Recombination Route Research Articles

Cyclic Peptides from Graspetide Biosynthesis and Native Chemical Ligation.

The ribosomally synthesized and post-translationally modified peptide (RiPP) superfamily of natural products includes many examples of cyclic peptides with diverse macrocyclization chemistries. The graspetides, one family of macrocyclized RiPPs, harbor side chain-side chain ester or amide linkages. We recently reported the structure and biosynthesis of the graspetide pre-fuscimiditide, a 22-amino-acid (aa) peptide with two ester cross-links forming a stem-loop structure. These cross-links are introduced by a single graspetide synthetase, the ATP-grasp enzyme ThfB. Here we show that ThfB can also catalyze the formation of amide or thioester cross-links in prefuscimiditide, with thioester formation being especially efficient. We further show that upon proteolysis to reveal an N-terminal cysteine residue, the thioester-linked peptide rapidly and quantitatively rearranges via native chemical ligation into an isopeptide-bonded head-to-tail cyclic peptide. The solution structure of this rearranged peptide was determined by using 2D NMR spectroscopy experiments. Our methodology offers a straightforward recombinant route to head-to-tail cyclic peptides.

KINETICS OF CATHODIC HYDROGEN EVOLUTION ON MOLYBDENUM DISILICIDE IN ACID SULPHATE MEDIA

The kinetics and mechanism of hydrogen evolution on the MoSi2 electrode in x M H2SO4 + (0.5 - x) M Na2SO4 (x = 0.50; 0.35; 0.20) solutions have been studied. The cathodic polarization curves of MoSi2 in the studied solutions are characterized by Tafel region with a slope of (-0.070)±0.002 V. The reaction order of the cathodic process with respect to hydrogen ions at the potentials of Tafel region is ~1.0; the derivative of the electrode potential with a change in electrolyte acidity is ~0.072 V. The impedance spectra of the MoSi2 electrode in the studied potential range have the shape of a semicircle located in the capacitive half-plane, with the centre in the region of positive values of the imaginary impedance component; in the region of the highest frequencies, a short straight section is recorded on the impedance plots, indicating the presence of pores in the surface layer of the electrode. To describe the hydrogen evolution reaction on MoSi2, we used an equivalent electrical circuit, the Faraday impedance of which consists of series-connected charge transfer resistance (R1) and a parallel R2C2Zd-chain responsible for the adsorption of atomic hydrogen on the surface and its diffusion into the depth of the electrode material. The equivalent circuit also includes the solution resistance (Rs) and the double layer capacitance impedance, which is modeled by the constant phase element CPE1. It is shown that the hydrogen evolution reaction on molybdenum disilicide in a sulphuric acid electrolyte proceeds along the discharge - recombination route with a quasi-equilibrium discharge stage when the Temkin logarithmic isotherm for adsorbed atomic hydrogen is fulfilled. The hydrogen evolution reaction is complicated by hydrogen absorption proceeding in the mode of solid-phase diffusion kinetics.

Performance enhancement of PbS quantum dot solar cells employing a hybrid solid-state ligand exchange protocol

In this work, a hybrid (HB) solid-state ligand exchange strategy was developed for PbS quantum dots (QDs) films, incorporating a synergistic utilization of the popular inorganic ligand tetrabutylammonium iodide (TBAI) and the organic short bidentate linker 1, 2-Ethanedithiol (EDT) in a two-stage process. The two-stage process consisted of a primary solid-state ligand treatment with TBAI in a controlled manner followed by a second-stage ligand treatment with EDT. We could achieve an optimal iodine/EDT ligand passivation ratio for the QDs films by controlling the TBAI ligand treatment time. The method integrates the benefits of both the ligands and resolves the intrinsic incompleteness of the solid-state TBAI ligand exchange. The QDs films thus created have an optimal surface coverage and reduced inter-dot spacing due to an improved QDs close packing. This in turn led to lesser recombination routes due to reduced mid-bandgap trap states and an improved charge transport property through an enhanced electronic coupling between the QDs. A power conversion efficiency of 8.2 % has been achieved in the device with an optimized TBAI /EDT ligand passivation ratio for the QDs films with an EDT hole transport layer.

In‐gap States and Carrier Recombination in Quasi‐2D Perovskite Films

In‐gap states and their effect on recombination rates in quasi‐2D lead–iodide‐based perovskites, intercalated with various spacer molecules, are studied using a combination of scanning tunneling spectroscopy and temperature‐dependent photoconductivity measurements. The results are further analyzed by a Shockley–Read–Hall model. Indications for shallow in‐gap states, positioned at about 0.15–0.2 eV below the bottom of the conduction band, are found. These states are identified as dominating the recombination route of photogenerated carriers in these systems, with a relatively large capture coefficient of about 10−5–10−6 cm3 s−1 at room temperature. First‐principles calculations based on density functional theory imply that these states are not an intrinsic effect of the inclusion of the spacer molecules, but rather one that arises from chemical defect formation or structural deformation of the perovskite layers. The results suggest that further improvement of the performance of solar cells that are based on quasi‐2D perovskites requires, along with enhancing carrier mobility, efforts to suppress the concentration of these detrimental defect states.

Regioselectivity of the Radical Cation Recombination in the Aniline Polymerization

The regioselectivity of the fast stages of the aniline polymerization mechanism is considered. Using the AM1 method, the approaching of the radical cation of an aniline trimer to the aniline radical cation with chloride counterions, as well as the radical cations of the monomer to each other is simulated. It is shown that on passing from the recombination of the aniline radical cations with each other to the recombination of the aniline radical cations with the radical cations of an aniline trimer, the main approaching direction changes from C/N to N/N, which is followed by the semidine rearrangement. The high para-selectivity of the aniline polymerization is explained and the ratio of the rate constants of various recombination routes of the radical cations is evaluated.

Binary heterojunctions of Mg/Al-LDH and carbon-based matrixes derived from self-assembly synthesis for inhibition of pyrene photopolymerizing: Elucidation of LDHs protecting bitumen against UV aging

Layered double hydroxides (LDHs) have been found to protect bitumen against UV aging that was a culprit to shorten service life of new paved roads and burden environment with toxic volatiles in case of repaving roads time and again. Utilizing LDHs to improve the UV resistance to bitumen is desirable but the corresponding mechanism is still not be clarified. In this work, a simple self-assembly strategy is used to synthesize binary-heterojunction catalysts consisting of Mg/Al-LDH and carbon-based matrixes, aiming at obtaining copious mesopores and tailoring photocatalytic routes. The specific surface areas of the binary-heterojunction catalysts reached 193.94 and 156.31 m2/g for Mg/Al-LDH@biocarbon and Mg/Al-LDH@g-C3N4, respectively. It was found that the as-synthesized catalyst of Mg/Al-LDH@g-C3N4 was an outstanding inhibitor in photopolymerizing polycyclic aromatics, which was verified by photochemical experiments using pyrene (PY) as a target. The Mg/Al-LDH@g-C3N4 enabled to decrease the proportion of exciplex of PY to 8.63% upon UV irradiation, while the proportion was as high as 39.81% in the absence of Mg/Al-LDH@g-C3N4. The test results revealed that photogenerated holes and photogenerated electrons were responsible for accelerating the photodegradation process of PY and suppressing the photopolymerization of PY molecules, respectively. The binary-heterojunction Mg/Al-LDH@g-C3N4 showed its outstanding photocatalytic activities under UV irradiation, including avoiding PY molecules from degradation and macromolecular polymerization, which was attributed to the new channel for electron-hole recombination and built-up photocatalytic routes between Mg/Al-LDH and g-C3N4. This work provided a perspective for tailoring promising protective agents for bitumen anti-UV aging through building reasonable photocatalytic routes for heterogeneous structures.

Optically detected magnetic resonance spectroscopic analyses on the role of magnetic ions in colloidal nanocrystals.

Incorporating magnetic ions into semiconductor nanocrystals has emerged as a prominent research field for manipulating spin-related properties. The magnetic ions within the host semiconductor experience spin-exchange interactions with photogenerated carriers and are often involved in the recombination routes, stimulating special magneto-optical effects. The current account presents a comparative study, emphasizing the impact of engineering nanostructures and selecting magnetic ions in shaping carrier-magnetic ion interactions. Various host materials, including the II-VI group, halide perovskites, and I-III-VI2 in diverse structural configurations such as core/shell quantum dots, seeded nanorods, and nanoplatelets, incorporated with magnetic ions such as Mn2+, Ni2+, and Cu1+/2+ are highlighted. These materials have recently been investigated by us using state-of-the-art steady-state and transient optically detected magnetic resonance (ODMR) spectroscopy to explore individual spin-dynamics between the photogenerated carriers and magnetic ions and their dependence on morphology, location, crystal composition, and type of the magnetic ion. The information extracted from the analyses of the ODMR spectra in those studies exposes fundamental physical parameters, such as g-factors, exchange coupling constants, and hyperfine interactions, together providing insights into the nature of the carrier (electron, hole, dopant), its local surroundings (isotropic/anisotropic), and spin dynamics. The findings illuminate the importance of ODMR spectroscopy in advancing our understanding of the role of magnetic ions in semiconductor nanocrystals and offer valuable knowledge for designing magnetic materials intended for various spin-related technologies.

Bicarbonate activation of the monomeric photosystem II-PsbS/Psb27 complex.

In thylakoid membranes, photosystem II (PSII) monomers from the stromal lamellae contain the subunits PsbS and Psb27 (PSIIm-S/27), while PSII monomers (PSIIm) from granal regions lack these subunits. Here, we have isolated and characterized these 2 types of PSII complexes in tobacco (Nicotiana tabacum). PSIIm-S/27 showed enhanced fluorescence, the near absence of oxygen evolution, and limited and slow electron transfer from QA to QB compared to the near-normal activities in the granal PSIIm. However, when bicarbonate was added to PSIIm-S/27, water splitting and QA to QB electron transfer rates were comparable to those in granal PSIIm. The findings suggest that the binding of PsbS and/or Psb27 inhibits forward electron transfer and lowers the binding affinity for bicarbonate. This can be rationalized in terms of the recently discovered photoprotection role played by bicarbonate binding via the redox tuning of the QA/QA•- couple, which controls the charge recombination route, and this limits chlorophyll triplet-mediated 1O2 formation. These findings suggest that PSIIm-S/27 is an intermediate in the assembly of PSII in which PsbS and/or Psb27 restrict PSII activity while in transit using a bicarbonate-mediated switch and protective mechanism.

Multiple-Route Exciton Recombination Dynamics and Improved Stability of Perovskite Quantum Dots by Plasmonic Photonic Crystal.

We have studied the excited-state exciton recombination dynamics of perovskite quantum dots (QDs) through time-resolved photoluminescence (PL), PL blinking, PL intensity-dependent lifetime modulation, and long-term photostability tests. The various spectroscopic characterizations elucidate that the perovskite QDs have multiple intrinsic exciton recombination routes even in a single QD, i.e., exciton, biexciton, and positive/negative trions, which are dissimilarly contributed to ON and OFF state emissions. We also find that the enhanced radiative recombination from placing green QDs on a photonic Ag nanotip array induces notably improved long-term PL stability. We consider that the accelerated radiative recombination of QDs by strong coupling with the plasmonics of the photonic Ag nanotip array, while eliminating nonradiative pathways, is proven to be a critical factor for improved long-term stability.

Modifications in the Kex2 P1' cleavage site in the α-MAT secretion signal lead to higher production of human granulocyte colony-stimulating factor in Pichia pastoris.

The human granulocyte colony-stimulating factor (G-CSF) is one of the hematopoietic growth factors administered for chemotherapy induced neutropenia and is currently produced through recombinant route in Escherichia coli. The methylotrophic unicellular yeast Pichia pastoris (syn. Komagataella phaffii) makes a good host for production of human therapeutics as the proteins are low-mannose glycosylated, disulfide bonded and correctly folded on their way to the cell exterior. Given the low level of production of G-CSF in P. pastoris, the present study examined modification of the Saccharomyces cerevisiae derived α-mating type secretory signal sequence to enhance its production. The substitution of Glu, at the P1' position of the Kex2 cleavage site, by Val/Ala led to extracellular production of ~ 60mg/L of G-CSF in the extracellular medium. Production was further increased to ~ 100mg/L by putting these mutations against rarely occurring methanol slow utilization P. pastoris X-33 host. Analysis of the modelled structure of the signal peptide indicated exposed loop structures, created by presence of Val/Ala, that favour cleavage by the Kex2 peptidase thereby leading to enhanced production of G-CSF. The conformational changes, induced on account of binding between the signal sequence and the cargo protein (G-CSF), also appear to play an important role in the final yield of the extracellular protein.

Illumination Intensity Dependence of the Recombination Mechanism in Mixed Perovskite Solar Cells.

Recombination mechanisms in solar cells are frequently assessed through the determination of ideality factors. In this work we report an abrupt change of the value of the "apparent" ideality factor (nAP ) in high-efficiency FA0.71 MA0.29 PbI2.9 Br0.1 based mesoscopic perovskite solar cells as a function of light intensity. This change is manifested as a transition from a regime characterized by nAP ∼1.8-2.5 at low light intensities (<10 mWcm-2 ) to one characterized by nAP ∼1. This transition is equally observed in the recombination resistance extracted from open-circuit impedance measurements. We use drift-diffusion simulations with explicit consideration of ion migration to determine the origin of this transition. We find that a change ofrecombination mechanism concurrent with a modification of the concentration of ionic vacancies is the most likely explanation of the observed behaviour. In the drift-diffusion simulations we show that the apparent ideality factor is in fact affected by the ion vacancy concentration so it is not the optimal parameter to assess the dominant recombination mechanism. We argue that a procedure based on a recently derived "electronic" ideality factor obtained from the high frequency feature of the impedance spectrum is better suited to determine the recombination route that dictates the photovoltage.

Small is beautiful: virus-like particles as vaccines

Virus-like particles (VLPs) are nanoscale structures that are mimics of virus particles themselves. They are stripped of any infection risk but can perform like viruses in some tasks although they are unable to spread. They are inherently safe and may offer additional advantages when compared to the viruses from which they derive. If they are produced by a recombinant route, as is very common, they can be modified by alteration of the sequences used to add functionality their parental versions did not possess, such as staying in a particular conformation, carrying different cargoes or targeting specific cells. It is probably true that VLPs are ascribed more promise than may ever be realized but their positive attributes are very real, they have already appeared as successful products and their potential is certainly far from exhausted.

Mechanistic Investigation of the Defect Activity Contributing to the Photoluminescence Blinking of CsPbBr3 Perovskite Nanocrystals.

Exploration of the full potential of the perovskite nanocrystals (NCs) for different applications requires a thorough understanding of the pathways of recombination of the photogenerated charge carriers and associated dynamics. In this work, we have tracked the recombination routes of the charge carriers by probing photoluminescence (PL) intermittency of the immobilized and freely diffusing single CsPbBr3 NCs employing a time-tagged-time-resolved method. The immobilized single CsPbBr3 NCs show a complex PL time-trace, a careful analysis of which reveals that nonradiative band-edge recombination through trap states, trion recombination, and trapping of the hot carriers contribute to the blinking behavior of any given NC. A drastically suppressed PL blinking observed for the NCs treated with a tetrafluoroborate salt indicates elimination of most of the undesired recombination processes. A fluorescence correlation spectroscopy (FCS) study on the freely diffusing single NCs shows that enhanced PL and suppressed blinking of the treated particles are the outcome of an increase in per-particle brightness, not due to any increase in the number of particles undergoing "off"-"on" transition in the observation volume. The mechanistic details obtained from this study on the origin of blinking in CsPbBr3 NCs provide deep insight into the radiative and nonradiative charge carrier recombination pathways in these important materials, and this knowledge is expected to be useful for better design and development of bright photoluminescent samples of this class for optoelectronic applications.

Engineered Rhodobacter capsulatus as a Phototrophic Platform Organism for the Synthesis of Plant Sesquiterpenoids.

Sesquiterpenoids are a large class of natural compounds offering manifold properties valuable for food, cosmetics, agriculture, and pharma industry. Production in microorganisms is a sustainable approach to provide sesquiterpenoids for research and industrial use independent of their natural sources. This requires the functional transfer of the respective biocatalytic pathways in an adequate host microorganism offering a sufficient supply of precursors that is ideally adjusted to the individual demand of the recombinant biosynthesis route. The phototrophic purple bacterium Rhodobacter capsulatus offers unique physiological properties that are favorable for biosynthesis of hydrophobic terpenes. Under phototrophic conditions, it develops a large intracytoplasmic membrane suitable for hosting membrane-bound enzymes and metabolites of respective biosynthetic pathways. In addition, Rhodobacter harbors an intrinsic carotenoid biosynthesis that can be engineered toward the production of foreign terpenes. Here, we evaluate R. capsulatus as host for the production of plant sesquiterpenoids under phototrophic conditions using patchoulol and valencene as a proof of concept. The heterologous expression of patchoulol synthase PcPS from Pogostemon cablin as well as the valencene synthases CsVS from Citrus sinensis and CnVS from Callitropsis nootkatensis led to the production of the respective sesquiterpenoids in R. capsulatus. To analyze, if gradually adjustable formation of the key precursor farnesylpyrophosphate (FPP) is beneficial for sesquiterpene synthesis under phototrophic conditions, the intrinsic 1-deoxy-D-xylulose 5-phosphate (DXP) pathway genes as well as the heterologous mevalonate pathway genes were modularly expressed in various combinations. To this end, different plasmids and chromosomally integrated expression tools were developed harboring the strong and tightly controlled Pnif promoter for heterologous gene expression. Notably, comparative studies identified a distinct combination of precursor biosynthetic genes as best-performing setup for each of the tested sesquiterpene synthases. In summary, we could demonstrate that R. capsulatus is a promising alternative platform organism that is suited for sustainable sesquiterpenoid formation under phototrophic cultivation conditions. A modular engineering of R. capsulatus strains via tailored co-expression of FPP biosynthetic genes further allowed adaptation of sesquiterpene precursor formation to its catalytic conversion by different plant terpene synthases.

Dissociative Recombination of CH+ Molecular Ion Induced by Very Low Energy Electrons

We used the multichannel quantum defect theory to compute cross sections and rate coefficients for the dissociative recombination of CH + initially in its lowest vibrational level v i + = 0 with electrons of incident energy below 0.2 eV. We have focused on the contribution of the 2 2 Π state which is the main dissociative recombination route at low collision energies. The final cross section is obtained by averaging the relevant initial rotational states ( N i + = 0 , ⋯ , 10 ) with a 300 K Boltzmann distribution. The Maxwell isotropic rate coefficients for dissociative recombination are also calculated for different initial rotational states and for electronic temperatures up to a few hundred Kelvins. Our results are compared to storage-ring measurements.

Synthesized and Photocatalytic Mechanism of the NiO Supported YMnO3 Nanoparticles for Photocatalytic Degradation of the Methyl Orange Dye

Abstract The YMnO3, NiO, and NiO/YMnO3 nanocomposites are successfully prepared by a polyacrylamide gel method and a simple two phase recombination route. The phase structure, surface morphology, optical, magnetic and electrochemical properties and photocatalytic activity of as-prepared samples were measured by X-ray diffraction (XRD), Scanning electron microscope (SEM), UV-visible spectrophotometer, superconducting quantum interference device (SQUID), electrochemical workstation and 721 spectrophotometer. Phase structure analysis indicate that the YMnO3, NiO, and NiO/YMnO3 nanocomposites has good crystallization and no other impurities. The NiO supported YMnO3 composites improved the surface morphology, optical, magnetic and electrochemical properties and photocatalytic activity of YMnO3 nanoparticles significantly. Photocatalytic experiment analysis indicate that the NiO supported YMnO3 composites exhibits highest photocatalytic activity for degradation of the methyl red dye with dye concentration of 25 mg/L. The excellent photocatalytic activity for the NiO supported YMnO3 composites can be ascribed to the fast interfacial charge transfer, high effective charge separation and the ⋅OH radicals.

The chemical structure effects of alkylbenzenes on soot formation in a laminar co-flow flame

Alkylbenzene isomers are often used in transportation fuel surrogates but have different sooting tendencies. There is a need to understand how their chemical structures affect the soot formation mechanism. In this study, the chemical structure effects of alkylbenzenes (1,2,4-trimethylbenzene (124TMB) and n-propylbenzene (PBZ)) on soot formation in a laminar diffusion flame were experimentally and numerically investigated. In the experiment, the optical time-resolved laser-induced incandescence (LII) and spectral soot emission (SSE) diagnostics were used to measure radial soot volume fraction, primary particle diameter and flame temperature profiles. The radial number density was also experimentally derived. The results are consistent with the literature as 124TMB exhibits higher soot concentration than PBZ. From the analyses of the primary particle diameters and the derived number density, this is caused by the higher soot nucleation rate for 124TMB. This conclusion is supported by numerical modeling, which utilized the detailed CoFlame code with a moderately reduced CRECK mechanism. The simulation results show that 124TMB has earlier soot inception and Polycyclic Aromatic Hydrocarbon (PAH) addition than PBZ. Consistent with both earlier soot inception and PAH addition, the 124TMB model predicts earlier pyrene (A4) formation, suggesting 124TMB has alternative reaction pathways for pyrene formation. The reaction pathway analysis suggests that pyrene is formed via the aromatic radical recombination route, as opposed to the conventional HACA mechanism. Bypassing the formation of the second ring could be the reason for 124TMB having earlier soot nucleation. In contrast, the PBZ model predicts that the formation of pyrene follows the slower HACA pathways, leading to later soot nucleation.

CFD and kinetic modelling study of methane MILD combustion in O2/N2, O2/CO2 and O2/H2O atmospheres

To deepen the understanding of combining moderate or intense low-oxygen dilution (MILD) combustion with oxy-fuel combustion for enhancing flame stability while realizing carbon capturing and storage, this paper presents a numerical study of methane MILD combustion in three atmospheres, i.e.: O2/N2, O2/CO2 and O2/H2O, with both computational fluid dynamics (CFD) and kinetic calculation approaches. Firstly, CFD predictions for the three conditions were performed following a systematic validation of the numerical method against experimental measurement from methane/air MILD combustion in a laboratory-scale closed furnace. Subsequently, kinetic calculations with a well-stirred reactor model was used to quantitatively identify the operating ranges of MILD combustion in the three atmospheres for methane. Moreover, the kinetic calculation provided additional insight into the fuel oxidation pathway. The results reveal that replacing N2 with either CO2 or H2O would help to establish MILD combustion mode from the viewpoint of lower temperature increase, due to both physical and chemical property discrepancies among the diluents. Specifically, the chemical effect and physical effect are responsible to the lower temperature rise for CO2-diluted case and H2O-diluted case, respectively. Inside the MILD combustion furnace, the negative heat release region disappears in regardless of atmospheres, indicating the eliminated fuel pyrolysis process under MILD combustion mode. Detailed analysis of the flame structure suggests that the combustion regimes inside the furnace in the three atmospheres are all in well-stirred combustion regime, and CO2-diluted case has the most extended reaction zone. Kinetic calculation indicates that CO2 or H2O dilution would result in a wider MILD combustion operating range compared to N2 dilution, while it is more pronounced for CO2. These observations all imply that MILD combustion will be more easily established with CO2 dilution than N2 or H2O dilution. However, higher CO formation is obtained in O2/CO2, forcing more attention to be paid on CO emission under CO2-diluted MILD combustion. Furthermore, the hydrocarbon recombination route is negligible under MILD combustion in spite of the atmospheres, implying lower sooting tendency as compared with conventional combustion.

Pyrolytic behavior of coal-related model compounds connected with C–C bridged linkages by in-situ pyrolysis vacuum ultraviolet photoionization mass spectrometry

Coal pyrolysis is generally considered to initiate by cleavage of weak covalent bonds bridged between aromatic rings. The C–C covalent bonds are predominant bridged linkages among the framework of coal, which have a critical influence on coal pyrolysis reaction but lack of direct online observation. Five representative coal-related model compounds containing C–C bridged bonds, polypropylene (PP), polyvinylpyrrolidone (PVP), poly-4-vinylpyridine (P4VP), polystyrene (PS) and poly-4-vinylphenol, were selected to pyrolyze in an in-situ pyrolysis vacuum ultraviolet photoionization mass spectrometry (Py-VUV-PIMS). The soft ionized mass spectral detection can provide product distribution and evolved information of original products and intermediates, which are the key evidence to understand the initiation, recombination and reaction routes during pyrolysis process. Online analysis of pyrolysis reaction was found to be priority with cracking of C–C bond in the five polymer samples, and homologous free radicals and original products, which mainly include monomers, dimers and their alkyl and alkenyl radicals, were detected. The results reveal the cleavage temperature of C–C covalent bond is deeply related to its chemical environment, and obvious conjugation effect and steric effect for the bridged linkage were observed. In addition, the effect of hydrogen bond was also observed during the pyrolysis of model compounds containing hydroxyl groups, and intramolecular or intermolecular hydrogen bonding reduced the temperature at which C–C bridged bonds break. The analogous fracture mode and pyrolysis behavior of coal-related model compounds, which are beneficial to understand the reaction route and mechanism of coal pyrolysis, were discussed based on the experimental observations and theoretical calculation.

Importance of Compact Blocking Layers to the Performance of Dye-Sensitized Solar Cells under Ambient Light Conditions

Power generation in indoor environments is the next step in dye-sensitized solar cell (DSSC) evolution. To achieve this goal, a critical recombination route which is usually inhibited by the TiCl4-derived blocking layers (BLs), that is, charge transfer at the fluorine-doped tin oxide substrate/electrolyte interface, is of concern. In this study, we demonstrate that because of low surface coverage, the conventional TiCl4 BLs are unable to suppress such electron leakage, thus limiting the photovoltaic performance of Co(bpy)32+/3+-mediated DSSCs (bpy = 2,2'-bipyridine) under ambient lighting. On the other hand, by introducing compact BLs prepared by spray pyrolysis, the DSSCs show lower dark current and operate efficiently not only under high-intensity sunlight but also under ambient light conditions. The better blocking function of the compact BL is verified by the cyclic voltammetry; other thin-film preparation methods, except for the common TiCl4 treatment, are anticipated to realize a similar blocking effect. This study illustrates that dense thin film with a predominant blocking function is highly required as the BL for DSSCs under low-light conditions, and this concept will pave the way for more development of indoor DSSCs.