Ground State Oxygen Research Articles

An Acceptor-Donor-Acceptor Structured Nano-Aggregate for NIR-Triggered Interventional Photoimmunotherapy of Cervical Cancer.

Compared with conventional therapies, photoimmunotherapy offers precise targeted cancer treatment with minimal damage to healthy tissues and reduced side effects, but its efficacy may be limited by shallow light penetration and the potential for tumor resistance. Here, an acceptor-donor-acceptor (A-D-A)-structured nanoaggregate is developed with dual phototherapy, including photodynamic therapy (PDT) and photothermal therapy (PTT), triggered by single near-infrared (NIR) light. Benefiting from strong intramolecular charge transfer (ICT), the A-D-A-structured nanoaggregates exhibit broad absorption extending to the NIR region and effectively suppressed fluorescence, which enables deep penetration and efficient photothermal conversion (η=67.94%). A suitable HOMO-LUMO distribution facilitates sufficient intersystem crossing (ISC) to convert ground-state oxygen (3O2) to singlet oxygen (1O2) and superoxide anions (·O2 -), and catalyze hydroxyl radical (·OH) generation. The enhanced ICT and ISC effects endow the A-D-A structured nanoaggregates with efficient PTT and PDT for cervical cancer, inducing efficient immunogenic cell death. In combination with clinical aluminum adjuvant gel, a novel photoimmunotherapy strategy for cervical cancer is developed and demonstrated to significantly inhibit primary and metastatic tumors in orthotopic and intraperitoneal metastasis cervical cancer animal models. The noninvasive therapy strategy offers new insights for clinical early-stage and advanced cervical cancer treatment.

Molecular Insights into the Quenching Mechanism of the Triplet Excited State of Rose Bengal through Oxidative and Reductive Organic Compounds.

In oxygenated aquatic environments, the predominant scavenging of the triplet excited state of chromophoric dissolved organic matter (3CDOM*) involves dissolved ground-state oxygen, diverting attention away from the scavenging mechanisms of 3CDOM* mediated through specific organic compounds. Previous studies demonstrated that model 3CDOM* exhibited quantum yields (i.e., 1-56%) in the formation of radical ions, resulting from the competition between physical and chemical quenching through a common exciplex intermediate. Physical quenching was rationalized through the reverse intersystem crossing of the exciplex, followed by back electron transfer, yielding ground-state reactants. Despite this, direct experimental evidence for exciplex involvement has been elusive, owing to detection challenges. Herein, employing density functional theory (DFT) and time-dependent DFT specifically for excited state surrogate CDOM and organic scavengers, we unveil, for the first time, the underlying mechanisms responsible for the quenching of Rose Bengal through oxidative and reductive scavengers. Our computational findings provide evidence for the involvement of exciplexes during the quenching process of the excited triplet state of Rose Bengal, highlighting the impact of electronic coupling between Rose Bengal and quenchers on the quantum yield for radical ion formation.

Influence of Singlet Oxygen in H + O2 Collision Reaction.

The collision reaction of H + O2 = OH + O is a pivotal step in combustion. To investigate the influence of singlet oxygen on this reaction, we computed potential energy surfaces (PESs) for all six lowest states using high-level ab initio methods and coupled them with embedded atom neural network (EANN) fitting. By integrating quasi-classical trajectory (QCT) with trajectory surface hopping (TSH) based on the fitted PESs, we simulated the dynamics of both ground- and excited-states to derive the reaction rate constants for the forward and reverse processes. The results reveal that the forward reaction facilitates radical generation, promoting combustion reactions. Furthermore, calculations of reverse reaction rate constants indicate that all electronic states ultimately yield ground-state oxygen, leading to radical deactivation and exerting an inhibitory effect on combustion processes.

Structure-Activity Relationship of Benzophenazine Derivatives for Homogeneous and Heterogenized Photooxygenation Catalysis.

Singlet oxygen is a powerful oxidant used in various applications, such as organic synthesis, medicine, and environmental remediation. Organic and inorganic photosensitizers are commonly used to generate this reactive species through energy transfer with the triplet ground state of oxygen. We describe here a series of novel benzophenazine derivatives as a promising class of photosensitizers for singlet oxygen photosensitization. In this study, we investigated the structure-activity relationship of these benzophenazine derivatives. Akin to a molecular compass, the southern fragment was first functionalized with either aromatic tertiary amines, alkyl tertiary amines, aromatic sulfur groups, alkyl sulfur groups, or cyclic ethers. Enhanced photophysical properties (in terms of triplet excited-state lifetime, absorption wavelength, triplet state energy, and O2 quenching capabilities) were obtained with cyclic ether and sulfur groups. Conversely, the presence of an amine moiety was detrimental to the photocatalysts. The western and northern fragments were also investigated and slightly undesirable to negligible changes in photophysical properties were observed. The most promising candidate was then immobilized on silica nanoparticles and its photoactivity was evaluated in the citronellol photooxidation reaction. A high NMR yield of 97 % in desired product was obtained, with only a slight decrease over several recycling runs (85 % in the fourth run). These results provide insights into the design of efficient photosensitizers for singlet oxygen generation and the development of heterogeneous systems.

Solar photocatalytic CeO2/g-C3N4 removal of micropollutants in the water environment through the generation of singlet oxygen

The synthesis of photocatalysts with good photocatalytic performance to selectively oxidize micropollutants in complex water environments has received widespread attention. This study successfully synthesized a CeO2/g-C3N4 composite, which could degrade sulfamethoxazole (SMX) up to 95 % under simulated sunlight (SSL) in 60 min. Additionally, it exhibited favorable selective oxidation characteristics in complex water environments. EPR and radical scavenging experiments proved the main oxidation contributions of singlet oxygen (1O2) in the system. Photoluminescence spectroscopy demonstrated that the composite material could generate more triplet excitons to generate 1O2 with ground-state oxygen (3O2) through an energy transfer pathway. The product analysis of the two models of micropollutants, SMX and carbamazepine, indicated an overall rise in the biodegradability of the majority of intermediates, accompanied by a decrease in acute toxicity. The composite showed high stability even after 5 cycles. Various micropollutants have degradation of varying degrees in different natural water matrices. In summary, this study introduced a novel photocatalytic oxidation strategy with selective oxidation capability, providing possibilities for practical applications and environmentally friendly photocatalytic processes.

Spatially resolved TALIF investigation of atomic oxygen in the effluent of a CO2 microwave discharge

A diagnostic setup for one-dimensionally spatially resolved two-photon absorption laser-induced fluorescence (TALIF) detection of ground state oxygen atoms ( 2p43P2,1,0 ) is developed. The goal of this study is to investigate the evolution of temperatures and absolute number densities of oxygen atoms along the effluent of a low-pressure CO2 microwave discharge in order to gain insights into some of the mechanisms governing the post-discharge regime. The plasma source is operated at conditions of 600 W– 1200 W of absorbed power with flow rates of 74 sccm and 370 sccm pure CO2 at pressures between 1.2 mbar and 5 mbar with specific energy inputs up to 111.9 eV/molecule. These operating conditions exhibit high CO2 conversions (up to 90%) at low energy efficiencies (2%–7.4%), due to direct electron impact dissociation driving the conversion process resulting in splitting of CO2 into CO and metastable oxygen atoms. The TALIF measurements yield spatially resolved translational temperatures between 1000 K– 1600 K for most operating conditions and axial positions along the effluent. Reference measurements with xenon 6p′[3/2]2 are used for absolute number density calibration. The resulting axially resolved number density profiles of ground state atomic oxygen increase along the effluent, even at considerable distances of several centimeters from the active discharge, before they reach a maximum between 5×1020 m−3 and 2.2×1021 m−3 depending on the condition, and decrease after that. This behavior indicates the potential significance of quenching of metastable oxygen atoms within the post-discharge regime of the investigated CO2 discharges. The measured spatially resolved number density evolutions are qualitatively consistent with quenching via wall collisions being the dominant deactivation mechanism, underlining the importance of particle-wall interactions.

Redirecting the electron flow to coordinate oxidation and reduction reactions for efficient photocatalytic H2O2 production

Energy-efficient photocatalytic production of H2O2 from water holds the potential to replace the anthraquinone process. However, the impracticality of oxygen bubbling in such processes necessitates addressing the H2O2 production in oxygen-deficient environments. Here, we demonstrated the generation of singlet oxygen (1O2) as a highly active water oxidation derivative that redirects the electron flow for H2O2 production in oxygen-deficient environments. Ground-state oxygen was in-situ generated on photocatalysts and undergoes transition to 1O2, surpassing other competitive electron-consuming reactions. Self-generated 1O2 undergoes preferential photo-reduction to H2O2, benefiting from a small activation energy (0.2 eV), facilitated electron trapping rate, adjacent oxidation/reduction sites and suppressed competitive energy transfer from excited-states to air 3O2. A remarkable solar-to-chemical conversion (SCC) efficiency of 0.25 % was obtained for H2O2 generation in oxygen-deficient conditions. This work unveils a novel concept of redirecting electron flow towards H2O2 production, taking advantage of highly active in-situ generated 1O2.

Singlet Oxygen Detection by Chemiluminescence Probes in Living Cells.

Singlet oxygen is a reactive oxygen species that causes oxidative damage to plant cells, but intriguingly it can also act as a signalling molecule to reprogram gene expression required to induce plant physiological/cellular responses. Singlet oxygen photosensitization in plants mainly occurs in chloroplasts after the molecular collision of ground-state molecular oxygen with triplet-excited-state chlorophyll. Singlet oxygen direct detection through phosphorescence emission in chloroplasts is a herculean task due to its extremely low luminescence quantum yield. Because of this, indirect alternative methods have been developed for its detection in biological systems, for example, by measuring the changes in the EPR signal or fluorescence intensity of singlet oxygen reaction-based probes. The singlet oxygen chemiluminescence (SOCL) is a chemiluminescence probe with high sensitivity and selectivity towards singlet oxygen and promising use to detect it in living cells without the inconvenience of low stability of the EPR signal of spin probes in the presence of redox compounds, spurious light scattering coming from the light source required for the excitation of fluorescence probes or the light emission of endogenous fluorescent molecules like chlorophyll in chloroplasts. The protocol presented in this chapter describes the first steps to characterizing singlet oxygen production within the biological system under study; this is accomplished through monitoring molecular oxygen consumption by SOCL using a Clark-type oxygen electrode and measuring the chemiluminescence generated by SOCL 1,2-dioxetane using a spectrofluorometer. For singlet oxygen detection within living cells, a version of SOCL with increased membrane permeability (SOCL-CPP) is described.

Chemical scanning of atomic oxygen at the gas-liquid interface of a NaCl solution via quantum mechanics/molecular mechanics molecular dynamics simulations

Atmospheric pressure plasmas can serve as double phase reactors to produce plasma activated water for water treatment. However, the physical-chemical processes involving plasma-supplied atomic oxygen and reactive oxygen species in an aqueous solution remain unclear. In this work, quantum mechanics (QM)/molecular mechanics (MM) molecular dynamics simulations (MDs) have been performed to directly observe the chemical reactions occurring between atomic oxygen and a NaCl solution at the gas-liquid interface using a model containing 10,800 atoms. During simulations, the atoms in the QM and MM Parts are dynamically adjusted. To examine the effects of local microenvironments on the chemical processes, atomic oxygen is used as a chemical probe to scan the gas-liquid interface. The excited atomic oxygen reacts with water molecules and Cl− ions to produce H2O2, OH, HOCl, ClO−, and HO2−/H3O+ species. The ground-state atomic oxygen is significantly more stable than the excited atomic oxygen, although it can react with water molecules to produce OH radicals. However, the branch ratio of ClO− computed for triplet atomic oxygen is significantly larger than that determined for singlet atomic oxygen. This study can help achieve a better understanding of the fundamental chemical processes during plasma-treated solution experiments and promotes advances in applications of QM/MM calculations at the gas-liquid interface.

Efficient inactivation of amoeba spores and their intraspore bacteria by solar/chlorine: Kinetics and mechanisms

Amoebae are widespread in water and serve as environment vectors for pathogens, which may threaten public health. This study evaluated the inactivation of amoeba spores and their intraspore bacteria by solar/chlorine. Dictyostelium discoideum and Burkholderia agricolaris B1qs70 were selected as model amoebae and intraspore bacteria, respectively. Compared to solar irradiation and chlorine, solar/chlorine enhanced the inactivation of amoeba spores and intraspore bacteria, with 5.1 and 5.2-log reduction at 20 min, respectively. The enhancement was similar in real drinking water by solar/chlorine under natural sunlight. However, the spore inactivation decreased to 2.97-log by 20 min solar/chlorine under oxygen-free condition, indicating that ozone played a crucial role in the spore inactivation, as also confirmed by the scavenging test using tert‑butanol to scavenge the ground-state atomic oxygen (O(3P)) as a ozone precursor. Moreover, solar/chlorine induced the shape destruction and structural collapse of amoeba spores by scanning electron microscopy. As for intraspore bacteria, their inactivation was likely ascribed to endogenous reactive oxygen species. As pH increased from 5.0 to 9.0, the inactivation of amoeba spores decreased, whereas that of intraspore bacteria was similar at pH 5.0 and 6.5 during solar/chlorine treatment. This study first reports the efficient inactivation of amoeba spores and their intraspore pathogenic bacteria by solar/chlorine in drinking water.

Unveiling Strong Ion-Electron-Lattice Coupling and Electronic Antidoping in Hydrogenated Perovskite Nickelate.

Despite being highly promising for applications in emergent electronic devices, decoding both the ion-electron-lattice coupling in correlated materials at the atomic scale and the electronic band structure remains a big challenge due to the strong and complex correlation among these degrees of freedom. Here, taking an epitaxial thin film of perovskite nickelate NdNiO3 as a model system, hydrogen-ion-induced giant lattice distortion and enhanced NiO6 octahedra tilting/rotation are demonstrated, which leads to a new robust hydrogenated HNdNiO3 phase with lattice expansion larger than 10% on a series of substrates. Moreover, under the effect of ion-electron synergistic doping, it is found that the proposed electronic antidoping, i.e., the doped electrons mainly fill the ground-state oxygen 2p holes instead of changing the Ni oxidation state from Ni3+ to Ni2+ , dominates the metal-insulator transition. Meanwhile, lattice modification with enhanced Ni-O-Ni bond tilting or rotation mainly modifies the orbital density of states near the Fermi level. Last, by electric-field-controlled hydrogen-ion intercalation and its strong coupling to the lattice and electron charge, selective micrometer-scale patterns with distinct structural and electronic states are fabricated. The results provide direct evidence for a strong ion-electron-lattice coupling in correlated physics and exhibit its potential applications in designing novel materials and devices.

Reticular polarization engineering of covalent organic frameworks for accelerated generation of superoxide anion radicals

The exploration of type I mechanism remains a great challenge in photodynamic therapy (PDT) due to the limited electron transfer from the photosensitizer to ground state oxygen to form superoxide anion radical (O2−). In this study, we design three kinds of nanoscale covalent organic frameworks (COFs) with tunable local polarization for accelerating the generation of O2−. Among three COFs, the tetrakis-(4-formylphenyl)benzene-based COF (TB-COF) exhibits highly aggravated local polarization with 3.29 Debye of the dipole moment, and thus drives the photoinduced e− reduction of O2/O2−, which matches with the energy level of TB-COF. The elongated charge-separated state of TB-COF is also identified by femtosecond transient absorption spectra and time-dependent density functional theory calculation. Significantly, the inhibited electron-hole recombination of COFs further improves the O2− production efficiency upon protonation and thus strengthens anti-cancer effect in the acidic microenvironment of tumor cell or in vivo. The reticular polarization engineering of COFs provides a new type I PDT paradigm in biomedical applications.

Measurement and simulation of temperature-dependent spontaneous Raman scattering of O2 including P and R branches

Evaluation methods for species and temperature determination in gaseous mixtures using spontaneous Raman scattering require detailed information on the spectra of the involved species. For most diatomic and some triatomic molecules that are relevant in combustion processes (H2, N2, O2, CO, CO2, H2O) these spectra can be simulated based on the underlying quantum mechanical processes. In contrast to the other diatomic molecules, the electronic ground state of oxygen has an electronic spin of S=1 which leads to the tripling of transitions and the occurrence of P and R branches. Though being neglected so far due to their small effect size, these additional transitions change the spectral shape and the integrated signal intensity which can lead to inaccuracies in evaluation methods such as the hybrid matrix inversion or full spectral fit. In this paper, P and R branches were simulated and their effect on the ro-vibrational oxygen spectrum evaluated by comparison to high-resolution experimental spectra in temperatures up to over 2000 K. Spectral fitting of O2 using this simulation allows for temperature determination of gaseous mixtures with a uncertainty better than 10 K and no significant difference to temperatures determined with the more established fitting of N2. Fitted temperatures deviate by 4 K or less when P and R transitions are considered but fitting quality improves significantly when including them in the simulation. More importantly, neglecting P and R transitions leads to an overestimation of the temperature-dependent Raman cross section of O2 which causes underestimations of O2 concentration measurements using the hybrid matrix inversion or full spectral fit method.

Cavity ringdown studies of the E–H transition in an inductively coupled oxygen plasma: comparison of spectroscopic measurements and modelling

The absolute number density of ground state oxygen atoms, O(3P), present in a 100 mTorr oxygen plasma has been determined as a function of operating power using cavity ringdown spectroscopy (CRDS). The dissociation fraction increases by an order of magnitude from ∼0.8% at 50 W to 8% at 250 W and reflects a similar increase in the electron density over this power range. Emission spectra show that the E–H switchover is accompanied by increased rotational heating of O2 and this behaviour is also observed in the translational temperatures determined by fitting the Doppler limited O(3P) CRDS data. The measurements are contextualised via a volume averaged kinetic model that uses the measured absolute densities of O(3P) and O2(a 1Δg, v = 0) as a function of power as its benchmarks. Despite the inherent spatial inhomogeneity of the plasma, the volume averaged model, which uses a minimal set of reactions, is able to both reproduce previous measurements on the absolute density of O− and to infer physically reasonable values for both the electron temperature and number density as the E–H switch over is traversed. Time-resolved emission measurements return a value of 0.2 for the wall loss coefficient for O2(b 1Σg +); as a consequence, the number density of O2(b 1Σg +) is (at least) one order of magnitude less than O2(a 1Δg).

Interaction between noble metals (Pt, Pd, Rh, Ir, Ag) and defect-enriched TiO2 and its application in toluene and propene catalytic oxidation

The particle size, electronic state, as well as metal-support interaction of supported noble metal catalysts significantly influence their VOC oxidation performance. A series of noble metals (including Pt, Pd, Rh, Ir, and Ag) was successfully loaded on TiO2 modified by hydrogen reduction to scrutinize their effects on toluene and propene combustion. The prepared catalysts were characterized by SEM, TEM, BET, XRD, ESR, UV–vis, H2-TPR, XPS, in-situ DRIFTS, GC–MS and DFT calculations. It was interesting to note that all the noble metals could be well-dispersed on the low-surface-area TiO2 support and modulated its properties. The electron transfer ability and oxygen mobility of the as-prepared materials were enhanced via noble metal doping. Among them, the Pd/TiO2 and Pt/TiO2 catalysts exhibited excellent catalytic performance by inducing local electron transfer from TiO2 to the noble metal NPs via the strong metal-support interaction. Experimental results and theoretical calculations revealed that the activation of toluene, propene and oxygen on suitable interfaces contributed to the good performance of the Pd and Pt catalysts. This work explored and elucidated the effects of electron-rich noble metal catalysts in enhancing the activation of ground-state oxygen.

β-Cyclocitral Does Not Contribute to Singlet Oxygen-Signalling in Algae, but May Down-Regulate Chlorophyll Synthesis.

Light stress signalling in algae and plants is partially orchestrated by singlet oxygen (1O2), a reactive oxygen species (ROS) that causes significant damage within the chloroplast, such as lipid peroxidation. In the vicinity of the photosystem II reaction centre, a major source of 1O2, are two β-carotene molecules that quench 1O2 to ground-state oxygen. 1O2 can oxidise β-carotene to release β-cyclocitral, which has emerged as a 1O2-mediated stress signal in the plant Arabidopsis thaliana. We investigated if β-cyclocitral can have similar retrograde signalling properties in the unicellular alga Chlamydomonas reinhardtii. Using RNA-Seq, we show that genes up-regulated in response to exogenous β-cyclocitral included CAROTENOID CLEAVAGE DIOXYGENASE 8 (CCD8), while down-regulated genes included those associated with porphyrin and chlorophyll anabolism, such as tetrapyrrole-binding protein (GUN4), magnesium chelatases (CHLI1, CHLI2, CHLD, CHLH1), light-dependent protochlorophyllide reductase (POR1), copper target 1 protein (CTH1), and coproporphyrinogen III oxidase (CPX1). Down-regulation of this pathway has also been shown in β-cyclocitral-treated A. thaliana, indicating conservation of this signalling mechanism in plants. However, in contrast to A. thaliana, a very limited overlap in differential gene expression was found in β-cyclocitral-treated and 1O2-treated C. reinhardtii. Furthermore, exogenous treatment with β-cyclocitral did not induce tolerance to 1O2. We conclude that while β-cyclocitral may down-regulate chlorophyll synthesis, it does not seem to contribute to 1O2-mediated high light stress signalling in algae.

The role of highly vibrationally excited H2 initiating the nitrogen chemistry

The formation of hydrides by gas-phase reactions between H2 and a heavy element atom is a very selective process. Reactions with ground-state neutral carbon, oxygen, nitrogen, and sulfur atoms are very endoergic and have high energy barriers because the H2 molecule has to be fragmented before a hydride bond is formed. In cold interstellar clouds, these barriers exclude the formation of CH, OH, NH, and SH radicals through hydrogen abstraction reactions. Here we study a very energetically unfavorable process, the reaction of N(4S) atoms with H2 molecules. We calculated the reaction rate coefficient for H2 in different vibrational levels, using quantum methods for v = 0−7 and quasi-classical methods up to v =12; for comparison purposes, we also calculated the rate coefficients of the analogous reaction S (3P)+ H2(v) → SH + H. Owing to the high energy barrier, these rate coefficients increase with v and also with the gas temperature. We implemented the new rates in the Meudon photodissociation region (PDR) code and studied their effect on models with different ultraviolet (UV) illumination conditions. In strongly UV-irradiated dense gas (Orion Bar conditions), the presence of H2 in highly vibrationally excited levels (v ≥ 7) enhances the NH abundance by two orders of magnitude (at the PDR surface) compared to models that use the thermal rate coefficient for reaction N(4S) + H2 → NH + H. The increase in NH column density, N(NH), across the PDR is a factor of ~25. We investigate the excitation and detectability of submillimeter NH rotational emission lines. Being a hydride, NH excitation is very subthermal (Trot ≪ Tk) even in warm and dense gas. We explore existing Herschel/HIFI observations of the Orion Bar and Horsehead PDRs. We report a 3σ emission feature at the ~974 GHz frequency of the NH NJ = 12 − 01 line toward the Bar. The emission level implies N(NH) ≃ 1013 cm−2, which is consistent with PDR models using the new rate coefficients for reactions between N and UV-pumped H2. This formation route dominates over hydrogenation reactions involving the less abundant N+ ion. JWST observations will quantify the amount and reactivity of UV-pumped H2 in many interstellar and circumstellar environments.

Rate constant and products of the reaction of O(3P) atoms with thiirane over the temperature range 220–950 K

AbstractA discharge‐flow modulated molecular beam mass spectrometry technique has been used to determine the rate constant for the reaction of ground state oxygen atoms with C2H4S in the temperature range 220–950 K. The reaction rate constant has been determined directly by monitoring C2H4S in an excess of O atoms and through competitive reaction of oxygen atoms with C2H4S and Br2. Weak, negative temperature dependence is observed below 300 K, whereas positive temperature dependence is observed above 380 K: k = 1.13 × 10–12 (T/298)2.18 exp(733/T) cm3 molecule–1 s–1. We estimate this expression to be accurate within 15% over the investigated temperature range. SO and C2H4 have been detected as reaction products and a branching ratio of unity (with uncertainty of 10%) has been found for the channel forming these two species in the temperature range 300–900 K, confirming that the title reaction is an efficient source of SO radicals.

Conjugated Molecule-Assisted Supramolecular Hydrogel with Enhanced Antibacterial and Antibiofouling Properties.

The hydrogel using natural and synthetic polymers to create a cross-linking network has drawn attention in diverse bioapplications. However, inhibition of bacterial infection is still a challenge for hydrogel's wide application. In this work, we reported a supramolecular hydrogel with a good antibacterial property built from conjugated molecules. The water-soluble molecular 4,7-bis[9,9-di(2-carboxy-ethyl)-fluoren-2-yl]-2,1,3-benzothiadiazole (OFBTCOOH) physically linked with monomers via hydrophobic interaction. The free-radical polymerized poly(N-acryloyl glycinamide) was hydrogen-bond cross-linked by dual amides in the side chains to form a hydrogel. An adjustable micro-network was obtained by increasing OFBTCOOH with evidence of enhanced intermolecular interaction. The successfully integrated OFBTCOOH could be excited upon light irradiation. The energy of triplet-state excitons of OFBTCOOH transferred to the ground-state oxygen to produce singlet oxygen, which endowed the hydrogel with the antibacterial property. Meanwhile, the superhydrophilic surface of the hydrogel can bind water molecules to form a stable hydration layer, which acted as barriers to resist protein and bacterial adsorption and achieve the anti-biofouling goal. The ease in introducing conjugated polyelectrolytes may provide a formulation to functionalize hydrogels via various physical interactions.

Histopathological Analysis of the Effect of Photodynamic Action on Post-Chemotherapy Excised Breast Cancer Tissue.

Background and objectives: Breast cancer is the most commonly diagnosed cancer in women and its mortality is increasing. Therefore, research to improve treatment is of paramount importance. One method of treatment is photodynamic therapy. Photodynamic therapy selectively stimulates apoptosis in photosensitizer-treated neoplastic breast cells as a result of cytotoxic singlet oxygen generation via collisions between triplet excited state photosensitizer and triplet ground state oxygen upon tissue irradiation. The aim of this study was to evaluate the effects of photodynamic action on cancerous breast tissue samples as a model of photodynamic therapy. Materials and Methods: Breast cancer tissue samples were obtained from post-operative material and the patterns of histopathological changes in breast cancer tissue before and after photodynamic action on post-chemotherapy tissue were evaluated. Excised tissue samples were obtained from 48 female breast cancer patients who had previously undergone chemotherapy. Breast cancer tissues for this study were taken from macroscopically visible tumors larger than 10 mm. Histopathological analysis was performed to evaluate any morphological changes prior to and after photodynamic action on the post-chemotherapy tissue samples. Eighteen breast cancer tissue samples were analyzed before chemotherapy, fifteen after chemotherapy, and fifteen samples were analyzed after chemotherapy and application of photodynamic action. The photosensitizer Rose Bengal was applied to the samples subjected to photodynamic action. Results: Photodynamic action on post-chemotherapy neoplastic tissue showed histological changes under a light microscope. The results showed that morphological changes in breast cancer tissues after chemotherapy and photodynamic action were dependent on the concentration of Rose Bengal. In all cases, follow-up imaging showed tumor shrinkage of an average of 35% from baseline size. Conclusions: Histopathological examination revealed photosensitizer-concentration-dependent changes after photodynamic action in excised post-chemotherapy tissue. The effects of photodynamic action observed in this study suggest that the application of photodynamic therapy after chemotherapy can aid in breast cancer cell eradication.