modest triplet production (that becomes substantial in the nitro-derivative) investigated by nanosecond laser flash photolysis. The solvent effect on the absorption and emission spectra and on the photobehaviour allowed to evidence the presence of charge transfer (CT) excited states in the dimethylamino- and, particularly, in the nitro-derivative.

Rotating Cell for in Situ Raman Spectroelectrochemical Studies of Photosensitive Redox Systems

A recently developed rotating spectroelectrochemical cell for in situ Raman spectroscopic studies of photoreactive compounds without marked decomposition of the sample is presented. Photochemically and thermally sensitive redox systems are difficult to be studied under stationary conditions by in situ spectroelectrochemistry using laser excitation as in Raman spectroscopy. A rotating spectroelectrochemical cell can circumvent these difficulties. It can be used for any type of a planar electrode and for all electrode materials in contact with aqueous or nonaqueous solutions as well as with ionic liquids. The innovative technical solution consists of the precession movement of the spectroelectrochemical cell using an eccentric drive. This precession movement allows a fixed electrical connection to be applied for interfacing the electrochemical cell to a potentiostat. Hence, any electrical imperfections and noise, which would be produced by sliding contacts, are removed. A further advantage of the rotating cell is a dramatic decrease of the thermal load of the electrochemical system. The size of the spectroelectrochemical cell is variable and dependent on the thickness of the cuvettes used ranging up to approximately 10 mm. The larger measuring area causes a higher sensitivity in the spectroscopic studies. The as constructed spectroelectrochemical cell is easy to handle. The performance of the cell is demonstrated for ordered fullerene C(60) layers and the spectroelectrochemical behavior of nanostructured fullerenes. Here the charge transfer at highly ordered fullerene C(60) films was studied by in situ Raman spectroelectrochemistry under appropriate laser power and accumulation time without marked photodecomposition of the sample.

OT‐674 Suppresses Photooxidative Processes Initiated by an RPE Lipofuscin Fluorophore

The pathological processes involved in age-related macular degeneration (AMD) include retinal pigment epithelial (RPE) cell degeneration; oxidative mechanisms likely contribute to the demise of these cells. Indeed, RPE cells may be particularly susceptible to photooxidative mechanisms since they accumulate retinoid-derived photoreactive compounds that constitute the lipofuscin of the cell. Thus we undertook to test the capacity of OT-674, the reduction product (Tempol-H) of the nitroxide Tempol, to suppress photooxidative processes initiated by the RPE lipofuscin fluorophore A2E. Accordingly, when ARPE-19 cells that had accumulated A2E were irradiated at 430 nm, pretreatment with OT-674 (0.01-10 mM) was found to confer a resistance to cell death. Monitoring by quantitative HPLC also showed that OT-674 reduced A2E photooxidation in a cell-free system. Moreover, when presented with a singlet oxygen generator, OT-674 served as a quencher of singlet oxygen that was more effective than Trolox and alpha-tocopherol. We conclude that OT-674 is a potent antioxidant that suppresses photooxidative processes generated in cultured RPE cells by the lipofuscin fluorophore A2E. As oxidative damage to RPE cells is considered to be a risk factor for AMD, antioxidant therapy with OT-674 may serve a protective role.