Effect of external electric fields on the ESDPT process and photophysical properties of 1,8-dihydroxy-2-naphthaldehyde.

In this work, by capitalizing on the density functional theory (DFT) and the time-dependent density functional theory (TD-DFT) methods, it has been systematically studied that the excited state double intramolecular proton transfer (ESDPT) process and the photophysical properties of 1,8-dihydroxy-2-naphthaldehyde (DHNA) are affected by the distinct external electric fields (EEFs). The obtained intramolecular hydrogen bond (IHB) parameters containing bond lengths and angles, as well as infrared (IR) vibrational spectra demonstrate that IHB strength changes in the distinct EEFs. Moreover, not only do the potential energy surfaces (PESs) indicate that the ESDPT process of DHNA is stepwise, but also increasing the positive EEF results in a decrease in the energy barrier accordingly, while vice versa. The absorption and fluorescence spectra also undergo a corresponding red or blue shift in the EEF; for instance, when the EEF changes from +10 × 10-4 a.u. to +20 × 10-4 a.u., the fluorescence peak undergoes a blue shift from 602 nm to 513 nm in the keto2 form. In a nutshell, the ESDPT process of DHNA can be influenced by the EEF, which will serve as a reference in regulating and controlling proton transfer that causes luminescence.

The evaluation of lateral incisor adjacent to treated labial inversely impacted maxillary central incisor: A retrospective follow-up study.

INTRODUCTION: This retrospective study aimed to evaluate the further development of the lateral incisor and its associated periodontium adjacent to the treated labial inversely impacted maxillary central incisor. METHODS: We enrolled 23 participants (average age, 8.24 ± 1.43 years) undergoing a mean follow-up period of 31.10 ± 13.05 months. Each participant had an unimpacted lateral incisor and a successfully treated unilateral labial inversely impacted maxillary central incisor. The contralateral lateral incisors served as controls. Cone-beam computed tomography data were available for treatment completion and follow-up stages. The variables (including root length, dental age, root canal width, root-crown angulation, and alveolar bone loss and thickness) were evaluated with Dolphin Imaging software (version 11.95; Dolphin Imaging and Management Solutions, Chatsworth, Calif). RESULTS: At the follow-up stage, the lateral incisors in the impacted side had significantly longer root lengths, smaller root canal widths, and thinner labial bone widths at the apex than at the posttreatment stage (P <0.001, P = 0.036, and P = 0.001, respectively). A significant lateral incisor root length reduction was noted when comparing the impacted and contralateral sides, although no variation was observed in root canal width. Similarly, crown-root angulation of the lateral incisor on the impacted side was significantly larger than that of the contralateral lateral incisor. The lateral incisor on the impacted side also had thicker labial and thinner lingual bone widths at the apex than the contralateral lateral incisor. CONCLUSIONS: The lateral incisor adjacent to the successfully treated labial inversely impacted maxillary central incisor showed continuous growth during follow-up stages, exhibiting a similar morphology and alveolar bone quality but shorter root length, larger root angulation, and thinner lingual bone width at the apex than those of the contralateral lateral incisors.

Pd-Catalyzed Selective B(6)-H Phosphorization of nido-Carboranes via Cascade Deboronation/B-H Activation from closo-Carboranes.

Efficient Pd-catalyzed regioselective B(6)-H phosphorization of nido-carboranes via cascade deboronation/B-H activation of readily available C-substituted o-carboranes with various phosphines using 3-methylpyridine or isoquinoline as a directing group in combination with pyridine ligands has been developed, affording unprecedented B(6)-phosphinated nido-carborane derivatives with high selectivity in a simple one-pot process.

Theoretical study on an intriguing excited-state proton transfer process induced by weakened intramolecular hydrogen bonds.

In the present work, we have systematically investigated the dual hydrogen-bonded system 2Z,2'Z-3,3'-(4,4'-methylenebis(4,1-phenylene)bis(azanediyl)bis(1,3-diphenylprop-2-en-1-one)) (abbreviated as L) utilizing quantum chemistry methods, in which the excited-state intramolecular proton transfer (ESIPT) does not conform to the usual stereotype but proceeds along the weakened intramolecular hydrogen bonds (IHBs). Two primary configurations were confirmed to coexist in the ground state (i.e., anti-L and syn-L) by calculating the Boltzmann distribution in three different solvents. Based on the cardinal geometrical parameters involved in IHBs and the interaction region indicator (IRI) isosurface, it can be revealed that the dual IHBs of L were both weakened upon photoexcitation, not least the N1-H2⋯O3 IHB was utterly destroyed in the excited state. The proton-transfer process of anti and syn in three solvents with different polarities has been analyzed by constructing S0- and S1-state potential energy surfaces (PESs). It can be concluded that only the single proton transfer behavior along N1-H2⋯O3 occurs in the S1 state, and the corresponding energy barrier is gradually enlarged with increasing solvent polarity. To further expound the weakened IHB-induced ESIPT mechanism, the scanned PESs connecting the transition state (TS) structures and the initial forms indicate that the ESIPT process is infeasible without the appropriate structural torsion. Our work not only unveils the extraordinary ESIPT process of L, but also complements the results obtained from previous experiments.

The photosynthetic physiological response and purification effect of Salix babylonica to 2, 4-dinitrophenol wastewater.

Phytoremediation technology based on living green plants would clean up water pollution. Through hydroponic experiment, the effects of different concentration of 2, 4-dinitrophenol (2, 4-DNP) on the photosynthetic and chlorophyll fluorescence parameters of Salix babylonica, and the absorption and purification effect of S. babylonica on 2, 4-DNP were measured to explore the tolerance of S. babylonica to 2, 4-DNP and the feasibility to purify dinitrophenol waste water by it. The biomass, actual photochemical efficiency (PSII), net photosynthetic rate (Pn), photochemical quenching coefficient (qP), stomatal conductance (Gs), transpiration rate (Tr), maximum photochemical efficiency (Fv/Fm) and chlorophyll content of the S. babylonica showed downward trend with the increasing exposure concentrations of 2,4-DNP, but the intercellular CO2 concentration (Ci) appeared upward trend. Non-photochemical quenching coefficient (NPQ) increased at 5 mg L-1, then declined with the increase concentrations of 2, 4-DNP. In addition, the percent removal of 2, 4-DNP in 20 mg L-1 waste water was 91.4%. In conclusion, 2, 4-DNP significantly inhibits Pn of S. babylonica and the reduction of Pn was caused by decreasing Gs, carboxylation efficiency and chlorophyll content. When the concentration of 2, 4-DNP is not more than 20 mg L-1, S. babylonica can remove 2, 4-DNP efficiently.

Theoretical Investigation on the ESIPT Process and Detection Mechanism for Dual-Proton Type Fluorescent Probe.

Recently, a new fluorescent probe AE-Phoswas reported to detect the activity of alkaline phosphatases (ALP) in different living cell lines. Here, we present an in-depth computational analysis of the mechanism and source of the fluorescence of the AE-Phos probe. There is an intermediate product (AE-OH-Phos) in the experiment as well as a different configuration of products that may emit fluorescence. It is essential to investigate the origin of fluorescence and the detection mechanism of the probe, which could help us eliminate the interference of other substances (including an intermediate product and possible isomers) on fluorescence during the experiment. According to the change of geometric parameters and Infrared spectra, we deduce that the dual intramolecular hydrogen bonds of salicylaldehyde azine (SA) were enhanced at the excited state, while AE-OH-Phos was attenuated. Considering the complex ESIPT behavior of the dual proton-type probe, the potential energy surfaces were further discussed. It can be concluded that the single proton transfer structure of SA (SA-SPT) is the most stable form. Both the concerted double proton transfer process and stepwise single proton transfer process of SA were forbidden. The fluorescence for SA was 438 nm, while that of SA-SPT was 521 nm, which agrees with the experimentally measured fluorescence wavelength (536 nm). The conclusion that single proton transfer occurs in SA is once again verified. In addition, the distribution of electron-hole and relative index was analyzed to investigate the intrinsic mechanism for the fluorescence quenching of the probe and the intermediate product. The identification of the origin of fluorescence sheds light on the design and use of dual-proton type fluorescent probes in the future.

Ultrafast carrier dynamics in all-inorganic CsPbBr3 perovskite across the pressure-induced phase transition.

The excited-state carrier dynamics of lead halide perovskites play a critical role in their photoelectric properties, and are greatly affected by lattice structural changes. In this work, the carrier dynamics of all-inorganic CsPbBr3 peroveskite, as a function of pressure, are investigated using in situ high-pressure femtosecond transient absorption spectroscopic experiments. Compression is found to drive crystal structural evolution, thereby markedly changing the behavior of charge carriers in CsPbBr3. Before the phase transition, simultaneous prolonging of the carrier relaxation and Auger recombination is achieved alongside a narrowing in the bandgap. The results favor improved efficiency and photovoltaic performance.

Tuning the Electron-Transport and Electron-Accepting Abilities of Dyes through Introduction of Different π-Conjugated Bridges and Acceptors for Dye-Sensitized Solar Cells.

A series of dyes, containing thiophene and thieno[3,2-b]thiophene as π-conjugated bridging units and six kinds of groups as electron acceptors, were designed for dye-sensitized solar cells (DSSCs). The ground- and excited-state properties of the designed dyes were investigated by using density functional theory (DFT) and time-dependent DFT, respectively. Moreover, the parameters affecting the short-circuit current density and open-circuit voltage were calculated to predict the photoelectrical performance of each dye. In addition, the charge difference density was presented through a three-dimensional (3D) real-space analysis method to investigate the electron-injection mechanism in the complexes. Our results show that the longer conjugated bridge would inhibit the intramolecular charge transfer, thereby affecting the photoelectrical properties of DSSCs. Similarly, owing to the lowest chemical hardness, largest electron-accepting ability, dipole moment (µnormal ) and the change in the energy of the TiO2 conduction band (ΔECB ), the dye with a (E)-3-(4-(benzo[c][1,2,5]thiadiazol-4-yl)phenyl)-2-cyanoacrylic acid (TCA) acceptor group would exhibit the most significant photoelectrical properties among the designed dyes.

Survival of labial inversely impacted maxillary central incisors: A retrospective cone-beam computed tomography 2-year follow-up.

INTRODUCTION: The aim of this study was to analyze the development and stability of roots and alveolar bone in orthodontically treated labial inversely impacted maxillary central incisors in a long-term follow-up by cone-beam computed tomography. Comparisons were made between the labial inversely impacted maxillary central incisors after treatment and normally erupted mature contralateral incisors. METHODS: The sample consisted of 12 participants, with a mean age of 7.80 ± 0.91 years. Cone-beam computed tomography scanning data at the completion of treatment and the long-term follow-up were available for each participant.The mean length of follow-up was 24.57 ± 4.33 months. Root length, crown height, root canal width, labial/lingual alveolar bone vertical loss, and bone thickness of the impacted and contralateral incisors were measured with the SimPlant Pro program (version 13.0; Materialise Dental, Leuven, Belgium). RESULTS: In the follow-up, the root lengths of both the labial inversely impacted dilacerated maxillary central incisors (10.99 ± 1.96 mm) and the contralateral mature maxillary central incisors (11.65 ± 1.37 mm) were significantly longer than at posttreatment (8.37 ± 1.74 mm and 9.81 ± 1.65 mm, respectively). The root canal widths of the impacted and contralateral incisors were significantly narrower during the follow-up. The size of the angle between the long axis of the crown and apical third of the root decreased significantly. The lingual alveolar bone loss of the impacted incisors was greater than that of the contralateral incisors. The labial bone thickness at the apex of the impacted incisors increased significantly during the follow-up period. CONCLUSIONS: The treated labial inversely impacted maxillary central incisors had continuous and similar growth as did the mature contralateral incisors in the follow-up period. The roots had an increase in length and a change in direction of the apex, with a relatively stable condition of the surrounding alveolar bone. Neither the labial inversely impacted maxillary central incisors nor the contralateral incisors had further alveolar bone loss.

Combined effects of proinflammatory cytokines and intermittent cyclic mechanical strain in inhibiting osteogenicity in human periodontal ligament cells.

Mechanical strain plays an important role in bone formation and resorption during orthodontic tooth movement. The mechanism has not been fully studied, and the process becomes complex with increased amounts of periodontal patients seeking orthodontic care. Our aims were to elucidate the combined effects of proinflammatory cytokines and intermittent cyclic strain (ICS) on the osteogenic capacity of human periodontal ligament cells. Cultured human periodontal ligament cells were exposed to proinflammatory cytokines (interleukin-1ß 5 ng/mL and tumor necrosis factor-α 10 ng/mL) for 1 and 5 days, and ICS (0.5 Hz, 12% elongation) was applied for 4 h per day. The autocrine of inflammatory cytokines was measured by enzyme-linked immunosorbent assay. The expression of osteoblast markers runt-related transcription factor 2 and rabbit collagen type I was determined using real-time polymerase chain reaction and Western blot. The osteogenic capacity was also detected by alkaline phosphatase (ALP) staining, ALP activity, and alizarin red staining. We demonstrated that ICS impaired the osteogenic capacity of human periodontal ligament cells when incubated with proinflammatory cytokines, as evidenced by the low expression of ALP staining, low ALP activity, reduced alizarin red staining, and reduced osteoblast markers. These data, for the first time, suggest that ICS has a negative effect on the inductive inhibition of osteogenicity in human PDL cells mediated by proinflammatory cytokines.

Root morphology and development of labial inversely impacted maxillary central incisors in the mixed dentition: a retrospective cone-beam computed tomography study.

INTRODUCTION: The aim of this study was to analyze 3-dimensional data of root morphology and development in labial inversely impacted maxillary central incisors. METHODS: Cone-beam computed tomography images from 41 patients with impacted incisors were divided into early and late dental age groups according to their dental age. Sagittal slices in which the labiolingual width of the tooth was the widest in the axial view were evaluated. The inverse angle, the dilaceration angle, and the length of both impacted and homonym teeth were evaluated with SimPlant Pro software (version 13.0; Materialise Dental NV, Leuven, Belgium). RESULTS: The Student t test indicated that the lengths of the impacted teeth were significantly shorter than those of the homonym teeth (P <0.05), and the root lengths of the early dental age group were significantly shorter than those of the late dental age group. The results from chi-square tests indicated that the incidence of dilacerations was significantly higher in the late dental age group when compared with the early dental age group. Multiple regression analyses indicated that the independent variables for root length of the impacted teeth were dental age (ß = 0.958; P <0.001) and length of the nondilacerated part of the root (ß = 0.435; P <0.001). CONCLUSIONS: Dilaceration was more common in the late dental age group. The roots of labial inversely impacted maxillary central incisors continue developing, but their potential is limited.

Synchronous or stepwise Mechanism? a theoretical study on the Excited-State double proton transfer properties of shikonin and acetylshikosin.

The excited state double proton transfer (ESDPT) mechanism of shikonin (Shk) and its derivative acetylshikosin (AcShk) were studied by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. The potential energy curves scanned along the coordinates of proton transfer indicate a preference for the ESDPT reaction to occur step by step. The AcShk molecule possesses an additional reaction pathway in comparison to the Shk molecule. Furthermore, efforts have been made to compute the absorption and fluorescence peak, which exhibits favorable conformity with the experimental findings of the system investigated. The fluorescence spectra in cyclohexane and acetonitrile solvents indicate that the solvent polarity affects the location of the ESDPT fluorescence peak in both Shk and AcShk systems. The fluorescence spectra concentrated in the green light region (504 nm âˆ¼ 550 nm) are obtained, which has the potential to promote human health through disinfection and boosting the immune system.

Effect of different substituent on the ESIPT process and fluorescence features of 2-(2-hydroxyphenyl)benzoxazole derivatives: A DFT/TD-DFT study.

In this contribution, four derivatives of 5'-(para-R-Phenylene) vinyl-2-(2'-hydroxyphenyl) benzoxazole (PVHBO) were ingeniously designed by introducing two electron-withdrawing substituents and two electron-donating substituents, aiming to investigate the influence of different substituents on the photophysical properties of PVHBO and the excited state intramolecular proton transfer (ESIPT) process via the density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. By utilizing the geometric parameters and the simulated infrared (IR) spectra, we compared the intramolecular hydrogen bonds (IHBs) strengths in the S0 and S1 states of the molecules. Via conducting the hole-electron analysis, the reduction in fluorescence intensity for the enol and keto forms of PVHBO, PVHBO-MeO, and PVHBO-NH2 were also well explicated. Besides, the potential energy curves (PECs) and corresponding transition state (TS) structures for both S0 and S1 states were also constructed to accurately obtain energy barriers of forward and reversed proton transfer processes. The calculated absorption and fluorescence spectra also show that PVHBO-NH2 has the largest Stokes shifts of 158 nm and 219 nm in both the enol and keto states, with a significant increase in fluorescence intensity observed upon the induction of electron-withdrawing groups. Through this work, it can provide the theoretical basis for the design of novel luminescent materials.

Unveiling microplastic's role in nitrogen cycling: Metagenomic insights from estuarine sediment microcosms.

Marine microplastics (MPs) pollution, with rivers as a major source, leads to MPs accumulation in estuarine sediments, which are also nitrogen cycling hotspots. However, the impact of MPs on nitrogen cycling in estuarine sediments has rarely been documented. In this study, we conducted microcosm experiment to investigate the effects of commonly encountered polyethylene (PE) and polystyrene (PS) MPs, with two MPs concentrations (0.3% and 3% wet sediment weight) based on environmental concentration considerations and dose-response effects, on sediment dissolved oxygen (DO) diffusion capacity and microbial communities using microelectrode system and metagenomic analysis respectively. The results indicated that high concentrations of PE-MPs inhibited DO diffusion during the mid-phase of the experiment, an effect that dissipated in the later stages. Metagenomic analysis revealed that MP treatments reduced the relative abundance of dominant microbial colonies in the sediments. The PCoA results demonstrated that MPs altered the microbial community structure, particularly evident under high concentration PE-MPs treatments. Functional analysis related to the nitrogen cycle suggested that PS-MPs promoted the nitrification, denitrification, and DNRA processes, but inhibited the ANRA process, while PE-MPs had an inhibitory effect on the nitrate reduction process and the ANRA process. Additionally, the high concentration of PE-MPs treatment significantly stimulated the abundance of genus (Bacillus) by 34.1% and genes (lip, pnbA) by 100-187.5% associated with plastic degradation, respectively. Overall, in terms of microbial community structure and the abundance of nitrogen cycling functional genes, PE- and PS- MPs exhibit both similarities and differences in their impact on nitrogen cycling. Our findings highlight the complexity of MP effects on nitrogen cycling in estuarine sediments and high concentrations of PE-MP stimulated plastic-degrading genus and genes.

The physiological response of the clam Ruditapes philippinarum and scallop Chlamys farreri to varied concentrations of microplastics exposure.

Microplastics (MPs) pollution's impact on the marine ecosystem is widely recognized. This study compared the effects of polyethylene (PE) and polyethylene terephthalate (PET) on two bivalve species, Ruditapes philippinarum (clam) and Chlamys farreri (scallop), at two particle concentrations (10 and 1000 µg/L). MPs were found in the digestive glands and gills of both species. Although clearance rates showed no significant changes, exposure to different MPs caused oxidative stress, energy disruption, and lipid metabolism disorders in both clam and scallop. Histopathological damage was observed in gills and digestive glands. IBR values indicated increasing toxicity with concentration, with PET being more toxic than PE. WOE model suggested increasing hazard with concentration, highlighting higher PET toxicity on clam digestive glands. In contrast, PE hazard increased in gills, showing different species responses. R. philippinarum exhibited higher sensitivity to MPs than C. farreri, providing insights for assessing ecological risk under realistic conditions and stress conditions.

The pollution characteristics and risk assessment of microplastics in mollusks collected from the Bohai Sea.

Microplastics (MPs) pollution in the marine environment has become a global problem. In this study, a number of 21 mollusk species (n = 2006) with different feeding habits were collected from 11 sites along the Bohai Sea for MPs uptake analysis. The MPs in mollusk samples were isolated and identified by micro-Fourier Transform Infrared Spectroscopy (µ-FTIR), and an assessment of the health risks of MPs ingested by mollusk consumption is also conducted. Approximately 91.9 % of the individuals among all the collected species inhaled MPs, and there was an average abundance of 3.30 ± 2.04 items·individual-1 or 1.04 ± 0.74 items·g-1 of wet weight. The shape of MPs was mainly fiber, and a total number of 8 polymers were detected, of which rayon had the highest detection rate (58.3 %). The highest abundance, uptake rate and polymer composition of MPs was observed in creeping types, suggesting that they might ingest these MPs from their food. The gastropod Siphonalia subdilatata contains the highest levels of MPs, which may increase the risk of human exposure if consumed whole without removing the digestive gland. The polymer risk level of MPs in these mollusks was Level III (H = 299), presenting harmful MPs such as polyvinyl chloride. In terms of human exposure risk, the average risk of human exposure to MPs through consumption of Bohai mollusks is estimated to be 3399 items·(capita·year)-1 (424-9349 items·(capita·year)-1). Overall, this study provides a basis for the ecological and health Risk assessment of MPs in mollusks collected from the coastline of China.

Potential threats of microplastics and pathogenic bacteria to the immune system of the mussels Mytilus galloprovincialis.

As one of the main components of marine pollution, microplastics (MPs) inevitably enter the mussel aquaculture environment. At the same time, pathogenic bacteria, especially pathogens such as Vibrio, can cause illness outbreaks, leading to large-scale death of mussels. The potential harm of MPs and pathogenic bacteria to bivalve remains unclear. This study designed two experiments (1) mussels (Mytilus galloprovincialis) were exposed to 100 particles/L or 1,000 particles/L polymethyl methacrylate (PMMA, 17.01 ± 6.74 µm) MPs and 1 × 107 CFU/mL Vibrio parahaemolyticus at the same time (14 days), and (2) mussels were exposed to 100 particles/L or 1,000 particles/L MPs for a long time (30 days) and then exposed to 1 × 107 CFU/mL V. parahaemolyticus to explore the effects of these two stresses on the mussel immune system. The results showed that after the combined exposure of V. parahaemolyticus and MPs, the lysosomal membrane stability of hemocytes decreased, lysozyme activity was inhibited, and hemocytes were induced to produce more lectins and defensins to fight pathogenic invasion. Long-term exposure to MPs caused a large amount of energy consumption in mussels, inhibited most of the functions of humoral immunity, increased the risk of mussel infection with pathogenic bacteria, and negatively affected mussel condition factor, the number of hemocytes, and the number of byssuses. Mussels may allocate more energy to deal with MPs and pathogenic bacterial infections rather than for growth. Above all, MPs exposure can affect mussel immune function or reduce its stress resistance, which in turn has an impact on mollusk farming.

First record of microplastics in the Gigantidas platifrons (Mytilidae: Bathymodiolus) and Shinkaia crosnieri (Munidopsidae: Shinkaia) from cold-seep in the South China Sea.

The deep sea is considered the final sink for microplastics (MPs) pollution in marine environments. Despite MPs being consumed by many organisms, their presence in cold-seep organisms remains unclear. At cold seep site F in the South China Sea, which lies 1155 m deep, MPs were investigated in Gigantidas platifrons and Shinkaia crosnieri, both ecologically important species. Microplastics ingestion rates were 80.98 % and 81.25 % in G. platifrons and S. crosnieri, respectively. The average MPs abundance for G. platifrons and S. crosnieri was 2.80 ± 0.69 MPs/ind (2.20 ± 2.75 MPs/g) and 2.30 ± 0.27 MPs/ind (4.74 ± 3.08 MPs/g), with no significant difference between species. There were predominantly fibrous MPs ingested by cold-seep organisms, sized 500-1000 µm, blue in color, and polyethylene terephthalate and cellophane in composition. The results confirm the presence of MPs in cold-seep organisms in the South China Sea, providing further evidence that MP pollution exists in the deep sea.

The adverse impact of microplastics and their attached pathogen on hemocyte function and antioxidative response in the mussel Mytilus galloprovincialis.

Microplastics (MPs) are widely distributed in marine environments, and they are easily attached by various microorganisms, including pathogenic bacteria. When bivalves mistakenly eat MPs, pathogenic bacteria attached to MPs enter their bodies through the Trojan horse effect, causing adverse effects. In this study, the mussel Mytilus galloprovincialis was exposed to aged polymethylmethacrylate MPs (PMMA-MPs, 20 µm) and Vibrio parahaemolyticus attached to PMMA-MPs to explore the effect of synergistic exposure by measuring lysosomal membrane stability, ROS content, phagocytosis, apoptosis in hemocytes, antioxidative enzyme activities and apoptosis-related gene expression in gills and digestive glands. The results showed that MP exposure alone did not cause significant oxidative stress in mussels, but after long-term coexposure to MPs and V. parahaemolyticus, the activities of antioxidant enzymes were significantly inhibited in the gills of mussels. Both single MP exposure and coexposure will affect hemocyte function. Coexposure can induce hemocytes to produce higher ROS, improve phagocytosis, significantly reduce the stability of the lysosome membrane, and induce the expression of apoptosis-related genes, causing apoptosis of hemocytes compared with single MP exposure. Our results demonstrate that MPs attached to pathogenic bacteria have stronger toxic effects on mussels, which also suggests that MPs with pathogenic bacteria might have an influence on the immune system and cause disease in mollusks. Thus, MPs may mediate the transmission of pathogens in marine environments, posing a threat to marine animals and human health. This study provides a scientific basis for the ecological risk assessment of MP pollution in marine environments.

Regulating the photophysical properties of ESIPT-based fluorescent probes by functional group substitution: a DFT/TDDFT study.

CONTEXT: In recent years, fluorescent probe technology has received more and more attention. However, the photophysical and photochemical properties of probe molecules still need to be further explored. This paper presents the excited state intramolecular proton transfer (ESIPT) processes and photophysical properties of the probe molecule 4-bromo-2-((E)-((Z)-((5-bromo-1H-indol-2-yl) methylene) hydrazono) methyl) phenol (BHPL) and its four derivatives (BHPL2, BHPL3, BHPL4, and BHPL5). Infrared spectra and geometric structure analyses revealed that introducing the -NH2 group on the benzene ring with the hydroxyl group will enhance the intramolecular hydrogen bond, which benefits the ESIPT process. Combining their absorption and fluorescence spectra, it can be concluded that BHPL2 and BHPL4 are both excellent probe candidates due to their large Stokes shift. The hole and electron and root mean square displacement analyses manifest that the fluorescence quenching of BHPL4 may be due to the intramolecular charge transfer process. Potential energy curves of BHPL and its four derivatives noted that ESIPT process of the BHPL2 is the most favorable to occur. The frontier molecular orbital and NBO analyses indicated that besides introducing electron-donating groups to reduce the energy gap and enhance fluorescence emission, introducing double electron-withdrawing groups can also achieve this effect, explaining why the energy barrier of ESIPT process for BHPL2 is lower than BHPL5. This work would provide the theoretical basis for designing novel fluorescence probes with more prominent properties. METHODS: The ground (S0) and excited (S1) state structures of all compounds were optimized by density functional theory (DFT) and time-dependent (TDDFT) method, with B3LYP/6-311+G(d,p) level, respectively. The infrared spectra and potential energy curves were simulated at the same theoretical level. The reduced density gradient scatter plots and interaction region indicator isosurfaces were drawn using Multiwfn and VMD programs. The absorption and fluorescence spectra were simulated by the TDDFT/B3PW91/6-311+G(d,p) method. All the calculations in this work are carried out in Gaussian 16 program package.