SINGLET OXYGEN QUANTUM YIELDS OF PORPHYRIN-BASED PHOTOSENSITIZERS FOR PHOTODYNAMIC THERAPY

The major cytotoxic agent with most current photosensitizers used in photodynamic therapy(PDT)is widely believed to be singlet oxygen(^(1)O_(2)).Determination of the ^(1)O_(2) quantum yields for porphyrin-based photosensitizers,including hematoporphyrin derivative(HiPorfin),hematoporphyrin monomethyl ether(HMME)and photocarcinorin(PsD-007)in air-saturated dimethylformamide(DMF)solutions were performed by the direct measurement of their near-infrared luminescence.In addition,^(1)O_(2) quencher sodium azide was employed to confirm the ^(1)O_(2) generation from the investigated photosensitizers.The maximal ^(1)O_(2) luminescence occurs at about 1280 nm with full width at half maximum of 30 nm.The ^(1)O_(2) quantum yields were found to be 0.61±0.03,0.60±0.02 and 0.59±0.03 for HiPorfin,HMME and PsD-007,respectively.These results provide that these porphyrin-based photosensitizers produce ^(1)O_(2) under irradiation,which is of significance for the study of their photodynamic action in PDT.

Dependence of Quantum Yields on Size of Ag Nano-particle Embedded in BaO Thin Film

Theoretical dependence of the quantum yields on the size of Agnano-particle distribution from 0.8 nm to 37 nm embedded in BaOsemiconductor is discussed. The calculation results show that theincrease in Ag nano-particle diameter leads to the increase of thequantum yield threshold and the emergence of the rough Gaussian form,the results also shown that the greater increase in Ag nano-particlediameter causes the emergence of the exact Gaussian form and makesthe peaks rise up.

High thermal stability and quantum yields of green-emitting Sr_3Gd_2(Si_3O_9)_2:Tb^(3+) phosphor by co-doping Ce^(3+)

A series of Tb^3＋ mono-doped and Ce^3＋-Tb^3＋ co-doped Sr3Gd2（Si3O9）2 phosphors with high thermal stability and quantum yields were successfully prepared via the solid state reaction. The as-prepared Sr3Gd2（Si3O9）2：Tb^3＋ samples showed broad excitation spectrum from 250 to 400 nm and presented characteristic emission transitions ^5D4→^7FJ（J=6, 5, 4, 3） of Tb^3＋ under 313 nm excitation, which were located at about 488, 541, 584 and 620 nm. The emission intensities of Tb^3＋ rose steadily in Sr3Gd2（Si3O9）2 host with the increase of Tb^3＋ concentration even though Gd^3＋ ions were completely replaced by Tb^3＋ ions. The Ce^3＋ ion as a sensitizer could efficiently improve the performance of Tb^3＋ ion. First, with Ce^3＋ co-doping, the excitation spectrum of Tb^3＋ monitored at 541 nm showed a similar band that responds to the violet emission of Ce^3＋ monitored at 416 nm. Second, the quantum yields of Sr3Gd2（Si3O9）2：Tb^3＋ phosphors could be enhanced from 26.6% to 80.2% by co-doping Ce^3＋. Finally, the co-doping of Ce^3＋ was also effective to improve the thermal stability of Sr3Gd2（Si3O9）2：Tb^3＋. As the temperature rose to 150 oC, the emission intensity of Tb^3＋ remained at about 83.6% of that measured at room temperature, which was better than the commercial YAG：Ce phosphor in terms of their thermal quenching properties. These results indicated that the as-prepared Sr3Gd2（Si3O9）2：Tb^3＋,Ce^3＋ samples could be used as green emission phosphors for possible applications in near ultraviolet based WLEDs.

Wide emission shifts and high quantum yields of solvatochromic carbon dots with rich pyrrolic nitrogen

Carbon dots(CDs)with solvatochromic emission colors in different solvents have attracted much attention as a new class of luminescent nanomaterial owing to their facile synthesis and low production cost.In this work,we prepared two kinds of CDs with solvatochromic emissions:green emission CDs(G-CDs)and multicolor emission CDs(M-CDs).G-CDs synthesized from o-phenylenediamine exhibited weak photoluminescence emission(quantum yield 2.8%-6.1%)and 39 nm solvatochromic shifts(492-531 nm).In contrast,M-CDs prepared from o-phenylenediamine and 4-aminophenol showed 87 nm solvatochromic shift range(505-592 nm)and much higher photoluminescence quantum yield(18.4%-32.5%).The two CDs exhibited different emission,absorption,and photoluminescence lifetime.The origin of solvatochromic shifts and the formation mechanism of CDs were demonstrated by analyzing the structures and compositions of two CDs.High percentages of pyrrolic nitrogen and amino nitrogen make wider solvatochromic shifts and higher quantum yields.The results were well supported by density functional theory calculations.This effective strategy to expand solvatochromic shift range and improve quantum yields could open a new window to prepare satisfied solvatochromic carbon dots.

Bioremediation Potential of the Macroalga Ulva lactuca (Chlorophyta) for Ammonium Removal in Elastomer Industry Wastewater

During the production of nitrile rubber, significant amounts of nitrogen in the form of ammonium are generated in the wastewater. The discharge of this high-nitrogen wastewater can lead to serious environmental issues, including eutrophication, disruption of aquatic ecosystems, and groundwater contamination. To mitigate these impacts, this research explored the bioremediation capabilities of the macroalgae Ulva lactuca (Chlorophyta) for removing nitrogen from nitrile rubber production wastewater. The study employed single-phase and Michaelis-Menten decay models based on ammonium consumption, using various dilutions of wastewater to identify the optimal concentration for treatment. The physiological state of the macroalgae was monitored by measuring the photosynthetic capacity and specific growth rate during the experiments. In the presence of U. lactuca, ammonium concentrations decreased in all treatment groups, confirming that the ammonium kinetics conformed to both applied models. Our results show that U. lactuca effectively reduces ammonium concentrations, with an approximate removal rate of 0.020 µM·g−1·min−1 across different wastewater concentrations (70%, 80%, 90%, and 100%). Notably, the treatments with 70%, 80%, and 90% wastewater strength achieved about 67% reduction in ammonium, demonstrating the alga’s capacity to treat high-nitrogen wastewater. The photosynthetic performance of U. lactuca initially declined in control conditions but stabilized across all treatments, highlighting its adaptability. The kinetic analysis using the Michaelis-Menten model indicated a Vmax of 1342 μM·g−1·DMh−1, suggesting a robust capacity for ammonium uptake when fully saturated. Our study underscores the potential of Ulva lactuca as a cost-effective and efficient agent for wastewater bioremediation, particularly in settings with high nitrogen loads.

Europium Coordination Compound with Highly Improved Luminescent Quantum Yield

The luminescent properties of two Eu3＋ compounds based on quinoline-2-car- boxylic acid （Hqc）, [Na2Eu2（qc）6（CH3COO）2（H2O）4].2DMF （1） and [Eu2（qc）6（H2O）6].3H2O （2）, as well as their syntheses and structures are reported. Both compounds are formed by slow evaporation at room temperature and exhibit zero dimensional dinuclear structures. It is worth mentioning that a 4.5-fold enhancement in luminescent quantum yield is achieved by reducing the nonradiative deactivation, through which the quantum yield increases remarkably to 67.62% for 1 compared with 12.18% for 2.

Exploiting Quantum Confinement for Future Solar Cell Application

Present solar cells are expensive making photovoitaic electricity only attractive whenever there is government incentive. This paper highlights the cost of photovoltaic classified according to first, second and third generations. The first and second generations make up the current photovoltaic. The reasons for the efficiency limitation of the first and second generation photovoltaic are given. Nanoparticles such as quantum dots have confinement properties that can be exploited to improve solar cell efficiency and help reduce the cost. Quantum effect that support hot electron collection and multiple exciton generation through impact ionization are discussed. These form the basis of the future generation quantum dot solar cell.

High photoluminescence Ag-In-Ga-S quantum dots based on ZnX_(2)-treated surface passivation

Quaternary Ag-In-Ga-S(AIGS)quantum dot(QD)is considered a promising,spectral-tunable,and environmentally friendly luminescent display material.However,the more complex surface defect states of AIGS QDs resulting from the coexistence of multiple elements lead to a low(<60%)photoluminescence quantum yield(PLQY).Here,we develop a novel convenient method to introduce Z-type ligands ZnX_(2)(X=Cl,Br,I)for passivating the surface defects of AIGS QDs to dramatically enhance the PLQY and stability without affecting the crystalline structure and morphology.Results show that the addition of ZnCl_(2) during the purified process of AIGS QDs leads to a 3-fold increase of PLQY(from 28.5% to 87%).Impressively,the highest PLQY is up to a recorded value of 92%,which is comparable to typical heavy metal QDs.Exciton dynamics studies have shown that the rapid annihilation process of excitons in treated QDs is inhibited.We also confirm that the improvement in PLQY is a result of the effective passivation of the non-coordinating atom on the QD surface by building a new bonding between sulfur dangling and Zn2+.The realization of high PLQY will further promote the application of AIGS QDs in luminescent displays.

Effects of the Liquid Conductivity on Pulsed High-voltage Discharge Modes in Water

Spark, stream and corona pulsed high-voltage discharges in water induced by the various initial conductivities have been examined in this paper. The discharge modes changed from spark to corona discharge with the liquid conductivity increasing. The apparent production of OH radical and quantum yield generated by spark discharge in distilled water were 11.57 ìmol/L and 0.0978 photon/s, respectively. A preliminary study on acid fuchsine (AF) treatment indicated that higher AF removal efficiency has been achieved by spark discharge. The process of degradation showed that the oxidative effects through OH radical oxidation did not play an important role and did increase with the discharge mode changing to spark discharge.

A Kinetic Approach to Photomineralization of Methane in Air by Membranes Based on TiO2/WO3

Photomineralization of methane in air(10.0-1,000 ppm(mass/volume)of C)at 100%relative humidity(dioxygen as oxygen donor),was systematically studied at 318±3 K,in an annular laboratory-scale reactor,by photocatalytic membranes immobilising titanium dioxide and tungsten trioxide as co-photocatalysts.Kinetics of both substrate disappearance,to yield intermediates,and total organic carbon(TOC)disappearance,to yield carbon dioxide,were followed.A kinetic model was employed,from which,by a set of differential equations,four final optimised parameters,k1 and K1,k2 and K2,were calculated,able to fit the whole kinetic profile adequately.Modelling of quantum yields,as a function of substrate concentration and irradiance,as well as of concentration of photocatalysts,was carried out very satisfactorily.Kinetics of hydroxyl radicals reacting between themselves,leading to hydrogen peroxide,other than with substrate or intermediates leading to mineralization,were considered,paralleled by second competition kinetics involving superoxide radical anion.When using appropriate blends of the two photocatalysts,limiting quantum yieldsF∞values increase considerably and approach the maximum allowable value for the investigated molecule,in a much wider range of irradiances than that shown by the single catalysts mainly at low irradiances.This may be interpreted by strong competition kinetics of superoxide radicals generated by the catalyst defects,in the corresponding range of high irradiances.By this way,operation at high irradiance values is possible,without losing any efficiency for the mineralization process.

Autumn Photoproduction of Carbon Monoxide in Jiaozhou Bay, China

Carbon monoxide(CO) plays a significant role in global warming and atmospheric chemistry. Global oceans are net natural sources of atmospheric CO. CO at surface ocean is primarily produced from the photochemical degradation of chromophoric dissolved organic matter(CDOM). In this study, the effects of photobleaching, temperature and the origin(terrestrial or marine) of CDOM on the apparent quantum yields(AQY) of CO were studied for seawater samples collected from Jiaozhou Bay. Our results demonstrat that photobleaching, temperature and the origin of CDOM strongly affected the efficiency of CO photoproduction. The concentration, absorbance and fluorescence of CDOM exponentially decreased with increasing light dose. Terrestrial riverine organic matter could be more prone to photodegradation than the marine algae-derived one. The relationships between CO AQY and the dissolved organic carbon-specific absorption coefficient at 254 nm for the photobleaching study were nonlinear, whereas those of the original samples were strongly linear. This suggests that: 1) terrestrial riverine CDOM was more efficient than marine algae-derived CDOM for CO photoproduction; 2) aromatic and olefinic moieties of the CDOM pool were affected more strongly by degradation processes than by aliphatic ones. Water temperature and the origin of CDOM strongly affected the efficiency of CO photoproduction. The photoproduction rate of CO in autumn was estimated to be 31.98 μmol m-2 d-1 and the total DOC photomineralization was equivalent to 3.25%- 6.35% of primary production in Jiaozhou Bay. Our results indicate that CO photochemistry in coastal areas is important for oceanic carbon cycle.

Assessment of Photochemical Reflectance Index as a Tool for Evaluation of Chlorophyll Fluorescence Parameters in Cotton and Peanut Cultivars Under Water Stress Condition

The relationships between photochemical reflectance index （PRI） and the chlorophyll fluorescence parameters were examined to assess suitability of PRI as a remote-sensing tool for the chlorophyll fluorescence parameters. A greenhouse experiment was conducted using cotton and peanut crops under water stress condition. Five cotton and six peanut cultivars were grown using Andosole soil in pots maintained at two water levels; the control and water stress treatment （WS） of 100 and 50% of the daily transpiration, respectively. Higher non-photochemical quenching （NPQ） was exhibited by peanut than that of cotton by the water stress. On the other hand, the decreases of the actual quantum yield of photosystem II （△F/F＇m） and PRI by the water stress in cotton were larger than those in peanut. There were positively significant correlation coefficients between PRI and △F/F＇m in cotton at noon and in the afternoon including the control and WS. The correlations of PRI with NPQ were negatively significant at noon and in the afternoon for cotton, and in the afternoon for peanut. No clear relationship was found among these parameters in the morning probably due to the diurnal increase in global solar radiation. It was concluded that there would be a possibility to detect the effects of water stress on △F/F＇m and NPQ by PRI with some exceptions, although PRI could not note varietals differences in △F/F＇m and NPQ for each treatment.

Photosynthetic activity and antioxidative response of seagrass Thalassia hemprichii to trace metal stress

This study concerned the accumulation of trace metals in tissues of seagrass ( Thalassia hemprichii) exposed to various concentrations of Zn2+,Cd2+,Pb2+ and Cu2+ for 10 d,and the effect of excessive metals on quantum yield (△F/F′m),photosynthetic pigments and antioxidative enzymes like superoxide dismutase (SOD),guaiacol peroxidase (POD) were also examined.Cadmium was the most highly accumulated metal.Meanwhile,high metals levels led to a remarkable breakdown of photosynthetic parameters.Especially,△F/F′m,chlorophyll and carotenoid were significantly low during prolonged Cu exposure.Besides,△F/F′m was more severely depressed by Cu and Zn than Pb and Cd.However,T.hemprichii had positive response by increasing the activity of SOD and POD.The results indicate that T.hemprichii is the most sensitive to Cu,and the antioxidative protection mechanisms of T.hemprichii are more efficiently activated to avoid damage of Zn,Cd and Pb stress. Finally,due to the high Cd-accumulation and strong Cd-tolerance capacity,T.hemprichii can be used for phytoremediation in Cd-contaminated areas.

Pyropia yezoensis can utilize CO_2 in the air during moderate dehydration

Pyropia yezoensis, an intertidal seaweed, experiences regular dehydration and rehydration with the tides. In this study, the responses of P. yezoensis to dehydration and rehydration under high and low CO2 concentrations （（600-700）×10^-6 and （40-80）×10^-6, named Group I and Group II respectively） were investigated. The thalli of Group I had a significantly higher effective photosystem II quantum yield than the thalli of Group II at 71% absolute water content （AWC）. There was little difference between thalli morphology, total Rubisco activity and total protein content at 100% and 71% AWC, which might be the basis for the normal performance of photosynthesis during moderate dehydration. A higher effective photosystem I quantum yield was observed in the thalli subjected to a low CO2 concentration during moderate dehydration, which might be caused by the enhancement of cyclic electron flow. These results suggested that P. yezoensis can directly utilize COz in ambient air during moderate dehydration.

Nonculturability of the pathogenic Vibrio parahaemolyticus in live culture of Grateloupia turuturu is associated with bacterial attachment to the algal thalli

The invasive red alga Grateloupia turuturu Yamada could turn Vibrio parahaemolyticus into nonculturable state in live algal culture.In order to elucidate the mechanism of such an effect,a series of culture experiments were performed in this investigation based on three hypothesized causes,namely bacterial attachment,production of reactive oxygen species （ROS） and the discharge of water soluble secondary metabolic compounds.The results reveal that attachment to the thallus surface of G.turuturu was the major reason for the decrease of V.parahaemolyticus in seawater.Further investigations show that V.parahaemolyticus attachment to the surface of algal thallus in live cultures of seaweeds was a common phenomenon.However,the disappearance of the culturability of V.parahaemolyticus occurred only on the thallus of G.turuturu over 72 h among all six algal species tested.Electron microscopic scanning shows that most of V.parahaemolyticus attached to G.turuturu changed from the initial normal bacilli to coccoid-shape after 72 h.The enclosure experiments by enclosing the algal thallus in tubes demonstrate that the nonculturability of V.parahaemolyticus in the water of live culture of G.turuturu occurred after the physical contact of the V.parahaemolyticus to the alga.The capacity of G.turuturu in affecting the culturability of V.parahaemolyticus was not influenced after inhibition of photosynthesis by treatment of 3（3,4dichlorophenyl）-1 ,1dimethyl urea （DCMU） at non-lethal levels.Production of reactive oxygen species after addition of live culture of bacteria was excluded by on-line analyzing the oxidation of dichlorohydrofluorescein （DCFH） to dichlorofluorescein （DCF） in the presence of peroxidase on a VersaFluor fluorometer.

Effect of overnight temperature on leaf photosynthesis in seedlings of Swietenia macrophylla King

After exposure of one-year old seedlings of Swietenia macrophylla to an overnight temperature (13 C, 19 C, 25 C, 31 C or 35 C), the leaf net photosynthetic rate (Pn) was researched through measuring photosynthetic light-response curves at 360 mmolmol-1 CO2, and photosynthetic CO2-response curves at light-saturated intensity (1500 mmolm-2 s-1). The optimal temperature for photosynthesis measured at 360 mmol穖ol-1 CO2 was from 25 C to 31 C, but which was from 31C to 35 C at saturating CO2 concentration. At temperature of below 25 C, the decline in Pn was mainly due to the drop in carboxylation efficiency (Ce), while as temperature was over 31 C, the reduction in Pn resulted from both decrease in Ce and increase in leaf respiration. The CO2-induced stimulation of photosynthesis was strongly inhibited at temperatures below 13 C. The results showed that, the leaf photosynthesis of tropical evergreen plants should not be accelerated at low temperature in winter season with elevated CO2 concentration in the future.

Improvement of photoemission performance of a gradient-doping transmission-mode GaAs photocathode

Two types of transmission-mode GaAs photocathodes grown by molecular beam epitaxy are compared in terms of activation process and spectral response, one has a gradient-doping structure and the other has a uniform-doping structure. The experimental results show that the gradient-doping photocathode can obtain a higher photoemission capability than the uniform-doping one. As a result of the downward graded band-bending structure, the cathode performance parameters, such as the electron average diffusion length and the surface electron escape probability obtained by fitting quantum yield curves, are greater for the gradient-doping photocathode. The electron diffusion length is within a range of from 2.0 to 5.4μm for doping concentration varying from 10^19 to 10^18 cm^-3 and the electron average diffusion length of the gradient-doping photocathode achieves 3.2 μm.

Meso-substituted cationic 3-and 4-N-Pyridylporphyrins and their Zn(II)derivatives for antibacterial photodynamic therapy

Photodynamic inactivation of microorganisms known as antibacterial photodynamic therapy(APDT)is one of the most promising and innovative approaches for the destruction of pathogenic microorganisms.Among the photosensitizers(PSs),compounds based on cationic porphyrins/metalloporphyrins are most successfully used to inactivate microorganisms.Series of meso-substituted cationic pyridylporphyrins and metalloporphyrins with various peripheral groups in the third and fourth positions of the pyrrole ring have been synthesized in Armenia.The aim of this work was to determine and test the most e®ective cationic porphyrins and metalloporphyrins with high photoactivity against Gram negative and Gram positive microorganisms.It was shown that the synthesized cationic pyridylporphyrins/metalloporphyrins exhibit a high degree of phototoxicity towards both types of bacteria,including the methicillinresistant S.aureus strain.Zinc complexes of porphyrins are more phototoxic than metal-free porphyrin analogs.The e®ectiveness of these Zn–metalloporphyrins on bacteria is consistent with the level of singlet oxygen generation.It was found that the high antibacterial activity of the studied cationic porphyrins/metalloporphyrins depends on four factors:the presence in the porphyrin macrocycle of a positive charge(+4),a central metal atom(Zn2þÞand hydrophobic peripheral functional groups as well as high values of quantum yields of singlet oxygen.The results indicate that meso-substituted cationic pyridylporphyrins/metalloporphyrins cannd wider application in photoinactivation of bacteria than anionic or neutral PSs usually used in APDT.

Comparison of the photoemission behaviour between negative electron affinity GaAs and GaN photocathodes

In view of the important application of GaAs and GaN photocathodes in electron sources, differences in photoe- mission behaviour, namely the activation process and quantum yield decay, between the two typical types of III-V compound photocathodes have been investigated using a multi-information measurement system. The activation exper- iment shows that a surface negative electron affinity state for the GaAs photocathode can be achieved by the necessary Cs-O two-step activation and by Cs activation alone for the GaN photocathode. In addition, a quantum yield decay experiment shows that the GaN photocathode exhibits better stability and a longer lifetime in a demountable vacuum system than the GaAs photocathode. The results mean that GaN photocathodes are more promising candidates for electron source emitter use in comparison with GaAs photocathodes.

Absorption,quenching,and enhancement by tracer in acetone/toluene laser-induced fluorescence

To measure the equivalent ratio distribution of the two-stage lean premixed(DLP)flame,we propose using acetone/toluene planar laser-induced fluorescence(PLIF)technology to simultaneously measure the concentrations of the two components.Appropriate excitation laser wavelength and filters are used to assess the influence of acetone and toluene on each other’s fluorescence signal at room temperature.Experimental results show that acetone has a strong absorption effect on toluene’s fluorescence signal,the effective absorption cross-section is 5.77×10-20 cm-2.Acetone has an obvious quenching effect on the toluene fluorescence signal,and the Stern–Volmer coefficient is 0.50 kPa-1.The collisions between the molecules of toluene and acetone will lead to the enhancement of the fluorescence signal of acetone,and the enhancement coefficient is exponential with the acetone’s concentration.The quantitative relationship between the fluorescence intensity and the concentrations of the two tracers is obtained by establishing the photophysical model of toluene and acetone’s fluorescence signals.