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Opis: Treatment of biologically complex diseases, such as cancer, can significantly benefit from combination therapies. These powerful therapies are able to simultaneously target different biological targets, thereby overcoming or reducing drug resistance, decreasing dose-related toxicity, and potentially exhibiting synergistic effects. Herein, we combine the effects of nitric oxide (NO) gas therapy and an anticancer drug Doxorubicin (Dox) using a porous organic polymer (POP) as a delivery vehicle for both. SH-POP, synthesized by a facile, room-temperature method, is rich in both thiol (-SH) and secondary amine (R-NH-R’) functional groups, which can be post-synthetically nitrosylated in a room-temperature reaction that uses water as a solvent, yielding SNO-POP. Fourier-transform infrared (FT-IR) and Raman spectroscopy confirm that both types of functional groups are nitrosylated. Upon white light irradiation, SNO-POP releases up to ~60 µmol of NO per g, and exhibits reversible switch on – switch off NO release behavior triggered by simple light irradiation for at least 20 cycles. Unlike many conventional systems, where a known small-molecule NO donor is incorporated into the pores, here, the porous polymer itself serves as a NO donor, so the pores remain available for the encapsulation of another therapeutic, i.e. Dox. The release of Dox from the Dox@SNO-POP system is pH-sensitive and occurs preferentially in a slightly acidic environment (pH = 5.4). HeLa cancer cell viability studies confirm an enhancement in toxicity that can be ascribed to the synergistic effects of light-triggered NO release and pH-triggered Dox release. Confocal microscopy imaging reveals the presence of both species inside cells. This study is expected to stimulate the development of porous polymers as potent vehicles for combination therapies in cancer treatment and beyond.
Ključne besede: porous organic polymer, nitric oxide, combination therapy, synergistic therapy, chemotherapy
Objavljeno v RUNG: 05.07.2024; Ogledov: 224; Prenosov: 1
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Opis: During the summer of 2012 a coordinated field campaign was conducted in multiple locations in Greece in order to characterize the ambient particulate matter (PM) levels, its chemical composition and the contribution of the regional and local sources. PM1, PM2.5 and PM10 samples were collected simultaneously at seven different sites in Greece: an urban and a suburban station in Patras, a suburban station in Thessaloniki, a suburban and an urban background station in Athens, a rural background station at the Navarino Environmental Observatory (NEO) in southwestern Peloponnese and a remote background site at Finokalia in the northeastern part of Crete. The sites were selected to facilitate the estimation of the contribution of the local emission sources and long range transport. Sulfate and organics were the major PM1 components in all sites suggesting that high sulfate levels still remain in parts of Europe. The photochemistry of the Eastern Mediterranean can convert rapidly the emitted sulphur dioxide to sulfate. Our analysis indicated significant sulfate production over the area, with high sulfate levels, especially in the remote site of Finokalia, associated with air masses that had passed over Turkey. There was high regional secondary organic aerosol production dominating organic aerosol levels even in a major city like Athens. High organic aerosol levels were associated with air masses that had crossed the Balkans with a significant biogenic component. The average PM2.5 concentration ranged from 13 to 18 μg m−3 in the different sites. There were unexpected significant gradients in the concentrations of secondary aerosol components in length scales of a few hundred kilometers. The low concentrations of measured PM2.5 nitrate are mostly organic nitrates and supermicrometer nitrate associated with sea-salt and dust. Dust was a significant PM10 constituent in all areas and was quite variable in space showing the importance of the local sources.
Ključne besede: PM2.5, sulfate aerosol, secondary inorganic aerosol, secondary organic aerosol, Greece
Objavljeno v RUNG: 13.05.2024; Ogledov: 392; Prenosov: 0
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Opis: Monoterpenes and isoprene are important constituents of the volatile organic compounds (VOCs) due to their high reactivity and participation in ozone and secondary aerosol formation. The current work focuses on the results of a 13-month intensive campaign of high resolution time-resolved measurements of these compounds, at an urban background site in Athens, Greece. On an annual basis, monoterpenes (α-pinene and limonene) surpass the isoprene levels presenting mean values of 0.70 ± 0.83 μg m−3, 0.33 ± 0.78 μg m−3 and 0.19 ± 0.36 μg m−3, respectively. The large standard deviation highlights the significant diurnal and day-to-day variability. Isoprene presents a typical seasonal cycle, with a photochemically induced summer-time maximum. Enhanced noon levels are observed during summer, whereas a morning peak in the autumn and winter profiles occurs, despite the generally low levels encountered during these seasons. The monoterpenes deviate from the expected biogenic pattern, presenting higher mean levels during the cold period and a night-to-early morning enhancement strongly related to local anthropogenic tracers such as BC, CO, NO or toluene, as well as increased levels under wind speeds lower than 3 m s−1. Estimations of the anthropogenic and biogenic fractions based on the enhancement ratios of α-pinene versus a variety of anthropogenic tracers, demonstrate a clear dominance of the anthropogenic sources in all studied seasons. Simultaneously, the biogenic fraction increased during summer relative to winter by more than 10 times. Both α-pinene and limonene significantly contribute to locally formed secondary organic aerosol (SOA), determined by means of an ACSM, accounting for at least 22% and 13% of their levels in summer and winter respectively. Additionally, monoterpenes and isoprene contribute 6% to the observed oxidants levels (O3 + NOx) during summer.
Ključne besede: volatile organic compounds, biogenic compounds, monoterpenes, isoprene, Athens
Objavljeno v RUNG: 10.05.2024; Ogledov: 386; Prenosov: 2
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Opis: This study analyses 4-years of continuous 7-λ Aethalometer (AE-33) measurements in an urban-background environment of Athens, to resolve the spectral absorption coefficients (babs) for black carbon (BC) and brown carbon (BrC). An important BrC contribution (23.7 ± 11.6%) to the total babs at 370 nm is estimated for the period May 2015–April 2019, characterized by a remarkable seasonality with winter maximum (33.5 ± 13.6%) and summer minimum (18.5 ± 8.1%), while at longer wavelengths the BrC contribution is significantly reduced (6.8 ± 3.6% at 660 nm). The wavelength dependence of the total babs gives an annual-mean AAE370-880 of 1.31, with higher values in winter night-time. The BrC absorption and its contribution to babs presents a large increase reaching up to 39.1 ± 13.6% during winter nights (370 nm), suggesting residential wood burning (RWB) emissions as a dominant source for BrC. This is supported by strong correlations of the BrC absorption with OC, EC, the fragment ion m/z 60 derived from ACSM and PMF-analyzed organic fractions related to biomass burning (e.g. BBOA). In contrast, BrC absorption decreases significantly during daytime as well as in the warm period, reaching to a minimum during the early-afternoon hours in all seasons due to photo-chemical degradation. Estimated secondary BrC absorption is practically evident only during winter night-time, implying the fast oxidation of BrC species from RWB emissions. Changes in mixing-layer height do not significantly affect the BrC absorption in winter, while they play a major role in summer.
Ključne besede: spectral aerosol absorption, brown carbon, wood burning, organic aerosols, chemical composition, Athens
Objavljeno v RUNG: 10.05.2024; Ogledov: 429; Prenosov: 1
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Opis: Abstract. Black carbon (BC) is recognized as the most important warming agent among atmospheric aerosol particles. The absorption efficiency of pure BC is rather well-known, nevertheless the mixing of BC with other aerosol particles can enhance the BC light absorption efficiency, thus directly affecting Earth's radiative balance. The effects on climate of the BC absorption enhancement due to the mixing with these aerosols are not yet well constrained because these effects depend on the availability of material for mixing with BC, thus creating regional variations. Here we present the mass absorption cross-section (MAC) and absorption enhancement of BC particles (Eabs), at different wavelengths (from 370 to 880 nm for online measurements and at 637 nm for offline measurements) measured at two sites in the western Mediterranean, namely Barcelona (BCN; urban background) and Montseny (MSY; regional background). The Eabs values ranged between 1.24 and 1.51 at the urban station, depending on the season and wavelength used as well as on the pure BC MAC used as a reference. The largest contribution to Eabs was due to the internal mixing of BC particles with other aerosol compounds, on average between a 91 % and a 100 % at 370 and 880 nm, respectively. Additionally, 14.5 % and 4.6 % of the total enhancement at the short ultraviolet (UV) wavelength (370 nm) was due to externally mixed brown carbon (BrC) particles during the cold and the warm period, respectively. On average, at the MSY station, a higher Eabs value was observed (1.83 at 637 nm) compared to BCN (1.37 at 637 nm), which was associated with the higher fraction of organic aerosols (OA) available for BC coating at the regional station, as denoted by the higher organic carbon to elemental carbon (OC:EC) ratio observed at MSY compared to BCN. At both BCN and MSY, Eabs showed an exponential increase with the amount of non-refractory (NR) material available for coating (RNR-PM). The Eabs at 637 nm at the MSY regional station reached values up to 3 during episodes with high RNR-PM, whereas in BCN, Eabs kept values lower than 2 due to the lower relative amount of coating materials measured at BCN compared to MSY. The main sources of OA influencing Eabs throughout the year were hydrocarbon OA (HOA) and cooking-related OA (COA), i.e. primary OA (POA) from traffic and cooking emissions, respectively, at both 370 and 880 nm. At the short UV wavelength (370 nm), a strong contribution to Eabs from biomass burning OA (BBOA) and less oxidized oxygenated OA (LO-OOA) sources was observed in the colder period. Moreover, we found an increase of Eabs with the ageing state of the particles, especially during the colder period. This increase of Eabs with particle ageing was associated with a larger relative amount of secondary OA (SOA) compared to POA. The availability of a long dataset at both stations from offline measurements enabled a decade-long trend analysis of Eabs at 637 nm, that showed statistically significant (s.s.) positive trends of Eabs during the warmer months at the MSY station. This s.s. positive trend in MSY mirrored the observed increase of the OC:EC ratio over time. Moreover, in BCN during the COVID-19 lockdown period in spring 2020 we observed a sharp increase of Eabs due to the observed sharp increase of the OC:EC ratio. Our results show similar values of Eabs to those found in the literature for similar background stations.
Ključne besede: black carbomn, coating, organic aerosol, light absorption
Objavljeno v RUNG: 10.05.2024; Ogledov: 428; Prenosov: 2
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