Molecular engineering of metal-based photosensitizers with narrow band gap for efficient photodynamic therapy.

Three iridium(III) complexes were designed with the purpose of elucidating the photo-physicochemical properties of iridium(III) complexes with narrow band gap at the electronic level. This study indicates that increasing the ligand rigidity and electron delocalization of the compounds can suppress the ring-stretching vibrations of the iridium(III) complex, thus improving their photo-chemical activity and photocytotoxicity.

A Self-Assembly-Induced Exciton Delocalization Strategy for Converting a Perylene Diimide Derivative from a Type-II to Type-I Photosensitizer.

Type-I photosensitizers have shown advantages in addressing the shortcomings of traditional oxygen-dependent type-II photosensitizers for the photodynamic therapy (PDT) of hypoxic tumors. However, developing type-I photosensitizers is yet a huge challenge because the type-II energy transfer process is much faster than the type-I electron transfer process. Herein, from the fundamental point of view, an effective approach is proposed to improve the electron transfer efficiency of the photosensitizer by lowering the internal reorganization energy and exciton binding energy via self-assembly-induced exciton delocalization. An example proof is presented by the design of a perylene diimide (PDI)-based photosensitizer (PDIMp) that can generate singlet oxygen (1O2) via a type-II energy transfer process in the monomeric state, but induce the generation of superoxide anion (O2˙-) via a type-I electron transfer process in the aggregated state. Significantly, with the addition ofcucurbit[6]uril (CB[6]), the self-assembled PDIMp can convert back to the monomeric state via host-guest complexation and consequently recover the generation of 1O2. The biological evaluations reveal that supramolecular nanoparticles (PDIMp-NPs) derived from PDIMp show superior phototherapeutic performance via synergistic type-I PDT and mild photothermal therapy (PTT) against cancer under either normoxia or hypoxia conditions.

Organic phosphorescent scintillation from copolymers by X-ray irradiation.

Scintillators that exhibit X-ray-excited luminescence have great potential in radiation detection, X-ray imaging, radiotherapy, and non-destructive testing. However, most reported scintillators are limited to inorganic or organic crystal materials, which have some obstacles in repeatability and processability. Here we present a facile strategy to achieve the X-ray-excited organic phosphorescent scintillation from amorphous copolymers through the copolymerization of the bromine-substituted chromophores and acrylic acid. These polymeric scintillators exhibit efficient X-ray responsibility and decent phosphorescent quantum yield up to 51.4% under ambient conditions. The universality of the design principle was further confirmed by a series of copolymers with multi-color radioluminescence ranging from green to orange-red. Moreover, we demonstrated their potential application in X-ray radiography. This finding not only outlines a feasible principle to develop X-ray responsive phosphorescent polymers, but also expands the potential applications of polymer materials with phosphorescence features.

Controllable room temperature phosphorescence, mechanoluminescence and polymorphism of a carbazole derivative.

Room temperature phosphorescence (RTP) and mechanoluminescence (ML) materials are in high demand because of their promising applications in optoelectronic devices. However, most materials bear only one of these properties and molecules bearing both of them are rarely reported. Here, we report a carbazole derivative 1, which displays both RTP activity and near-ultraviolet ML properties. These properties are highly related to the packing modes and molecular configuration as revealed by the analysis of their crystal structures and theoretical calculations. The near-ultraviolet ML of 1 can further serve as the exciting light source to transfer its energy to luminescent dyes to realize colorful ML. The thermal-responsive RTP of 1 can be utilized to prepare anti-counterfeiting tags for simple security protection. This work has put forward a simple but efficient strategy to prepare multifunctional molecular systems bearing both RTP and ML properties.

Theoretical Insight Into the Ultralong Room-Temperature Phosphorescence of Nonplanar Aromatic Hydrocarbon.

Purely aromatic hydrocarbon materials with ultralong room-temperature phosphorescence (RTP) were reported recently, but which is universally recognized as unobservable. To reveal the inherent luminescent mechanism, two compounds, i.e., PT with a faint RTP and HD with strong RTP featured by nonplanar geometry, were chosen as a prototype to study their excited-state electronic structures by using quantum mechanics/molecular mechanics (QM/MM) model. It is demonstrated that the nonplanar ethylene brides can offer σ-electron to strengthen spin-orbit coupling (SOC) between singlet and triplet excited states, which can not only promote intersystem crossing (ISC) of S1→Tn to increase the population of triplet excitons, but also accelerate the radiative decay rate of T1→S0, and thus improving RTP. Impressively, the nonradiative decay rate only has a small increase, owing to the synergistic effect between the increase of SOC and the reduction of reorganization energy of T1→S0 caused by the restricted torsional motions of aromatic rings. Therefore, a bright and long-lived RTP was obtained in aromatic hydrocarbon materials with twisted structure. This work provided a new insight into the ultralong RTP in pure organic materials.

Influence of Isomerism on Radioluminescence of Purely Organic Phosphorescence Scintillators.

There are few reports about purely organic phosphorescence scintillators, and the relationship between molecular structures and radioluminescence in organic scintillators is still unclear. Here, we presented isomerism strategy to study the effect of molecular structures on radioluminescence. The isomers can achieve phosphorescence efficiency of up to 22.8 % by ultraviolet irradiation. Under X-ray irradiation, both m-BA and p-BA show excellent radioluminescence, while o-BA has almost no radioluminescence. Through experimental and theoretical investigation, we found that radioluminescence was not only affected by non-radiation in emissive process, but also highly depended on the material conductivity caused by the different molecular packing. This study not only allows us to clearly understand the relationship between the molecular structures and radioluminescence, but also provides a guidance to rationally design new organic scintillators.

Diffraction based single pulse measurement of air ionization dynamics induced by femtosecond laser.

A single pulse diffraction method to probe the plasma column evolution of the air ionization induced by the femtosecond laser pulse has been proposed. By utilizing a linearly chirped pulse as the probe light, the spatiotemporal evolution spectrum of the plasma column can be acquired in a single measurement. A method based on the Fresnel diffraction integral is proposed to extract the evolution of the phase shift after the probe light is crossing through the plasma column. Results show that the plasma expands rapidly within 7 ps due to the ionization, and then reaches a steady state with a diameter of about 80 µm with the pump pulse energy of 1 mJ. Furtherly, the temporal profile of the free electron density and the refractive index in the plasma region were determined using the corresponding physical models. The single-shot method can be expected to broaden the way for detecting the dynamics of the femtosecond laser-induced plasma.

Synergistic effect of photocatalysis and adsorption of nano-TiO2 self-assembled onto sulfanyl/activated carbon composite.

We report a significant synergistic effect of photocatalysis and adsorption by depositing 3-6 nm TiO2 particles onto sulfanyl (HS)/activated carbon composite using molecular self-assemble method in low-temperature aqueous system. The synergistic effect was studied by comparing pure TiO2 and TiO2/sulfanyl/activated carbon composite to photocatalytic degrade methylene blue (MB) in a quartz glass reactor. The results showed that the photocatalytic activity of the TiO2/HS/AC composite compared to pure TiO2 has been greatly enhanced calculated from a simulated first-order kinetics model. The synergistic enhancement at low MB concentration was significantly stronger than that at high concentration, and the synergistic effect calculated from the model at initial concentration of 1 mg/L was approximately 64 times than at initial concentration of 15 mg/L. This is because when the adsorption rate was much faster than the photocatalytic degradation rate, strong adsorption of MB molecules may inhibit subsequent photocatalytic degradation reaction. The enhancement was found mainly due to the strong synergistic effect of the adsorption of MB of sulfanyl/activated carbon substrate and the photocatalysis of TiO2 nanoparticles.

Treatment of sulfate-rich and low pH wastewater by sulfate reducing bacteria with iron shavings in a laboratory.

Sulfate-rich wastewater is an indirect threat to the environment especially at low pH. Sulfate reducing bacteria (SRB) could use sulfate as the terminal electron acceptor for the degradation of organic compounds and hydrogen transferring SO(4)(2-) to H2S. However their acute sensitivity to acidity leads to a greatest limitation of SRB applied in such wastewater treatment. With the addition of iron shavings SRB could adapt to such an acidic environment, and 57.97, 55.05 and 14.35% of SO(4)(2-) was reduced at pH 5, pH 4 and pH 3, respectively. Nevertheless it would be inhibited in too acidic an environment. The behavior of SRB after inoculation in acidic synthetic wastewater with and without iron shavings is presented, and some glutinous substances were generated in the experiments at pH 4 with SRB culture and iron shavings.

[Reductive degradation of chlorophenols in aqueous solution by gamma irradiation].

Because chlorine is an electron withdrawing group, the highly chlorinated phenols may react quickly with hydrated electrons rather than with hydroxyl radicals. The process of reactions of four chlorophenols (4-CP, 2-CP, 2,4-DCP, 2,4,6-TCP) with e(aq)(-) was investigated in aqueous solutions by detecting the concentration of CPs, Cl- and intermediates. In the e(aq)(-) reductive system, the experimental results showed that the order of four kinds of chlorophenol degradation and dechlorination was 2,4,6-TCP > 2,4-DCP > 2-CP > 4-CP. The greater the chlorine content was the higher reactivity of hydrated electrons towards chlorophenols was. Furthermore, hydrated electrons may preferentially attack the ortho-position of chlorine atom rather than the para-position of chlorine atom. Phenol and Cl- were detected as the final product of the reductive reaction. Additionally, processes of degradation and dechlorination of CPs were observed as the pseudo-first-order kinetics. The reaction constant of degradation of 4-CP, 2-CP, 2,4-DCP and 2,4,6-TCP were 0.154, 0.253, 0.750 and 1.188 kGy(-1), respectively. Meanwhile, the dechlorination of 4-CP, 2-CP, 2,4-DCP and 2,4,6-TCP were 0.137, 0.219, 0.251 and 0.306 kGy(-1), respectively.

Anaerobic biodegradation of ethylthionocarbamate by the mixed bacteria under various electron acceptor conditions.

Biodegradation behavior and kinetics of ethylthionocarbamate under nitrate, sulfate and ferric reducing conditions by mixed cultures enriched from the anaerobic digester sludge was investigated. The results showed that ethylthionocarbamate could be degraded independently by the mixed cultures coupled to nitrate, sulfate, and ferric reduction, and meanwhile, nitrite, sulfide, and ferrous were accumulated as a result of nitrate, sulfate and ferric reduction, respectively. Ferric was a more favorable terminal electron acceptor compared to nitrate and sulfate. The order of the electron acceptors with decreasing biodegradation rates of the ethylthionocarbamate was: ferric>nitrate>sulfate, and the corresponding maximum biodegradation rate was 7.240, 6.267, and 4.602 mg/(L·d), respectively. The anaerobic biodegradation of ethylthionocarbamate under various electron acceptor conditions can be accurately described by first order exponential decay kinetics.

Removal of Neutral Red from aqueous solution by adsorption on spent cottonseed hull substrate.

Cottonseed hull, a low-cost widely available agricultural waste in China, after used as substrate for the white rot fungus Pleurotus ostreatus cultivation, was tested for the removal of Neutral Red (NR), a cationic dye, from aqueous solution. A batch adsorption study was carried out with varied solution pH, adsorbent dosage, reaction time and initial NR concentration. The results show that the kinetics of dye removal by the spent cottonseed hull substrate (SCHS) is prompt in the first 5 min and the adsorption equilibrium can be attained after 240 min. The biosorption kinetics and equilibrium follow typical pseudo-second-order and Langmuir adsorption models. Thermodynamic parameters of ΔG°, ΔH° and ΔS° show that the adsorption is a spontaneous and endothermic process. Fourier transform infrared (FTIR) spectroscopy was used for the characterization of possible dye-biosorbent interaction. This study provides a facile method to produce low-cost biosorbent for the purification of dye contaminated water.

Preparation of nanosized Bi3NbO7 and its visible-light photocatalytic property.

A nanosized Bi(3)NbO(7) was synthesized by the sol-gel method. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), UV-vis diffuse reflectance spectrum, X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmet-Teller (BET). The UV-vis diffuse reflectance spectrum of the sample obtained by the sol-gel method showed a markedly blue-shift as compared to that of the sample obtained by the solid-state reaction. The band gap of the Bi(3)NbO(7) nanoparticles was estimated to be about 2.43-2.59eV. XPS analysis confirmed that the mixed valence bismuth existed in the crystal structure of the photocatalyst and niobium in the compound Bi(3)NbO(7) was in the Nb(5+) valence state. The as-prepared nanopowders exhibited a high photocatalytic activity in the decomposition of acid red G in water and acetone in air under visible-light irradiation, which may be assigned to larger specific surface area and the oxygen vacancies and mixed valence bismuth in the structure of Bi(3)NbO(7).

[FTIR study of adsorption of PCP on hematite surface].

The adsorption of pentachlorophenol on hematite was studied through adsorption experiments and FTIR analysis. The pH adsorption isotherms of pentachlorophenol onto hematite were obtained by the static state experiments. The largest adsorption quantity occurred at about pH 6. The adsorption quantity at pH 8.5 of the isoelectric point of hematite was about 31% of the largest adsorption quantity. Fourier transform infrared (FTIR) spectroscopy was used to analyse the change of hematite before and after PCP adsorption, and the species of PCP on hematite. It was discovered that: (1) the typical peak at 565 cm(-1) of the Fe-O bond in alpha-Fe2O3 did not change before and after adsorption, and the adsorption occurred on the surface of hematite. (2) At pH 6.0, the stretching vibration peak at 3 438 cm(-1) due to the hydrogen bond formed between O-H on the surface of alpha-Fe2O3 and water molecules shifted to 3 417 cm(-1). The bending vibration peak of H-O-H+ on the surface at 1 643 cm(-1) was weakened because of complex reaction. The peak owing to Fe-OH bond was displaced from 1 050-1 100 cm(-1) to 950 cm(-1) with increased intensity. The C-O bond stretching vibration peak of PCP was displaced from 1 215 to 1 122 cm(-1). The main interaction between PCP and hematite was static electric interaction. (3) At pH 8.5, the stretching vibration peak of the hydrogen bond formed between O-H on the surface of alpha-Fe2O3 and water molecules was displaced from 3 438 to 3 428 cm(-1). The bending vibration peak at 1 643 cm(-1) was obviously weakened because of the hydrogen bonding. The H-O-H+ bending vibration peak at 1 050-1 100 cm(-1) was displaced to 947 cm(-1) with obviously increased intensity, indicating that the interaction was mainly through hydrogen bond.

[FTIR study of nano-iron oxyhydroxides' decoloration on the azo dye].

IR spectra were used to analyse the azo dye solution decoloration action by two kinds of iron oxyhydroxides. It was discovered that: (1) Acid Red G and methyl orange are apt to form complex on the surface of iron oxyhydroxides > FeOH, especially Acid Red G. which possesses two -SO3Na structures has a relatively high decoloration efficiency as a result of complexation reaction; (2) after 2 hours adsorption, the IR spectra of iron oxyhydroxides show characteristic wave numbers at 1 033 and 1 030 cm(-1) which belong to -SO3Na, whereas the peaks at wave numbers between 1 450 and 1 400 cm(-1), which belong to azo dye, disappear. These phenomena indicate that azo dye molecules are adsorbed on the surface of iron oxyhydroxides due to the negative -SO3Na structure, and at the moment azo dye molecules are adsorbed on the surface of iron oxyhydroxides, the electron transfer occurs between the azo dye molecules and the iron oxyhydroxides surface's Fe3+ centre, which could lead to the rupture of azo bond. It can be infered that the decoloration of azo dye molecules is the co-effect of the selective chemical absorption and the oxidation-deoxidation effect on the surface of iron oxyhydroxides.