Regulating PdC3/PtC3···thiophene interaction by small molecule doping (AgOTf,CuBr, CuI,CuBr2, PdCl2)

Structural Chemistry - The influences of small molecule doping on PdC3/PtC3···thiophene interaction have been investigated by atoms in molecules (AIM) theory, electron location...     

Recent advances of organometallic complexes in emerging photovoltaics

Organometallic complexes (OMCs) consisting of organic and metal active moieties have shown immense potential for application in solar cells. The diverse structure, rich porosity, and unique charge centers of OMCs enable them to be functional in solar cells. In this review, we introduced four types of OMCs, such as crown organometallic complexes, β-diketone metal complexes, cyclometallic complexes, and main chain metal-containing polymers, providing an in-depth analysis of the structure-performance relationship. OMCs could serve as active or interlayer materials in a variety of solar cell systems such as organic solar cells, perovskite solar cells, and dye-sensitized solar cells, especially some metals to improve the photoelectric performance of the device as dopants. In the end, perspectives on the opportunities and challenges of OMCs are given.     

Study of nano‐Cu/SiO2 catalysts for highly selective hydrogenation of acetophenone

Hydrogenation of acetophenone over nano‐Cu/SiO₂ catalysts was investigated. The catalysts, prepared by a liquid precipitation method using various precipitating agents, were characterized using low‐temperature nitrogen adsorption, X‐ray diffraction, temperature‐programmed desorption of ammonia, hydrogen temperature‐programmed reduction, transmission electron microscopy and X‐ray photoelectron spectroscopy. It was found that the catalysts prepared by a homogeneous precipitation method had better activity and stability than those prepared by a co‐precipitation method. The catalyst prepared using urea as precipitating agent had well‐dispersed copper species, high surface area and abundant pore structure. The catalytic performance and mechanism of the Cu/SiO₂ catalysts were further studied. It was found that the activity and stability of the catalysts could be improved by adjusting the proportion of Cu⁺/(Cu⁺ + Cu⁰). The sample prepared using urea as precipitating agent presented higher activity and selectivity. Also, the catalyst prepared using urea maintained a high catalytic performance while being continuously used for 150 h under the optimal reaction conditions.     

Monodisperse Six-Armed Starbursts based on Truxene-Cored Multibranched Oligofluorenes: Design,Synthesis, and Stabilized Lasing Characteristics

A series of monodisperse six-armed conjugated starbursts ( Tr1F , Tr2F , and Tr3F ) containing a truxene core and multibranched oligofluorene bridges capped with diphenylamine (DPA) units has been designed, synthesized, and investigated as robust gain media for organic semiconductor lasers (OSLs). The influence of electron-rich DPA end groups on their optoelectronic characteristics has been discussed at length. DPA cappers effectively raise HOMO levels of the starbursts, thus enhancing the hole injection and transport ability. Solution-processed electroluminescence devices based on the resulting six-armed starbursts exhibited efficient deep-blue electroluminescence with clear reduced turn-on voltages (3.2–3.5 V). Moreover, the resulting six-armed molecules showed stabilized electroluminescence and amplified spontaneous emission with low thresholds (27.4–63.9 nJ pulse⁻¹), high net gain coefficients (80.1–101.3 cm⁻¹), and small optical loss (2.6–4.4 cm⁻¹). Distributed feedback OSLs made from Tr3F exhibited a low lasing threshold of 0.31 kW cm⁻² (at 465 nm). The results suggest that the construction of truxene-centered six-armed conjugated starbursts with the incorporation of DPA units can effectively enhance EL properties by precisely regulating the HOMO energy levels, and further optimizing their optical gain properties.     

Impact of post-injection strategy on the physicochemical properties and reactivity of diesel in-cylinder soot

Post injection has significant benefit in the reduction of diesel soot emissions. Therefore, there is a need to understand the effect of post-injection strategy on soot physicochemical properties and reactivity because they play an important role in soot oxidation process that governs the final soot emissions. This work focuses on the impact of post injection on the physicochemical properties and reactivity of diesel in-cylinder soot using a main plus post injection (M*P) and a single injection (M) strategy. The soot was sampled by a developed total cylinder sampling system, and the dividing points of soot formation-dominant and oxidation-dominant phases were used for studying the impacts of post injection on the characteristics of in-cylinder soot. The physicochemical properties of the soot samples, including primary particle size, nanostructure, carbon chemical state and surface functional groups, were characterized. The soot reactivity was evaluated in terms of peak temperature, burnout temperature and apparent activation energy. In the oxidation-dominant phase, the M*P soot initially possesses smaller primary particle size, shorter fringe length, larger tortuosity, lower sp²/sp³ hybridization ratio of carbon atoms and higher content of aliphatic CH groups than the M soot. The beneficial influence of physicochemical properties on soot reactivity when using post injection is validated by the thermogravimetric data, which shows that the M*P soot is more reactive than the M soot at the onset of the oxidation-dominant phase. In the M*P case, the soot generated from the main-injection combustion has lower reactivity than the soot from the post-injection combustion after they experience the soot formation-dominant phase. The results indicate that the use of post injection leads to in-cylinder soot with physicochemical properties that favor reactivity. The enhancement of reactivity means that the soot will be more readily oxidized in the subsequent combustion process, and consequently contributes to a reduction in final soot emissions.     

Photoinduced dynamics of a cyanine dye: parallel pathways of non-radiative deactivation involving multiple excited-state twisted transients

Cyanine dyes are broadly used for fluorescence imaging and other photonic applications. 3,3′-Diethylthiacyanine (THIA) is a cyanine dye composed of two identical aromatic heterocyclic moieties linked with a single methine, –CH. The torsional degrees of freedom around the methine bonds provide routes for non-radiative decay, responsible for the inherently low fluorescence quantum yields. Using transient absorption spectroscopy, we determined that upon photoexcitation, the excited state relaxes along two parallel pathways producing three excited-state transients that undergo internal conversion to the ground state. The media viscosity impedes the molecular modes of ring rotation and preferentially affects one of the pathways of non-radiative decay, exerting a dominant effect on the emission properties of THIA. Concurrently, the polarity affects the energy of the transients involved in the decay pathways and further modulates the kinetics of non-radiative deactivation.     

Catalytic activities of NHC‐PdCl2 species based on functionalized tetradentate imidazolium salt in three types of C‐C coupling reactions

A functionalized tetradentate imidazolium salt 9,10‐bis{di[2′‐(N‐ethylimidazolium‐1‐yl)ethyl]aminomethyl}anthracene tetrakis(hexafluorophosphate) ( 1 ) has been synthesized and characterized. The catalytic activity of the NHC‐PdCl₂ species formed by compound 1 and PdCl₂ was tested in Suzuki‐Miyaura, Heck‐Mizoroki and Sonogashira reactions. The results showed that this catalytic system was effective for above three types of C‐C coupling reactions.     

The protective effect of electroacupuncture on the renal cortex of SHRs: A metabonomic analysis

Hypertension affects multiple organs in the body during the development of the disease. The antihypertensive effect of acupuncture has been confirmed. How the protective effect of electroacupuncture on the renal cortex of the spontaneously hypertensive rat (SHR) is achieved has not yet been determined. The purpose of this study was to understand the impact of electroacupuncture on the blood pressure of SHRs and the impact on metabolites in the renal cortex, looking for potential differential metabolites and then proceeding to the next step of exploratory research. The experimental animals were divided into four groups: control group, model group, electroacupuncture group and losartan potassium group. Electroacupuncture on bilateral Taichong (LR3) and Zusanli (ST36) lasted for 3 weeks, and the renal cortex was collected for metabonomics research. UHPLC–MS was used to analyze the changes in the metabolic spectrum of renal cortex tissue. The results showed that electroacupuncture can significantly reduce the blood pressure of SHRs. A total of 12 metabolites changed significantly in the comparison between each group and the model group.The possible mechanism is that the primary bile acid biosynthesis, bile secretion, tryptophan metabolism and other metabolic pathways affect the renal cortex.     

Mechanically strong and stiff supramolecular polymers enabled by fiber reinforced long-chain alkane matrix

Fiber-reinforced-concrete (FRC) mechanism refers short discrete fibers that are uniformly distributed and randomly oriented, which offers an effective way to improve the mechanical performance of concrete. In the design of supramolecular polymers, an analogous concept of FRC appears to have been considered very rarely-although fibrous structure has been frequently observed/generated during the supramolecular polymerization. In this work, we apply the alkane thermosets, octadecane (C₁₈H₃₈) and tetracosane (C₂₄H₅₀), taking the role of “concrete”, and the low-molecular-weight monomer with long alkyl chains as the essential “fiber” component, to fabricate the “fiber reinforced supramolecular polymer”. Very much like FRC mechanism in material science, the resulting fiber reinforced supramolecular polymer thus exhibit unusually high mechanical strength and stiffness, which is unprecedented in the conventional supramolecular strategy.