Theoretical Study on the Reaction between Carcinogenic 2,5-Dichloro-1,4-benzoquinone and tert-Butyl Hydroperoxide: Self-Catalysis and Water Catalysis.

The potentially carcinogenic halobenzoquinones (HBQs) have been recently identified in drinking water as disinfection byproducts. Several radical intermediates in the reaction of 2,5-dichloro-1,4-benzoquinone (DCBQ) and t-butyl hydroperoxide (t-BuOOH), which may induce DNA damage, were detected experimentally, and metal-independent decomposition reactions of t-BuOOH by DCBQ were proposed. It has not yet been confirmed by theoretical calculations. The theoretical study in this work provides insights into the details of the reaction. An unprecedented self-catalysis mechanism of organic hydroperoxides, that is, the reactant t-BuOOH also has a catalytic effect, was uncovered at the molecular level. Moreover, as the solvent, water molecules also clearly have an efficient catalytic effect. Due to the catalysis of t-BuOOH and water, the metal-independent reaction of t-BuOOH and DCBQ can occur under moderate conditions. Our findings about the novel catalytic effect of organic hydroperoxides t-BuOOH could offer a unique perspective into the design of new catalysts and an understanding of the catalytic biological, environmental, and air pollution reactions. Furthermore, organic hydroperoxide t-BuOOH could serve as a proton shuttle, where the proton transfer process is accompanied by simultaneous charge transfer. Therefore, organic hydroperoxides may disrupt the vital proton transfer process in biological systems and may give rise to unexpected toxicity.

Correlation analysis of lung mucosa-colonizing bacteria with clinical features reveals metastasis-associated bacterial community structure in non-small cell lung cancer patients.

BACKGROUND: Microbes colonizing lower airways can regulate the host immune profile and consequently participate in lung disease. Increasing evidence indicate that individual microbes promote lung cancer progression and are involved in metastasis incidence. To date, however, no study has revealed the community structure of lung bacteria in metastatic non-small cell lung cancer (NSCLC) patients. METHODS: We prospectively enrolled 50 healthy subjects and 57 NSCLC patients. All healthy subjects and NSCLC patients underwent bronchoscope procedures for brush specimen collection. The 16 S ribosomal RNA gene was sequenced to characterize the community structure of lung mucosa-colonizing bacteria. The peripheral blood of NSCLC patients was also measured for leukocytes and cancer markers. RESULTS: The lung bacteria of healthy subjects and NSCLC patients were divided into four communities. All community 2 members showed increased abundance in NSCLC patients compared with healthy subjects, and most community 2 members showed increased abundance in the metastatic NSCLC patients compared with the non-metastatic group. These bacteria were significantly and positively correlated with eosinophils, neutrophils and monocytes in the metastatic NSCLC group. In addition, the correlation between lung bacteria and cancer markers differed between the metastatic and non-metastatic NSCLC patients. Furthermore, bronchoalveolar lavage fluid from lung adenocarcinoma patients directly promoted NSCLC cell migration. CONCLUSIONS: The community structure of lung mucosa-colonizing bacteria was relatively stable, but changed from the healthy population to NSCLC patients, especially the metastatic group. This distinct community structure and specific correlation with immune cells and cancer markers could help to distinguish NSCLC patients with or without metastasis.

Spin-orbit charge-transfer intersystem crossing in heavy-atom-free orthogonal covalent boron-dipyrromethene heterodimers.

Boron-dipyrromethene (BODIPY) derivatives are prospective organic-based triplet photosensitizers. Since the triplet generation yield of the parent BODIPY is low, heavy atoms are widely used to improve the triplet yield. However, the dimerization of BODIPYs can also significantly improve their ability to produce triplets. Through a comparative study of the triplet formation dynamics of two heavy-atom-free orthogonal covalent BODIPY heterodimers that differ in their dihedral angles, we have demonstrated that the mechanism of spin-orbit charge-transfer intersystem crossing (SOCT-ISC) promotes the triplet generation of BODIPY heterodimers in solution. Different from the general understanding of SOCT-ISC, the heterodimer with a smaller dihedral angle and low structural rigidity showed better triplet generation due to (a) the stronger inter-chromophoric interaction in the heterodimer, which promoted the formation of a solvent-stabilized charge-transfer (CT) state, (b) the more favorable energy level alignment with sizeable spin-orbit coupling strength, and (c) the balance between the stabilized singlet CT state and limited direct charge recombination to the ground state in a weakly polar solvent. The complete spectral characterization of the triplet formation dynamics clarified the SOCT-ISC mechanism and important factors affecting the triplet generation in BODIPY heterodimers.

Symmetry-breaking charge separation in a nitrogen-bridged naphthalene monoimide dimer.

The photophysical properties of 4-aminonaphthalene-1,8-imide-based derivatives, bis-ANI, consisting of two naphthalimide (NI) units linked by a butylamine bridge and its monomer ANI have been intensively investigated by steady-state and transient spectroscopy combined with quantum chemical calculations. The excited state relaxation dynamics of the two molecules are studied in three solvents of varying polarity - from hexane to tetrahydrofuran to acetone. A strong reduction in the fluorescence quantum yields and larger red shifts of the emission spectra are observed when going from the monomer ANI to dimer bis-ANI with increasing solvent polarity. It is found that the presence of the central amino linker in bis-ANI facilitates the formation of an asymmetric CS state between the ANI and NI moieties in bis-ANI, where NI˙- is the dominant radical anion unit after CS, evidenced by the femtosecond transient absorption measurements and spectroelectrochemistry in polar solvents. Femtosecond transient absorption spectra and quantum chemical calculations reveal the conformational change after the formation of the symmetry-breaking charge separation (SBCS) state upon photoexcitation, while a near-orthogonal structure in the excited state of bis-ANI retards charge recombination. In addition, it is evidenced that the rate of SBCS can be tuned by changing the different polar solvents.

Conformation-related excited-state charge transfer/separation of donor-π-acceptor chromophores.

Understanding the excited-state charge transfer/separation (CT/CS) of donor-π-acceptor chromophores can provide guidance for designing and synthesizing advanced dyes to improve the performance of dye-sensitized solar cells (DSSCs) in practical applications. Herein, two newly synthesized electronic push-pull molecules, CS-14 and CS-15, that consist of carbazole donor and benzothiadiazole acceptor segments are chosen to explore the ultrafast dynamics of intramolecular CT/CS processes. The theoretical calculation results depict an excited-state intramolecular CT character for both dyes, while the dihedral angle between donor and acceptor of CS-14 is larger than that of CS-15, suggesting a more significant CT character of CS-14. Furthermore, compared to CS-14, the bond rotation of CS-15 between donor and π-bridge is restricted by employing the hexatomic ring, indicating the stronger molecular planarization of CS-15. Ultrafast spectroscopy clearly shows a solvent polarity-dependent excited-state species evolution from CT to CS-the CT character is observed in low-polar toluene solvent, while the feature of the CS state in polar tetrahydrofuran and acetone solvents is captured, which successfully proved a solvent polarity modulated excited-state CT/CS characters. We also found that though the generation of the CS state within CS-14 is slightly faster than that of CS-15, the charge recombination process of CS-15 with excellent planar conformation is much slower, providing enough time for a higher charge migration efficiency in DSSCs.

Supramolecular Polymeric Radicals: Highly Promoted Formation and Stabilization of Naphthalenediimide Radical Anions.

The supramolecular polymeric radicals are developed to promote the generation efficiency and stability of naphthalenediimide (NDI) radical anions. To this end, a water-soluble bifunctional monomer bearing two naphthalene-viologen end groups and a NDI center is designed and synthesized. The supramolecular polymeric NDI radical anions are fabricated on the basis of host-guest complexation between the NDI-containing bifunctional monomer and cucurbit[8]uril (CB[8]) and followed by the photoinduced electron transfer process under UV light irradiation. The electrostatic effect of CB[8] and the bulky and rigid structure of supramolecular polymer are combined to stabilize the excited state of NDIs and NDI radical anions, contributing to the high enhancement of the formation of NDI radical anions with excellent stability. It is found that the highest occupied molecular orbital energy and lowest unoccupied molecular orbital energy of NDI are also lowered by the formation of supramolecular polymer. In addition, the supramolecular polymeric NDI radical anions could be utilized as a supramolecular photoreducing agent to reduce cytochrome C with a higher efficiency. It is anticipated that other radicals can also be stabilized through this strategy, and this line of research may lead to the development of novel polymeric radical materials.

Electron-donating strength dependent symmetry breaking charge transfer dynamics of quadrupolar molecules.

The excited state symmetry breaking charge transfer (SBCT) dynamics of two diacetylide-triphenylamine (DATPA) derivatives with different electron-donating abilities are investigated by femtosecond transient absorption and fluorescence spectroscopy. By tracking the evolution of the excited states by transient absorption spectra and the kinetics of the instantaneous emission dipole moments obtained from transient fluorescence spectroscopy, it is found that, in nonpolar solvent, the relaxed S1 state is quadrupolar with little change of emission dipole moments for the two molecules within 30 ps, whereas in polar solvent, the quadrupolar state evolves to a symmetry broken S1 state, in which, the emission dipole moment exhibits a fast reduction in the first few picoseconds. The larger reduction in emission transition dipole moment for the molecule with stronger electron-donating methoxy groups indicates a larger extent of symmetry breaking compared with the one with weak electron-donating methyl groups. Consequently, we revealed that the magnitude of symmetry breaking can be tuned by changing the electron-donors in quadrupolar molecules.

Bridge-Mediated Charge Separation in Isomeric N-Annulated Perylene Diimide Dimers.

The possibility and rate of charge separation (CS) in donor-bridge-acceptor molecules mainly depend on two factors: electronic coupling and solvent effects. The question of how CS occurred in two identical chromophores is fundamental, as it is particularly interesting for potential molecular electronics applications and the photosynthetic reaction centers (RCs). Conjugated bridge definitely plays a crucial role in electronic coupling. To determine the bridge-mediated charge separation dynamics between the two identical chromophores, the isomeric N-annulated perylene diimide dimers (para-BDNP and meta-BDNP) with different conjugated bridge structures have been comparatively investigated in different solvents using femtosecond transient absorption spectra (fs-TA). It is found that the charge separation is disfavored in weak polar solvent, whereas direct spectroscopic signatures of radicals are observed in polar solvents, and the rate of charge separation increases as the solvent polarity increasing. To our surprise, the rate of charge separation in m-BDNP is more than an order of magnitude slower than that in p-BDNP, although there is a larger negative ΔGCS in m-BDNP. The slow CS rate that occurred in m-BDNP mainly results from the intrinsic destructive interference of the wave function through the meta-substituted bridge. The roles of solvent effects in free energy and electronic coupling for charge separation are further identified with quantum calculations.

Solvent modulated excited state processes of push-pull molecule with hybridized local excitation and intramolecular charge transfer character.

Recently, a type of synthetic highly efficient OLED molecule based on a hybridized local excitation and charge transfer (HLCT) character has received much attention as a potential high-efficiency fluorescent OLED material. In this article, we report the relaxation dynamics of the excited states of cyano-substituted oligo α-phenylenevinylene-1,4-bis(R-cyano-4-diphenylaminostyryl)-2,5-diphenylbenzene (CNDPASDB) with HLCT character using steady-state and time-resolved spectroscopy as well as quantum chemical calculations. The dramatic dependence of the fluorescence quantum yield, radiative and non-radiative rate, as well as the excited state relaxation pathways on solvent polarity reveals that the solvation process controls the energy levels of two closely spaced electronic excited states. By employing femtosecond transient absorption spectra, the gradual transition from the LE state to the intramolecular CT state with an increase in solvent polarity is clearly resolved. In low-polarity solvents the fluorescence of CNDPASDB is mainly emission from the LE state, whereas in high-polarity solvents non-radiative decay from the CT state dominates. And in medium-polarity solvents, because of the relatively weaker solvation-induced stabilization of the CT state, its energy could be equal to or slightly lower than that of the LE state, leading to a smaller driving force for LE → CT interconversion; therefore complete LE → CT interconversion cannot take place. In this situation, LE ↔ CT intercrossed equilibration is established and the equilibrium constant is further estimated to be about 4 according to the obtained kinetics, and the equilibrium population of the CT state is about 80%. DFT/TDDFT analysis also confirmed an efficient intercrossing of LE and CT states with an increase in solvent polarity. It is found that upon increasing the solvent polarity, the hole and electron on a molecule are entirely separated, suggesting a complete CT character. These results provide guidance for understanding the relationship between solvent polarity and the HLCT process, as well as for designing and synthesizing advanced OLED materials.

Intramolecular charge transfer and solvation dynamics of push-pull dyes with different π-conjugated linkers.

The solvation-dependent excited state dynamics of two push-pull fluorophores with donor-π-acceptor (D-π-A) structures were investigated using steady-state and ultrafast transient absorption (TA) spectroscopy, backed by theoretical calculations. Identical D and A groups were present in both dyes, which differed only in the structure of their central π-conjugated linkers. Dye 1 features a p-phenylenediethynyl linker, while dye 2 contains a 2,5-diethynylthiophene linker. From the steady-state spectra, no appreciable shifts in absorption bands were observed, whereas large red-shifts in emission were seen with increasing solvent polarity, which indicated that the excited states were more polar than the ground state. Theoretical calculations support charge transfer from the triphenylamine (TPA) donor to the pentafluorosulfanyl (SF5) acceptor viaπ-conjugated linkers to form an intramolecular charge transfer (ICT) state. TA spectra revealed that a solvation-stabilized conformationally relaxed intramolecular charge transfer (ICT') state was formed in polar solvents, but only an ICT state was observed in nonpolar solvent. The SE band was quenched within 1 ps in high-polarity solvent, which corresponds to the low fluorescence quantum yield. It can be concluded that the dye with the p-phenylenediethynyl π-linker (i.e., dye 1) exhibits a larger degree of ICT than the thiophene analogue (i.e., dye 2). These findings demonstrate how solvation can fine-tune the photophysical properties of push-pull dyes, and this study highlights the importance of π-conjugated linkers in the excited state ICT process.

Label-Free Dynamic Detection of Single-Molecule Nucleophilic-Substitution Reactions.

The mechanisms of chemical reactions, including the transformation pathways of the electronic and geometric structures of molecules, are crucial for comprehending the essence and developing new chemistry. However, it is extremely difficult to realize at the single-molecule level. Here, we report a single-molecule approach capable of electrically probing stochastic fluctuations under equilibrium conditions and elucidating time trajectories of single species in non-equilibrated systems. Through molecular engineering, a single molecular wire containing a functional center of 9-phenyl-9-fluorenol was covalently wired into nanogapped graphene electrodes to form stable single-molecule junctions. Both experimental and theoretical studies consistently demonstrate and interpret the direct measurement of the formation dynamics of individual carbocation intermediates with a strong solvent dependence in a nucleophilic-substitution reaction. We also show the kinetic process of competitive transitions between acetate and bromide species, which is inevitable through a carbocation intermediate, confirming the classical mechanism. This unique method creates plenty of opportunities for carrying out single-molecule dynamics or biophysics investigations in broad fields beyond reaction chemistry through molecular design and engineering.

Insights into the effect of donor ability on photophysical properties of dihydroindeno[2,1-c]fluorene-based imide derivatives.

The photophysical properties of dihydroindeno[2,1-c]fluorene-based imide (DHIFI) derivatives were investigated by steady-state and time-resolved spectroscopy as well as quantum chemical calculations. The hybridized local excited and charge transfer state (HLCT) was introduced to interpret the intercrossing of localized excited (LE) and charge transfer (CT) states. The large extent of CT in the HLCT state of a molecule with a strong electron donor (dimethylaniline) at the terminal site results in strong interaction between the dipole moments of the excited state and polar solvents. Time-resolved spectroscopy results show the formation of a stabilized ICT state in several picoseconds, which results in fluorescence quenching and less possibility of intersystem crossing to the triplet state. In contrast, a molecule with a weak electron donor (benzene) displays less fluorescence quenching. The slowing down of geometry relaxation in the weak-electron-donor molecule increases the possibility of ISC to the triplet state from the unrelaxed HLCT state.

Probing Laser-Induced Heterogeneous Microenvironment Changes in Room-Temperature Ionic Liquids.

Modulating the heterogeneous microenvironment in room-temperature ionic liquids (RTILs) by external stimuli is an important approach for understanding and designing external field-induced chemical reactions in natural and applied systems. Here, we report for the first time the redistribution of oxygen molecules related to microstructure changes in RTILs induced by an external laser field, which is probed simultaneously by the triplet-state dynamics of porphyrin. A remarkably long-lived triplet state of porphyrin is observed with changes of microstructures after irradiation, suggesting that charge-shifted O2 molecules are induced by the external field and/or rearranged intrinsic ions move from nonpolar domains into the polar domains of RTILs through electrostatic interactions. The results suggest that heterogeneous systems like ionic liquids in the presence of external stimuli can be designed for reaction systems associated with not only O2 but also for CO2 , CS2 , etc. and many other similar solvent molecules for many promising applications.

High-Efficiency Selective Electron Tunnelling in a Heterostructure Photovoltaic Diode.

A heterostructure photovoltaic diode featuring an all-solid-state TiO2/graphene/dye ternary interface with high-efficiency photogenerated charge separation/transport is described here. Light absorption is accomplished by dye molecules deposited on the outside surface of graphene as photoreceptors to produce photoexcited electron-hole pairs. Unlike conventional photovoltaic conversion, in this heterostructure both photoexcited electrons and holes tunnel along the same direction into graphene, but only electrons display efficient ballistic transport toward the TiO2 transport layer, thus leading to effective photon-to-electricity conversion. On the basis of this ipsilateral selective electron tunnelling (ISET) mechanism, a model monolayer photovoltaic device (PVD) possessing a TiO2/graphene/acridine orange ternary interface showed ∼86.8% interfacial separation/collection efficiency, which guaranteed an ultrahigh absorbed photon-to-current efficiency (APCE, ∼80%). Such an ISET-based PVD may become a fundamental device architecture for photovoltaic solar cells, photoelectric detectors, and other novel optoelectronic applications with obvious advantages, such as high efficiency, easy fabrication, scalability, and universal availability of cost-effective materials.

Synergetic Integration of Cu1.94S-ZnxCd1-xS Heteronanorods for Enhanced Visible-Light-Driven Photocatalytic Hydrogen Production.

In this Communication, we present the integration of synergetic designs into high-quality, well-defined Cu1.94S-ZnxCd1-xS heteronanorods (0 ≤ x ≤ 1) for enhanced photocatalytic hydrogen evolution. These heteronanorods possess two light absorbers, intimate heterointerfaces, tunable band gaps over a wide range, and uniform one-dimensional morphology. As verified by experimental and density functional theory studies, these heteronanorods with continuous composition adjustment fully exploit the benefits of both interfacial charge separation and optimized band alignments. Even without any cocatalysts, Cu1.94S-Zn0.23Cd0.77S heteronanorods exhibit efficient hydrogen production activity (7735 µmol h(-1) g(-1)) under visible-light irradiation (λ > 420 nm), representing a 59-fold enhancement compared with the pristine CdS catalyst. Meanwhile, deposition of a Pt cocatalyst on the Cu1.94S-ZnxCd1-xS surface substantially enhances the hydrogen production performance (13 533 µmol h(-1) g(-1)) with an apparent quantum efficiency of 26.4% at 420 nm, opening up opportunities to promote the overall photocatalytic performance using rationally designed nanostructures.

A Study of Excitation Delocalization/Localization in Multibranched Chromophores by Using Fluorescence Excitation Anisotropy Spectroscopy.

We describe a simple approach to study the excitation localization/delocalization in multibranched chromophores by using fluorescence excitation anisotropy spectroscopy at room temperature. As examples, the electronic excitations in three different multibranched chromophores (dimers) are investigated. For a weakly coupled dimer, fluorescence anisotropy is independent of excitation wavelength, due to localized excitation as well as the degenerate electronic excited states. In contrast, in the case of a strongly coupled dimer, owing to excitonic splitting, a redistribution of the excitation energy is demonstrated by the dependence of anisotropy spectra on the excitation wavelength, which leads to significant deviation from the anisotropy signal of localized excitation. In particular, based on the law of additivity for anisotropy, the degree of delocalized excitation can be simply estimated for a given dimer.

Intramolecular Charge Transfer and Solvation of Photoactive Molecules with Conjugated Push-Pull Structures.

A comparative investigation on the photophysical properties and solvation-related ICT dynamics of three push-pull compounds containing different donors including carbazole, triphenylamine and phenothiazine, was performed. The steady-state spectra and theoretical calculations show the charge transfers from the central donors to the acceptors at each side. The characterization of the extent of charge transfer was determined by various means, including estimation of the dipole moment, the electron density distribution of HOMO and LUMO, CDD and change in Gibb's free energy, which show the charge transfer strength to be in the order PDHP > BDHT > PDHC. This suggests that the electron-donating ability of the donor groups plays a crucial role in the charge transfer in these compounds. The TA data show the excited-state relaxation dynamics follow a sequential model: FC→ICT→ICT'→S0 , and are affected by the solvent polarity. The results presented here demonstrate that the compound with a higher degree of ICT characteristic interacts more strongly with stronger polar solvent molecules, which can accelerate the solvation and spectral evolution to lower energy levels. The A-π-D-π-A architectures with prominent ICT characteristics based on carbazole, triphenylamine and phenothiazine might be potential scaffolds for light-harvesting and photovoltaic devices. These results are of value for understanding structure-property relationships and the rational design of functional materials for photoelectric applications.

Synthesis and Properties of Axially Symmetrical Rigid Visible Light-Harvesting Systems Containing [60]Fullerene and Perylenebisimide.

Two visible light-harvesting perylenebisimide (PDI)-[60]fullerene (C60) systems, dyad P1 with one C60 unit and triad P2 with two C60 units, have been synthesized. Both systems are axially symmetrical with a rigid biphenyl linker, ensuring a relatively fixed spatial distance between the donor and acceptor, preventing through-space interaction, and enhancing energy transfer. Steady-state and transient spectroscopy, electrochemistry, as well as theoretical calculations have been used to investigate the electrochemical and photophysical properties of the two systems. Steady-state and time-resolved spectroscopy demonstrate that the excited state is featured by an efficient intramolecular energy transfer from PDI to C60. Then, the high efficient intrinsic intersystem crossing of C60 eventually leads to the production of the triplet C60. The extensive visible light absorption of PDI in the range of 400-650 nm and the final localization of the excited energy at the triplet C60 make these compounds ideal singlet oxygen inducers. Further investigation shows that the photooxidation capability for both compounds is significantly enhanced with respect to either PDI or C60 and even better than that of the commonly used triplet photosensitizer methylene blue (MB). The double C60 moieties in P2 display a better result, and the photooxidation efficiency of P2 increases 1.3- and 1.4-fold compared to that of P1 and MB, respectively. The combination of a light-harvesting unit with an intersystem crossing unit results in a highly efficient photooxidation system, which opens up a new way to triplet photosensitizer design.

Excited-state localization and energy transfer in pyrene core dendrimers with fluorene/carbazole as the dendrons and acetylene as the linkages.

A multi-leveled theoretical investigation combining TD-DFT (B3LYP and CAM-B3LYP) methods and a semi-empirical method was conducted to determine the structure-related spectral properties of T-series dendrimers composed of nearly hundreds of atoms, based on a proposed molecular model. Both one- and two-photon absorption spectra of the dendrimer molecules were well reproduced. The "antenna effect" in the dendrimers molecule was theoretically studied. The process of excitation energy localization from chromophores in the branches to the pyrene core before the fluorescence emission was visualized using contours of the charge different density (CDD) between the electronic states. Conclusions based on the theoretical model were drawn about the observed photophysical properties of T-series dendrimers as follows: (a) increasing the generation of a branch would enhance the absorption of photons with a wavelength below 430 nm; (b) enlarging the conjugation of branches would enhance the coupling among the chromophores and would lower the excitation energy;

Photophysical properties of octupolar triazatruxene-based chromophores.

The photophysical properties of three octupolar chromophores containing planar triazatruxene (TAT) as the central electron donor with different electron-withdrawing groups in the tribranched arrangement have been systematically investigated by means of steady state and transient spectroscopy. The multidimensional intramolecular charge transfer (ICT) properties of these tribranched chromophores related to the observed two-photon absorption (TPA) properties are explored by estimating the TPA essential factors (Mge and Δµge). Besides the large Stokes shift between steady state absorption and fluorescence spectra in different polar solvents, photoinduced ICT was further demonstrated by quantum-chemical calculations and transient absorption measurements. Both quantum calculations and spectral experiments show that a multidimensional ICT occurs from the electron-rich core to the electron-deficient periphery of these TAT derivatives. The results of solvation effects and the dynamics of the excited states show that the excited states of these three chromophores tend to exhibit an excitation localization on one of the dipolar branches, which is beneficial to achieve large Mge and Δµge, thus leading to enhanced TPA properties.