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Three photoactive Cd(II) coordination polymers (CPs), [Cd (Fsbpe)(DBBA) 2 ]·2DMF (CP 1 ), [Cd(Fepbpe)(DBBA) 2 ]·2DMF (CP 2 ) and [Cd(Fsbpeb)(DBBA) 2 ] (CP 3 ) (DBBA = 3,5-dibromobenzoic acid, DMF = dimethyl formamide) with similar 1D chain motifs exhibited completely different photosalient behaviors (PS) in response to UV light. Mechanical motion was triggered by [2+2] photocycloaddition and regulated by positioning of the photoactive alkene centers relative to the crystal axis. This solid-state reaction was reversed by heating and photomechanical behaviour was repeated over several cycles. A simple photoactuating device was prepared using a CP3-PVA composite.

Two new cationic meso -thiazolium-BODIPY-based water-soluble and red-shifted fluorescent probes were constructed for the first time. They can monitor cellular viscosity in dual organelles and show aggregation-induced emission (AIE), which is ascribed to the efficient restricted rotation of meso -thiazolium in viscous or hindered systems. Probe 3 with an N -benzyl group shows better AIE as compared to probe 2 with an N -methyl group.

Group theory is a powerful tool to explore fundamental symmetry constraints for the physical properties of crystal structures, e.g. it is well-known that only a few components of the elastic constants are independent due to the symmetry constraint. This work further applies group theory to derive constraint relationships for high-order elastic constants with respect to the orientation angle, where the constraint relationships are more explicit than the traditional tensor transformation law. These analytic symmetry constraints are adopted to explain the molecular dynamics simulation results, which disclose that the high-order elastic constants are highly anisotropic with an anisotropy percentage of up to 25% for the hexagonal boron nitride monolayer. The elastic constant is a basic quantity in the mechanics field, so its high anisotropy shall cause strong anisotropy for other mechanical properties. Based on the anisotropic high-order elastic constants, we demonstrate that Poisson's ratio is highly anisotropic for the hexagonal boron nitride at large strains. These findings provide fundamental insights into the symmetry dependence of high-order elastic constants and other mechanical properties.

Mechanical computers have gained intense research interest at size scales ranging from nano to macro as they may complement electronic computers operating in extreme environments. While nanoscale mechanical computers may be easier to integrate with traditional electronic components, most current nanomechanical computers are based on volatile resonator systems that require continuous energy input. In this study, we propose a non-volatile nanomechanical bit based on the quasi-stable configurations of few-layer graphene with void defects, and demonstrate its multiple quasi-stable states by deriving an analytic relationship for the void configuration based on a competition between the bending energy and the cohesive energy. Using this nanomechanical bit, typical logic gates are constructed to perform Boolean calculations, including NOT, AND, OR, NAND and NOR gates, and demonstrate reprogrammability between these logic gates. We also study the accuracy and the stability of the nanomechanical bits based on the few-layer graphene. These findings provide a novel approach to realize the nanomechanical computing process.

The heat transport properties of van der Waals layered structures are crucial for ensuring the reliability and longevity of high-performance optoelectronic equipment. Owing to the two-dimensional nature of atomic layers, the presence of bubbles is commonly observed within these structures. Nevertheless, the effect of bubbles on the interfacial thermal conductance remains unclear. Based on the elastic membrane theory and the improved van der Waals gas state equation, we develop an analytical formula to describe the influence of bubble shape on the interfacial thermal conductance. It shows that the presence of bubbles has a considerable impact on reducing the interfacial thermal conductance across graphene/graphene interfaces. More specifically, the presence of nanobubbles can result in a reduction of up to 53% in the interfacial thermal conductance. The validity of the analytical predictions is confirmed through molecular dynamic simulations. These results offer valuable insights into the thermal management of van der Waals layered structures in the application of next-generation electronic nanodevices.

Exploration of novel carbon allotropes has been a central subject in materials science, in which carbon peapods hold great potential as a precursor for the development of new carbon allotropes. To enable precise large-scale molecular dynamics simulations, we develop a high-accurate and low-cost machine-learned potential (MLP) for carbon materials using the neuroevolution potential framework. Based on the MLP, we conduct an investigation into the structural transitions of peapod arrays under high-temperature and high-pressure conditions and disclose the impact of vacancy defects. Defects promote the transition from the ordered crystalline structure to the disordered amorphous structure in peapods at low temperatures, while impeding the transition to the ordered diamond structure. Benefiting from the accurate MLP, we are able to reproduce the experimentally observed carbon structures in numerical simulations. We build a diagram summarizing all the structures that appear in the compression simulation of peapod arrays at various temperatures. The present work not only discloses the underlying mechanism of structural transitions from carbon peapods into various functional carbon materials, but also provides a high-accurate and low-cost interatomic potential that shall be valuable in the exploration of novel carbon allotropes.

Bladder cancer (BC) is one of the most common malignant tumors in the urinary system, and its high recurrence rate is a great economic burden to patients. Traditional diagnosis and treatment methods have the disadvantages of insufficient targeting, obvious side effects and low sensitivity, which seriously limit the accurate diagnosis and efficient treatment of BC. Due to their small size, easy surface modification, optical properties such as plasmon resonance, and surface enhanced Raman scattering, good electrical conductivity and photothermal conversion properties, nanomaterials have great potential application value in the realization of specific diagnosis and targeted therapy of BC. At present, the application of nanomaterials in the diagnosis and treatment of BC is attracting great attention and achieving rich research results. Therefore, this paper summarizes the recent research on nanomaterials in the diagnosis and treatment of BC, clarifies the existing advantages and disadvantages, and provides theoretical guidance for promoting the accurate diagnosis and efficient treatment of BC.

The mechanism of Sn and Nb influence on the fraction of tetragonal ZrO 2 in oxide films on Zr alloys and their influence mechanism on corrosion resistance of Zr alloys, despite decades of research, are ambiguous due to the lack of kinetic knowledge of phase evolution of ZrO 2 with doping. Using stochastic surface walking and density functional theory calculations, we investigate the influence of Nb and Sn on the stability of tetragonal (t) and monoclinic (m) ZrO 2 , and t-m phase transition in oxide films. We found that though Nb and Sn result in similar apparent variation trends in the t-phase fraction in oxide films, their influences on t-m phase transition differ significantly, which is the underlying origin of different influences of the t-phase fraction in oxide films on the corrosion resistance of Zr alloys with Sn and Nb alloying. These results clarify an important aspect of the relationship between the microstructure and corrosion resistance of Zr alloys.

Single-walled carbon nanotubes (SWCNTs) possess extremely high thermal conductivity that benefits their application in high-performance electronic devices. The characteristic hollow configuration of SWCNTs is not favorable for the buckling stability of the structure, which is typically resolved by fullerene encapsulation in practice. To investigate the fullerene encapsulation effect on thermal conductivity, we perform molecular dynamics simulations to comparatively study the thermal conductivity of pure SWCNTs and fullerene encapsulated SWCNTs. We focus on disclosing the relationship between the vacancy defect and the fullerene encapsulation effect on thermal conductivity. It is quite interesting that vacancy defects weaken the coupling strength between the nanotube shell and the fullerene, especially for narrower SWCNTs (9, 9), which will considerably reduce the effect of fullerene encapsulation on the thermal conductivity of narrower SWCNTs. However, for thicker SWCNTs (10, 10) and (11, 11), vacancy defects have an ignorable effect on the coupling strength between the nanotube shell and the fullerene due to plenty of free space in thicker SWCNTs, so vacancy defects are not important for the fullerene encapsulation effect on the thermal conductivity of thicker SWCNTs. These findings shall be valuable for the application of SWCNTs in thermoelectric fields.

A cascade spiroannulation of 2-mercaptoquinoline-3-carbaldehydes with α,α-dicyanoalkenes as well as a cascade spiroannulation of 2-mercaptoquinoline-3-carbaldehydes aldehydes with α-bromocarbonyl compounds was investigated based on a synergistic strategy, providing a series of diverse spiro-fused heterocyclic compounds containing more different functional groups. The features of this strategy directed towards molecular complexity and diversity include step economy, mild conditions, and high bond-forming efficiency, but important polycyclic heterocyclic products, which could be transformed into potential biologically interesting heterocyclic structures.

Four Cd(II)/diene coordination polymers (CPs) with similar 1D chain motifs exhibit different photosalient (PS) behaviours in response to UV light. The [2+2] photoreaction between the CC groups within these CPs results in diverse PS behaviours of their crystals with different CC pair arrangements. The interesting PS behaviours of these CPs can be applied in design and fabrication of advanced photoactuating materials.

Two novel meso -CF 3 BODIPY-based fluorescent rotors have been rationally prepared and found to sensitively respond to viscosity in living cells with a fluorescence "turn-on" effect, attributed to the special restricted rotation of meso -CF 3 group in viscous environments. Interestingly, a monostyryl probe with one cationic group exhibits good mitochondrial localization and AIE property.

We report here that polysubstituted cyclopent-2-enols can be constructed by the one-pot reaction of doubly activated cyclopropanes and α-EWG substituted acetonitriles under mild basic conditions via a domino-ring-opening-cyclization/deacylation/oxidation sequence. Moreover, the synthetic applications of these cyclopent-2-enols have been demonstrated in the late-stage derivatization into functionalized cyclopentapyrimidin-4-ones and 2-hydroxy cyclopentanones with good yields.

Because of their advanced properties inherited from their constituent atomic layers, van der Waals heterostructures such as graphene/MoS 2 are promising candidates for many optical and electronic applications. However, because heat tends to be generated during the operation of nanodevices, thermal expansion is an important phenomenon to consider for the thermal stability of such heterostructures. In the present work, molecular dynamics simulations are used to investigate the thermal expansion coefficient of the graphene/MoS 2 heterostructure, and how the unavoidable misfit strain affects that coefficient is revealed. The misfit strain can tune the thermal expansion coefficient by a factor of six, and this effect is quite robust in the sense that it is insensitive to the size or direction of the heterostructure. Further analysis shows that the misfit strain offers an efficient means of engineering thermally induced ripples, this being the key mechanism for how the misfit strain affects the thermal expansion coefficient. These findings provide valuable information about the thermal stability of van der Waals heterostructures and offer help for practical applications of nanodevices based on such heterostructures.

Forming heterostructures is a well-established technique to utilize different constituent materials to achieve novel properties like efficient light emission and high-quality electron tunneling. Recent experiments have successfully synthesized one-dimensional van der Waals heterostructures and have discovered plenty of superior properties benefiting from the dimension reduction. Inspired by the success of the van der Waals counterparts, we propose a one-dimensional lateral heterostructure based on transition metal dichalcogenide nanotubes. Molecular simulations show that the misfit strain is restricted to the radial direction due to the one-dimensional tubular confined structure, and the regular exponential distribution of the radial misfit strain can be well interpreted by a mechanics model. Besides the normal exponential distribution, there also exists an abnormal strain distribution within a narrow domain nearby the interface, in which the structure of the larger lattice constant is stretched instead of compressed by the misfit strain. The abnormal misfit strain is due to the interplay between several bending interactions and the stretching interaction. Possible experiments to synthesize this new type of heterostructure are discussed based on current experimental techniques.

Epsilon-near-zero (ENZ) properties have been reported in organic molecular films. In particular, cyanine and squaraine films have been shown to exhibit ENZ properties in the visible spectral region with a strong 3 rd order nonlinear optical response near the ENZ spectral region. Noting both cyanine and squaraine belong to the polymethine family, a series of six curcuminoid borondifluoride (Curc) derivatives were developed to examine whether such a polymethine character is positively correlated with the ENZ property of the organic films. Those Curc derivatives possess a Donor-Acceptor-Donor (D-A-D) architecture with acceptor, AcacBF 2 , located at the molecular center. The backbone of Curc is designed such that the donor strength can be tuned to transit between charge transfer (CT) and polymethine character. This balance between CT and polymethine character of the Curc series is examined based on the Lippert-Mataga plot. As donor strength in the D-A-D structure increases, CT character is less marked resulting in a more dominant polymethine character. The structural and optical properties of the Curc films with a thickness in the order of 30 nm were examined to correlate the polymethine character with the ENZ response. The results obtained in isotropic Curc thin films demonstrate that an increase of polymethine character associated with a stronger donor strength leads to an appearance/enhancement of the ENZ property in the visible spectrum range from 500 to 670 nm. Overall, this study provides useful guidelines to engineer new organic materials showing ENZ properties in a desired spectral range., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

We report here that a series of bridged O,O-ketal fused spiro piperidone-cyclopropane derivatives 3 can be constructed with excellent yields and good diastereoselectivity by the one-pot reaction of 1-acylcyclopropanecarboxamides 1 with electron-deficient alkene 2a (EWG = CHO) via the domino process involving [4 + 2] annulation/intermolecular electrophilic addition/intramolecular cyclization. Furthermore, reactions of 1 with 2b/2c (EWG = CN, COOMe), leading to spiro piperidone-cyclopropane derivatives 4 or 5 by base catalyst selection, were also presented.

The microfluidic flow is typically laminar due to the dominant viscous effects. At Reynolds numbers far below 1 (Re ≪ 1), the fluid inertia can be neglected. For the steady flow of incompressible Newtonian fluids, it approaches linear Stokes flow. At intermediate Re, there exists a weak-inertia flow regime where secondary flows such as Dean vortices are accessible for microfluidic manipulations. Apart from the fluid inertia, other nonlinear factors such as the non-Newtonian fluid properties, concurrent flow of dissimilar fluids, compliant fluidic structures and stimuli-responsive materials can also cause intriguing flow behaviours. Through proper designs, they can be applied for a variety of microfluidic components including mixers, valves, oscillators, stabilizers and auto-regulators etc., greatly enriching the microfluidic flow control and manipulation strategies. Due to its unique working characteristics and advantages, nonlinear microfluidics has increasingly attracted extensive attention. This review presents a systematic survey on this subject. The designs of typical nonlinear microfluidic devices, their working mechanisms, key applications, and the perspective of their future developments will be discussed. The nonlinear microfluidic techniques are believed to play an essential role in the next generation of highly-integrated, automated, and intelligent microfluidics.

As hydrogen-bond donors and acceptors, N , N '-disubstituted sulfamides have been used in a range of applications from medicinal chemistry to anion-binding catalysis. However, compared to ureas or thioureas, the utilization of this unique moiety remains marginal, in part because of a lack of general synthetic methods to access unsymmetrical sulfamides. Specifically, polysulfamides are a virtually unknown type of polymer despite their potential utility in non-covalent dynamic networks, an intense area of research in materials science. We report herein a practical and efficient process to prepare unsymmetrical sulfamides via Sulfur(vi)-Fluoride Exchange (SuFEx) click chemistry. This process was then applied to synthesize polysulfamides. Thermal analysis showed that this family of polymers possess high thermal stability and tunable glass transition temperatures. Finally, hydrolysis studies indicated that aromatic polysulfamides could be recycled back to their constituting monomers at the end of their life cycle., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A lysosome-targeting dual-functional fluorescent probe was rationally designed and developed for imaging intracellular lysosomal viscosity and beta-amyloid. More importantly, the real-time tracking of the dynamic movement of lysosomes, as vesicle structures, has been achieved using Lyso-MC.

A new 3D MOF [MnLi 2 (ip) 2 (H 2 O) 2 ] (1) with a 1D heterometallic inorganic Mn(ii)-Li(i) chain is reported. With the assistance of diamagnetic {LiO 4 } connectors, which separate the paramagnetic Mn(ii) ions and act as magnetic spacers, very weak magnetic interactions were obtained. Remarkably, 1 showed a significant magnetocaloric effect (MCE) with a large entropy change value of 30.4 J kg -1 K -1 for ΔH = 8 T at 2 K.

Two neutral merocyanine-based near-infrared fluorescent probes were for the first time developed through rational engineering of the classical cationic cyanine scaffold IR-780 for in vivo imaging of amyloid-β plaques. In vivo NIRF imaging revealed that the probe could penetrate the blood-brain barrier and efficiently differentiate the living transgenic and wild-type mice.

A hemicurcuminoid boron difluoride complex is used as an emitter in organic light-emitting diodes, showing far red/near-infrared electroluminescence with an external quantum efficiency as high as 2.1%. This dye blended in CBP thin films shows amplified spontaneous emission with a threshold of 22 μJ cm -2 at 750 nm, making this compound attractive for organic semiconductor lasers operating in the near-infrared region.

Apoptosis and necrosis are distinct cell death processes related to many cellular pathways. In situ , quantitatively and dynamically monitoring such processes may provide vitally important information for cell studies. However, such a method still remains elusive, even though current immunochemical methodologies have developed extremely valuable tools. Herein, we demonstrate Raman spectroscopic metrics for validating and quantifying apoptotic and necrotic cells based on their distinct molecular vibrational fingerprints. It not only allows us to quantify apoptotic and necrotic cell populations in situ in adherent cell samples, but also to be capable of continuously monitoring the dynamical processes of apoptosis and necrosis at the same time in one sample. This method provides comparable results with the "gold standard" of flow cytometry, moreover, with several incomparable advantages. Our work offers a powerful new tool for cell apoptosis and necrosis assays and is expected to become a benchmark technology in biological and medical studies.

A general and effective method for the synthesis of amides through decarboxylative amidation of α-keto acids with amines has been developed. The reaction proceeded smoothly to afford the corresponding amide products in good yield under air and shows excellent functional group tolerance. In addition, the protocol can be further applied in the synthesis of heterocyclic compounds like benzimidazoles.

A colorimetric and fluorescent dual probe for palladium species was rationally developed by combining the resorufin fluorophore with allyl chloroformate. The probe enables the visual detection of palladium based on its vivid color change from pale yellow to pink and its fluorescence off-on response to palladium in PBS solution. The detection limit was calculated to be as low as 2.1 nM. The live cell imaging results showed that this probe could be used as an effective fluorescent probe for detecting intracellular palladium species. All these results featured its promising application prospects in the palladium analytical field.

We investigate the photophysical properties of organic donor-acceptor dyad and triad molecular systems based on triphenylene and perylene diimide units linked by a non-conjugated flexible bridge in solution using complementary optical spectroscopy techniques. When these molecules are diluted in dichloromethane solution, energy transfer from the triphenylene to the perylene diimide excited moieties is evidenced by time-resolved fluorescence measurements resulting in a quenching of the emission from the triphenylene moieties. Simultaneously, another quenching process that affects the emission from both donor and acceptor units is observed. Solution ultrafast transient absorption measurements provide evidence of photo-induced charge transfer from either the donor or the acceptor depending upon the excitation. Overall, the analysis of the detailed time-resolved spectroscopic measurements carried out in the dyad and triad systems as well as in the triphenylene and perylene diimide units alone provides useful information both to better understand the relations between energy and charge transfer processes with molecular structures, and for the design of future functional dyad and triad architectures based on donor and acceptor moieties for organic optoelectronic applications.

Hemicurcuminoids are based on half of the π-conjugated backbone of curcuminoids. The synthesis of a series of such systems and their borondifluoride complexes is described. The electrochemical and photophysical properties of difluorodioxaborine species were investigated as a function of the nature of electron donor and acceptor groups appended at either terminal positions of the molecular backbone. The emissive character of these dipolar dyes was attributed to an intraligand charge transfer process, leading to fluorescence emission that is strongly dependent on solvent polarity. Quasi-quantitative quenching of fluorescence in high polarity solvents was attributed to photoinduced electron transfer. These dyes were shown to behave as versatile fluorophores. Indeed, they display efficient two-photon excited fluorescence emission leading to high two-photon brightness values. Furthermore, they form nanoparticles in water whose fluorescence emission quantum yield is less than that of the dye in solution, owing to aggregation-induced fluorescence quenching. When cos7 living cells were exposed to these weakly-emitting nanoparticles, one- and two-photon excited fluorescence spectra showed a strong emission within the cytoplasm that originated from the individual molecules. Dye uptake thus involved a disaggregation mechanism at the cell membrane which restored fluorescence emission. This off-on fluorescence switching allows a selective optical monitoring of those molecules that do enter the cell, which offers improved sensitivity and selectivity of detection for bioimaging purposes.

A kinked silicon nanowire (KSiNW) is a zigzag-shaped nanowire with its growth direction changing regularly at the kinking joints, resulting in a quasi-two-dimensional structure. An intrinsic tendency for the two-dimensional system is to generate some out-of-plane vibrations to withstand the mechanical instability in the third dimension. In the present work, we report a lattice dynamical study of the intrinsic out-of-plane twisting vibration of KSiNWs. We derive the dynamical matrix analytically, and explore the kinking effect on the phonon spectrum of the KSiNWs. Based on lattice dynamical analysis, we obtain an analytical formula for the geometrical dependence of the twisting amplitude of the KSiNWs. The analytical formula provides valuable information on the kinking induced twisting stability of KSiNWs serving as bio-probes for intracellular recording application.

A colorimetric and red-emitting fluorescent dual probe for G-quadruplexes was devised with a conjugated coumarin-benzothiazole scaffold. Its significant and distinct changes in both color and fluorescence enable the label-free and visual detection of G-quadruplex structures. In addition, this probe gives a distinct strong emission response to the nucleoli in fixed cells imaging, which might be attributed to the interaction between the probe and rDNA G-quadruplex based on the chromatin immunoprecipitation assay. All these results suggest its promising application prospects in the G-quadruplex research field.

Nanotubular TiO2 has attracted considerable attention owing to its unique functional properties, including high surface area and vectorial charge transport along the nanotube, making it a good photocatalytic material. Anodic TiO2-nanotube (TiNT) arrays on a Ti foil substrate were prepared by electrochemical anodic oxidation and SEM/HRTEM/XRD analyses have suggested that the walls of TiO2 tubes are formed from stacked [101] planes (anatase). Both HRTEM and XRD indicate an interplanar spacing of d101 = 0.36 nm in the wall structure. Despite the large amount of work done on nanotube synthesis, a thorough investigation of the electronic and atomic structures of free-standing TiNT arrays has not yet been carried out. X-ray absorption spectroscopy (XAS), resonant inelastic X-ray scattering (RIXS) and scanning photoelectron microscopy (SPEM) are employed herein to examine the electronic and atomic structures at the top and bottom of TiNT arrays. These analyses demonstrate the presence of mixed valence states of the Ti ions (Ti(3+) and Ti(4+)) and a structural distortion at the bottom cap region of the TiNT. Additionally, the results obtained herein suggest the formation of a defective anatase phase at the bottom cap barrier layer between the Ti foil substrate and TiNT during the growth of electrochemically anodized nanotubes.

A novel Au NP mediated dual-potential ECL ratiometric approach for highly sensitive protein kinase activity and inhibition assay has been developed based on the simultaneous decrease of cathodic ECL from GQDs and enhancement of anodic ECL from luminol in the same bioanalysis.

A series of spirooxindole tetrahydrofuran derivatives 3 were obtained in moderate to good yields via oxindole derivatives 1 and β-arylacrylonitrile derivatives 2via base-mediated cascade [3 + 2] double Michael reactions under mild conditions and the application of this method in the synthesis of bioactive analogues, such as functionalized spirooxindole octahydrofuro[3,4-c]pyridine derivatives 4 which contain two new heterocyclic rings and two quaternary carbon centers, has also been developed. Subsequently, antifungal activities of all of the synthesized compounds were evaluated against five phytopathogenic fungi (Rhizoctonia solani, Fusarium semitectum, Alternaria solani, Valsa mali and Fusarium graminearum) using the mycelium growth rate method. The preliminary results showed that the spirooxindole octahydrofuro[3,4-c]pyridine derivative 4 showed higher growth inhibition of Valsa mali and Fusarium graminearum, than spirooxindole tetrahydrofuran derivatives 3. For example, spirooxindole octahydrofuro[3,4-c]pyridine derivative 4ab, having a bromine atom at the meta position of the benzene ring, was the best compound in inhibiting F. g. with an IC50 value of 3.31, in particular with inhibition of 4ab on F. g. being similar to that of the control cycloheximide (IC50 = 3.3 μg mL(-1)).

We investigate the photophysical and amplified spontaneous emission properties of a series of monodisperse solution-processable oligofluorenes functionalized with hexyl chains at the C9 position of each fluorene unit. Thin films of these oligofluorenes are then used in organic field-effect transistors and their charge transport properties are examined. We have particularly focused our attention on the influence of oligofluorene length on the absorption and steady-state fluorescence spectra, on the HOMO/LUMO energy levels, on the photoluminescence lifetime and quantum yield as well as on the amplified spontaneous emission properties and the charge carrier mobilities. Differential scanning calorimetry and X-ray diffraction measurements demonstrate that, among all oligofluorene derivatives used in this study, only the structure and morphology of the pentafluorene film is significantly modified by a thermal treatment above the glass transition temperature, resulting in a 9 nm blue-shift of the fluorescence spectrum without significant changes in the photoluminescence quantum yield and in the amplified spontaneous emission threshold. In parallel, hole field-effect mobility is significantly increased from 8.6 × 10(-7) to 3.8 × 10(-5) cm(2) V(-1) s(-1) upon thermal treatment, due to an increase of crystallinity. This study provides useful insights into the morphological control of oligofluorene thin films and how it affects their photophysical and charge transport properties. Moreover, we provide evidence that, because of the low threshold, the tunability of the amplified spontaneous emission and the photostability of the films, these oligofluorenes are promising candidates for organic solid-state laser applications.

A tailor-made colorimetric and red-emitting fluorescent dual probe for G-quadruplex nucleic acids was developed by incorporating a coumarin-hemicyanine fluorophore into an isaindigotone framework. The significant and distinct changes in both the color and fluorescence of this probe enable the label-free and visual detection of G-quadruplex structures.

Plasmonics have been proven to be an effective way to harness more incident light to achieve high efficiency in photovoltaic devices. Herein, we explore the possibility that plasmonics can be utilized to enhance light trapping and power conversion efficiency (PCE) for polymer-quantum dot (QD) hybrid solar cells (HSCs). Based on a low band-gap polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and a CdSe QD bulk-heterojunction (BHJ) system, gold nanoparticles were doped at different locations of the devices. Successfully, an improved PCE of 3.20 ± 0.22% and 3.16 ± 0.15% was achieved by doping the hole transporting layer and the active layer, respectively, which are among the highest values reported for CdSe QD based HSCs. A detailed study of processing, characterization, microscopy, and device fabrication is conducted to understand the underlying mechanism for the enhanced device performance. The success of this work provides a simple and generally applicable approach to enhance light harnessing of polymer-QD hybrid solar cells.

We report on singlet-singlet annihilation and exciton diffusion in as-prepared p-type and annealed n-type thin films of the low-bandgap quinoidal quaterthiophene [QQT(CN)4] using ultrafast transient absorption measurements. The decay dynamics of exciton populations are well described by a one-dimensional diffusion-limited bimolecular recombination, indicating that the singlet excitons migrate preferentially along the stacking direction. Our results show that the exciton diffusion constants in QQT(CN)4 films do not vary significantly upon thermal annealing. Exciton diffusion lengths are measured to be as high as 4 and 5 nm in as-prepared and annealed QQT(CN)4 films, respectively. We also observe an influence of the excitation densities on the singlet exciton diffusion, which is attributed to phonon scattering. Because of the possibility of patterning p-n regions in QQT(CN)4 films by thermal nanolithography techniques, this study provides important insight not only into the photophysical properties of quinoidal oligothiophene derivatives but also for their future integration into high-performance p-n nanostructured near infrared light-sensing devices.

The non-precious metal copper-catalyzed enantioselective hydrosilylation of a vast array of aryl cycloalkyl ketones with different ring sizes was studied systematically for the first time (up to 99% enantiomeric excess). The results demonstrated that the steric size of cycloalkyl groups has a significant influence on the reaction outcomes. The first stereoselective formation of a selection of cyclohexyl heteroaryl alcohols of up to 97% enantiopurity was realized as well. Dramatic temperature effects on both the enantiopurity and the absolute configuration of the alcohol products were observed in the reduction of some cyclohexyl pyridyl ketones.

The electrochemical sensing properties of graphene-based and carbon nanotube (CNT)-based electrodes towards ascorbic acid, dopamine, uric acid, and glucose are systematically compared. Nano-sized Pd catalyst particles are uniformly dispersed on both carbon supports using a supercritical fluid deposition technique to increase the sensing performance. The CNT/Pd electrode shows higher detection current than that of the graphene/Pd electrode, which is attributed to the three-dimensional architecture interwoven by the CNTs that creates a larger number of reaction sites. With the incorporation of ionic liquid (IL), the detection sensitivity of the IL/graphene/Pd electrode significantly increases, becoming noticeably higher than that of the IL/CNT/Pd counterpart. The synergistic interactions between graphene and IL that lead to the superior sensing performance are demonstrated and discussed.

A highly regio-, chemo-, diastereo- and enantioselective organocatalytic [4 + 1] annulation of 2-halo-1,3-dicarbonyl compounds with Morita-Baylis-Hillman adducts catalyzed by commercially available, low cost quinidine for the preparation of synthetically unique and medicinally multi-functionalized isoxazoline N-oxides with three stereogenic centers including adjacent quaternary and tertiary stereocenters has been developed. Notably, the unexpected product ethyl 2-((tert-butyldimethylsilyl)oxy)-2-(5,5-diacetyl-3-((methylsulfonyl)oxy)-4-phenylisoxazolidin-3-yl)acetate (8) bearing a quaternary stereocenter and two tertiary stereocenters was obtained from the undocumented 5,5-diacetyl-3-(2-ethoxy-1-hydroxy-2-oxoethyl)-4-phenyl-4,5-dihydroisoxazole 2-oxide (4ba).

A series of functionalized 2,3-dihydro-1,4-benzoxazines were obtained in moderate to excellent yields via domino [5 + 1] annulations of 2-halo-1,3-dicarbonyl compounds 2 with imines 1 under mild conditions and the application of this method in the synthesis of bioactive analogues, such as functionalized tetracyclic-1,4-benzoxazines which contain two new heterocyclic rings and one quaternary carbon center has also been developed.

α,α-Dicyanoolefins react with hydroxylamine to afford 2,3-dihydroisoxazoles (2,3-dihydroisoxazoles can be easily isolated by filtration) in excellent yields under mild and environmentally benign conditions. A one-pot reaction in tandem with an unexpected ring-opening of 2,3-dihydroisoxazoles has been developed as well.

In this paper, we demonstrated a highly discriminated and reliable molecular switch based on the interaction between the self-duplex of (Py)A-substituted oligodeoxyadenylate and graphene oxide in aqueous solution. This system showed a clear on/off state through the association and dissociation of (Py)A-modified oligodeoxynucleotide with graphene oxide in manipulated pH conditions, high amplitude efficiency for at least 50 cycles, and rapid response within seconds. Our molecular switch system has high reproducibility and simple operation by using pH stimulus.

G-quadruplex structures are a new class of attractive targets for DNA-interactive anticancer agents. The primary building block of this structure is the G-quartet, which is composed of four coplanar guanines and serves as the major binding site for small molecules. NMR studies and molecular dynamics simulations have suggested that the planarity of G-quartet surface has been highly dynamic in solution. To better investigate how the planarity of unfused aromatic ligand impacts on its quadruplex binding properties, a variety of planarity controllable isaindigotone derivatives were designed and synthesized. The interaction of G-quadruplex DNA with these designed ligands was systematically explored using a series of biophysical studies. The FRET-melting, SPR, and CD spectroscopy results showed that reducing the planarity of their unfused aromatic core resulted in their decreased binding affinity and stabilization ability for G-quadruplex. NMR studies also suggested that these compounds could stack on the G-quartet surface. Such results are in parallel with subsequent molecular modeling studies. A detailed binding energy analysis indicated that van der Waals energy (ΔE(vdw)) and entropy (TΔS) are responsible for their decreased quadruplex binding and stabilization effect. All these results provided insight information about how quadruplex recognition could be controlled by adjusting the planarity of ligands, which shed light on further development of unfused aromatic molecules as optimal G-quadruplex binding ligands.

We synthesized five novel uridine-based cationic nucleolipids, introducing basic amino acid residues at the 5' position of uridine, through 1,3-dipolar cycloaddition, and hydrophobic alkyl moieties at the 2' and 3' positions, through carbamate linkages. Their lipoplexes delivered siRNAs efficiently to cells, in vitro, without any severe toxicity.

The diversely functionalized tricyclic tetrazoles were synthesised from readily available substrates via intramolecular 1,3-dipolar cycloaddition as the key step in good yields (53-78% yield for two steps) with high enantioselectivities (81-99% ee).

Homogeneous oligodeoxyguanylates incorporating small-molecule intercalator pyrene moieties in a 1,5 relationship form various structures of dimer, trimer, tetramer and internal hairpin form that are yellowish in color because of the intermolecular interactions between the pyrene units.