Synthesis of Azabicyclo[3.1.1]heptenes Enabled by Catalyst-Controlled Annulations of Bicyclo[1.1.0]butanes with Vinyl Azides.

Bridged bicyclic scaffolds are emerging bioisosteres of planar aromatic rings under the concept of "escape from flatland". However, adopting this concept into the exploration of bioisosteres of pyridines remains elusive due to the challenge of incorporating a N atom into such bridged bicyclic structures. Herein, we report practical routes for the divergent synthesis of 2- and 3-azabicyclo[3.1.1]heptenes (aza-BCHepes) as potential bioisosteres of pyridines from the readily accessible vinyl azides and bicyclo[1.1.0]butanes (BCBs) via two distinct catalytic annulations. The reactivity of vinyl azides tailored with BCBs is the key to achieving divergent transformations. TiIII-catalyzed single-electron reductive generation of C-radicals from BCBs allows a concise (3 + 3) annulation with vinyl azides, affording novel 2-aza-BCHepe scaffolds. In contrast, scandium catalysis enables an efficient dipolar (3 + 2) annulation with vinyl azides to generate 2-azidobicyclo[2.1.1]hexanes, which subsequently undergo a chemoselective rearrangement to construct 3-aza-BCHepes. Both approaches efficiently deliver unique azabicyclo[3.1.1]heptene scaffolds with a high functional group tolerance. The synthetic utility has been further demonstrated by scale-up reactions and diverse postcatalytic transformations, providing valuable azabicyclics including 2- and 3-azabicyclo[3.1.1]heptanes and rigid bicyclic amino esters. In addition, the related sp2-hybridized nitrogen atom and the similar geometric property between pyridines and corresponding aza-BCHepes indicate that they are promising bioisosteres of pyridines.

Microstructural Evolution of P(NDI2OD-T2) Films with Different Molecular Weight during Stretching Deformation.

Conjugated polymers exhibit excellent electrical and mechanical properties when their molecular weight (Mw) is above the critical molecular weight (Mc). The microstructural changes of polymers under strain are crucial to establish a structure-performance relationship. Herein, the tensile deformation of P(NDI2OD-T2) is visualized, and cracks are revealed either along the (100) crystal plane of side chain packing or along the main chain direction which depends on the Mw is below or above the Mc. When Mw < Mc, the film cracks along the (100) plane under small strains. When Mw > Mc, the polymer chains first undergo stretch-induced orientation and then fracture along the main chain direction at large strains. This is attributed to the fact that the low Mw film exhibits large crystalline domains and the absence of interdomain connectivity, which are vulnerable to mechanical stress. In contrast, the high Mw film displays a nearly amorphous morphology with adequate entanglements, the molecular chains can endure stresses in the stretching direction to release substantial strain energy under greater mechanical deformation. Therefore, the film with Mw > Mc exhibits the optimal electrical and mechanical performances simultaneously, i.e., the electron mobility is retained under 100% strain and after 100 stretching-releasing cycles.

High atomic utilization conversion of ethers into furancarbaldehydes via an ether oxidation iminium-ion activation cascade strategy.

A novel organocatalytic one-pot cascade ether oxidation iminium-ion activation strategy for the synthesis of naphtho[2,1-b]furan-1-carbaldehyde and benzofuran-3-carbaldehyde from high atomic utilization transformation of aryl allyl ethers has been developed. Its synthetic application will provide a new ether oxidation iminium-ion activation cascade tool for the efficient synthesis of complex molecules.

Enhancing the Molecular Order and Vertical Component Distribution of the P3HT/O-IDTBR System during Layer-by-Layer Processing.

The molecular order and vertical component distribution are critical to enhance the charge transport in layer-by-layer (LbL) processed active layer. However, the excessive inter-diffusion between donor and acceptor layers during LbL processing irrepressibly reduces their ordered packing. Herein, a novel tactic to optimize the molecular order and vertical morphology of the active layer through suppressing the deep penetration of (5Z,5'Z)-5,5'-((7,7'-(4,4,9,9-tetraoctyl-4,9-dihydro-s-indaceno[1,2-b:5,6 -b']dithiophene-2,7-diyl)bis(benzo[c][1,2,5]thiadiazole-7,4-diyl))bis(methanylylidene)) bis(3-ethyl-2-thioxothiazolidin-4-one) (O-IDTBR) to poly(3-hexylthiophene) (P3HT) film during LbL processing is proposed. This is enabled by inducing the formation of P3HT nanofibers through ultraviolet (UV) irradiation and solution aging. During the LbL processing, these nanofibers with high crystallinity reduce the damage of O-IDTBR solution to P3HT film and restrict the penetration of O-IDTBR into P3HT matrix. As a result, the P3HT nanofibers are preserved and the degree of vertical phase separation is enlarged in the LbL-processed film. Meanwhile, the molecular order of both components is enhanced. The resulting morphology that featured as intertwined P3HT nanofibers/O-IDTBR network efficiently promotes charge transport and extraction, boosting the power conversion efficiency (PCE) of the devices from 6.70 ± 0.12% to 7.71 ± 0.10%.

Catalyst-Free α-Alkylation-α-Hydroxylation of Oxindole with Alcohols.

3-Alkyl-3-hydroxyoxindoles, a subclass of oxindole products, have antioxidant, neuroprotective, anticancer, and anti-HIV activities. In this study, a green and economical protocol for the synthesis of 3-alkyl-3-hydroxyoxindoles is developed for the first time via α-alkylation-α-hydroxylation of oxindole with benzyl alcohols without using any transition-metal catalysts in yields of 29-93%.

One-pot three-component access to 5-hydroxyindoles based on an oxidative dearomatization strategy.

A one-pot three-component reaction based on an oxidative dearomatization strategy has been performed to provide facile access to 5-hydroxyindole derivatives through a ZnI2-catalyzed tandem process. The multi-unit reactions for the construction of a new C-C bond and two C-N bonds are simple and efficient under mild conditions, and the yield of the target product is as high as 91%.

Optimizing the Intercrystallite Connection of a Donor-Acceptor Conjugated Semiconductor Polymer by Controlling the Crystallization Rate via Temperature.

The charge carrier transport of conjugated polymer thin film is mainly decided by the crystalline domain and intercrystallite connection. High-density tie-chain can provide an effective bridge between crystalline domains. Herein, the tie-chain connection behavior is optimized by decreasing the crystal region length (lc ) and increasing the crystallization rate. Poly[4-(4,4-bis(2-octyldodecyl)-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-alt-[1,2,5]-thiadiazolo[3,4-c]pyridine] (PCDTPT-ODD) is dissolved in nonpolar solvent isooctane and high ordered rod-like aggregations are formed. As the temperature increases, the changes in solution state and crystallization behavior lead to three different chain arrangement morphologies in the films: 1) at 25 °C, large and separated crystal regions are formed; 2) at 55 °C, small and well-connected crystal regions are formed due to faster crystallization rate and smaller nucleus size; 3) at 90 °C, the amorphous film is formed. Further results show that the film prepared at 55 °C has a smaller crystal region length (lc , 7.6 nm) and higher tie-chains content. Thus, the film exhibits the best device mobility of 2.3 × 10-3 cm2 V-1 s-1 . This result shows the great influence of crystallization kinetics on the microstructure of conjugated polymer films and provides an effective way for the optimization of the intercrystallite tie-chain.

Porous layer open-tubular column with styrene and itaconic acid-copolymerized polymer as stationary phase for capillary electrochromatography-mass spectrometry.

Enhancing the specific surface area of stationary phase is important in chromatographic science, especially in open-tubular column in which the coating only exists on the inner surface. In this work, a porous layer open-tubular (PLOT) column with stationary phase of styrene and itaconic acid-copolymerized polymer was developed. Thermal-initiated polymerization method with strategies like controlling the ratio of reaction reagents to solvents and reaction time, confinement by the narrow inner diameter of capillary were used for preparing the stationary phase with uniform structure and relatively thick layer. Due to the high separation efficiency and capacity, the PLOT column was used for capillary electrochromatography (CEC) separation of multiple groups of analytes like alkylbenzenes, phenyl amines, phenols, vanillins, and sulfonamides with theoretical plates (N) up to 1,54,845 N/m. In addition, due to high permeability of the CEC column and large electroosmotic flow mobility generated by abundant carboxyl groups in the coating material, the PLOT-CEC column was successfully coupled with mass spectrometry (MS) through a sheath flow interface. The developed PLOT-CEC-MS method was used for the analysis of antiseptics like parabens and herbicides like pyridines.

Recent Advances on Functional Nucleic-Acid Biosensors.

In the past few decades, biosensors have been gradually developed for the rapid detection and monitoring of human diseases. Recently, functional nucleic-acid (FNA) biosensors have attracted the attention of scholars due to a series of advantages such as high stability and strong specificity, as well as the significant progress they have made in terms of biomedical applications. However, there are few reports that systematically and comprehensively summarize its working principles, classification and application. In this review, we primarily introduce functional modes of biosensors that combine functional nucleic acids with different signal output modes. In addition, the mechanisms of action of several media of the FNA biosensor are introduced. Finally, the practical application and existing problems of FNA sensors are discussed, and the future development directions and application prospects of functional nucleic acid sensors are prospected.

Dietary Garcinol Attenuates Hepatic Pyruvate and Triglyceride Accumulation by Inhibiting P300/CBP-Associated Factor in Mid-to-Late Pregnant Rats.

BACKGROUND: Increased hepatic glycolysis and lipogenesis are characteristic of pregnancy. OBJECTIVES: The present study aimed to investigate the mechanism of garcinol on the amelioration of hepatic pyruvate and triglyceride (TG) accumulation in mid-to-late pregnant rats. METHODS: Forty Sprague-Dawley pregnant rats (aged 9 wk, n = 10/diet) were fed a basal diet (control) or that diet plus garcinol at 100 ppm (Low Gar), 300 ppm (Mid Gar), or 500 ppm (High Gar) for 14 d. The livers were processed for Western blotting analyses and measuring enzymatic activity and pyruvate and TG concentrations. Hepatocytes from other pregnant Sprague Dawley rats were transfected with P300/CBP associating factor (PCAF) short interfering (si)RNAs; hepatocytes from nonpregnant Sprague-Dawley rats with overexpression of PCAF were treated with garcinol (5 µM). The activity and acetylation of upstream stimulatory factor (USF-1) and glycolytic enzymes were analyzed. RESULTS: Dietary garcinol significantly decreased (P < 0.05) concentrations of hepatic and plasma TG (27.1-45.8%) and total cholesterol (25.3-49.5%), plasma free fatty acids (24.4-37.8%), and hepatic pyruvate (31.5-43.5%) and lactate (33.4-65.7%) in mid-to-late pregnant rats. Garcinol promoted (P < 0.05) antioxidant capacity in the liver and plasma by 27.4-32.1%. Garcinol downregulated (P < 0.05) lipid synthesis-related enzyme expression by 30.6-85.3% and decreased (P < 0.05) glycolytic enzyme activities by 22.5-74.6% and PCAF activity by 18.6-55.4%. Transfection of PCAF siRNAs to hepatocytes of pregnant rats decreased USF-1 and glycolytic enzyme activities by PCAF; garcinol treatment downregulated (P < 0.05) the acetylation and activities of USF-1 and glycolytic enzymes by 35.6-83.7%. CONCLUSIONS: Garcinol attenuates hepatic pyruvate and TG accumulation in the liver of mid-to-late pregnant rats, which may be due to downregulating the acetylation of USF-1 and the glycolytic enzymes induced by PCAF in isolated hepatocytes.

Rh(III)-Catalyzed Hydroarylation of Alkyne MIDA Boronates via C-H Activation of Indole Derivatives.

An efficient approach to trans-indolylvinylboronate derivatives has been developed using an Rh-catalyzed hydroarylation of alkyne N-methyliminodiacetic acid boronates via C-H activation. This protocol constitutes a straightforward route for the synthesis of B-containing aza-heterocycles in good yields with excellent functional group tolerance.

An Unconventional Redox Cross Claisen Condensation-Aromatization of 4-Hydroxyprolines with Ketones.

Reaction of α-amino acids, particularly prolines and their derivatives with carbonyl compounds via decarboxylative redox process, is a viable strategy for synthesis of structurally diverse nitrogen centered heterocyclics. In these processes, the decarboxylation is the essential driving force for the processes. The realization of the redox process without decarboxylation may offer an opportunity to explore new reactions. Herein, we report the discovery of an unprecedented redox Claisen-type condensation aromatization cascade reaction of 4-substituted 4-hydroxyproline and its esters with unreactive ketones. We found that the use of propionic acid as a catalyst and a co-solvent can change the reaction course. The commonly observed redox decarboxylation and aldol condensation reactions are significantly minimized. Moreover, unreactive ketones can effectively participate in the Claisen condensation reaction. The new reactivity enables a redox cyclization via an unconventional Claisen-type condensation reaction of in situ formed enamine intermediates from ketone precursors with 4-substituted 4-hydroxyproline and its esters as electrophilic acylation partners. Under the reaction conditions, the cascade process proceeds highly regio- and stereoselectively to afford highly synthetically and biologically valued cis-2,3-dihydro-1H-pyrrolizin-1-ones with a broad substrate scope in efficient 'one-pot' operation, whereas such structures generally require multiple steps.

Decreased domain size of p-DTS(FBTTh2)2/P(NDI2OD-T2) blend films due to their different solution aggregation behavior at different temperatures.

Nanoscale interpenetrating networks play a key role in determining the optoelectrical properties of functional blends. However, phase separated large domain sizes could probably be observed in pristine films composed of two crystalline components. For example, p-DTS(FBTTh2)2/P(NDI2OD-T2) 3/2 blend films with interpenetrating networks are obtained, however, large domain sizes are found when they are prepared from a 20 °C solution due to the simultaneous process of crystallization and phase separation during solvent evaporation. In this paper, we proposed to reduce the domain size of p-DTS(FBTTh2)2/P(NDI2OD-T2) blend films using their different solution aggregation behaviors at different temperatures. The aggregation of p-DTS(FBTTh2)2 molecules in chlorobenzene (CB) was insensitive to the solution temperature. However, the in situ absorption spectra of the neat P(NDI2OD-T2) solution from 80 °C to room temperature indicated that P(NDI2OD-T2) aggregation increased with decreasing temperature due to intrachain interactions. Therefore, in order to reduce the domain size, we employed a hot solution to prepare the blend films. During the solidification process, the majority of p-DTS(FBTTh2)2 molecules were confined in the P(NDI2OD-T2) networks prior to occurrence of severe p-DTS(FBTTh2)2 aggregation. Thus, the domain size of the p-DTS(FBTTh2)2 phase became smaller than that of the pristine films, leading to a decrease in the corresponding photoluminescence intensity of the blend films. In addition, the crystallinity of the blend films improved after thermal annealing, which resulted from the ordered alignment of p-DTS(FBTTh2)2 molecules facilitated by their enhanced diffusion ability. Based on the various morphologies, a possible phase diagram of the p-DTS(FBTTh2)2/P(NDI2OD-T2) blend system was depicted, which could be a guide to directly control the morphology of blend films.

Novel polymeric monolith materials with a ß-cyclodextrin-graphene composite for the highly selective extraction of methyl jasmonate.

A novel polymeric monolith column with a  ß-cyclodextrin-graphene composite was prepared for extraction of methyl jasmonate. A simple, sensitive, and effective polymeric monolith microextraction with high-performance liquid chromatography method has been presented for the determination. To carry out the best microextraction efficiency, several parameters such as sample flow rate, sample volume, and sample pH value were systematically optimized. In addition, the method validation showed a wide linear range of 5-2000 ng/mL, with a good linearity and low limits of detection for methyl jasmonate. The proposed method was successfully applied for the determination of methyl jasmonate in wintersweet flowers with recoveries of 90.67%. The result was confirmed by high-performance liquid chromatography with mass spectrometry.

Evaluation of 660 nm LED light irradiation on the strategies for treating experimental periodontal intrabony defects.

This study aims to investigate the therapeutic value of 660 nm light-emitting diode (LED) light irradiation on the strategies for treating experimental periodontal intrabony defects in vivo. Large-sized periodontal intrabony defects were created bilaterally on the mesial aspect of the maxillary second molars of 48 Sprague-Dawley rats, and the rats were equally divided into four treatment groups with primary wound intention (n = 6/treatment/time point), including open flap debridement alone (OD), barrier membrane alone (MB), xenograft alone (BG), and xenograft plus barrier membrane (MG). Each group received daily 0 or 10 J/cm(2) LED light irradiation. The animals were sacrificed after 1 or 4 weeks. The treatment outcome was evaluated by gross observation of wound dehiscence and healing, micro-CT imaging for osteogenesis, and histological assessments for inflammatory cell infiltration and periodontal reattachment. With LED light irradiation, the extent of wound dehiscence was reduced, wound closure was accelerated, epithelial downgrowth was prevented, inflammation was reduced, and periodontal reattachment was promoted in all treatment strategies. Significant reduction of inflammation with LED light irradiation was noted at 1 week in the groups BG and MG (p < 0.05). Osteogenesis was significantly promoted only in the group OD at both time points (p < 0.05). Our study showed that 660 nm LED light accelerates mucoperiosteal flap healing and periodontal reattachment. However, the enhancement of osteogenesis appeared to be limited while simultaneously treating with a barrier membrane or xenograft.

Stereoselective α-indolylation of enals via an organocatalytic formal cross-coupling with indoles.

We report a novel organocatalytic one-pot cascade bromination-Michael-type Friedel-Crafts alkylation dearomatization-nucleophilic rearrangement aromatization cascade process for the direct α-indolylation of unfunctionalized enals from readily available indoles with good yields and high E selectivity. The simplicity and practicality of its high efficiency for formation of a new C(sp(2))-C(sp(2)) bond constitute the most attractive advantage of this reaction.

Ordered fibrillar morphology of donor-acceptor conjugated copolymers at multiple scales via blending with flexible polymers and solvent vapor annealing: insight into photophysics and mechanism.

The ordered, aligned fibrillar morphology at multiple scales of a donor-acceptor (D-A) conjugated copolymer of 3,6-bis-(thiophen-2-yl)-N,N'-bis(2-octyl-1-dodecyl)-1,4-dioxo-pyrrolo[3,4-c]pyrrole and thieno[3,2-b]thiophene (PDBT-TT) was prepared via blending with flexible polymers (PS13.7k, PDBT-TT/PS = 1/10 w/w) followed by chloroform (CF) solvent vapor annealing (SVA) for 24 h. The aligned fibrillar bundles were of about 500 nm width, consisting of parallel aligned nanofibrils of ab. 10 nm width. It was found that the direction of backbones in nanofibrils was parallel to the long axis of nanofibrils, which implied an intense intra-chain conjugation associated with extended backbones and J-aggregation of PDBT-TT. This ordered morphology corresponded to the characteristic photophysical features of (i) red-shifted absorption arising from J-aggregation, (ii) larger Davydov splitting, (iii) the prevailing absorbance of J-aggregation over H-aggregation in its UV-Vis spectrum and (iv) more red-shifted max photoluminescence emission, compared with the films prepared via the other methods. By investigating the Raman spectra and XRD profiles, it is proposed that the origin of the best morphological and photophysical order is the combination of blending and SVA. The limited and "flexible" space formed due to phase separation between PDBT-TT and PS facilitated the motion of rigid PDBT-TT chains and promoted their stacking order as templates, and CF vapor assisted the conformational transition of chains to more "coil-like" to help them reorganize in a thermodynamic stable way.

Achieving balanced intermixed and pure crystalline phases in PDI-based non-fullerene organic solar cells via selective solvent additives.

Herein, balanced intermixed and pure crystalline phases in N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (EP-PDI)-based non-fullerene organic solar cells (OSCs) were achieved via selective solvent additives (SAs). Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7) and 7,7'-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole) (F-DTS) possessing different compatibilities with EP-PDI were selected as model systems to investigate the guideline of SAs selection for different non-fullerene-based systems. According to the solubility parameter difference (Δδ) between EP-PDI and SAs, five different SAs were divided into two types: (I) strong intermolecular interactions with EP-PDI molecules (with Δδ values less than 5 MPa(1/2)), (II) weak intermolecular interactions with EP-PDI molecules (with large Δδ values). For PTB7:EP-PDI system with large and obvious phase separation, the introduction of type (II) SAs provided extra interactions with EP-PDI molecules, thus effectively reducing EP-PDI aggregate domains and increasing intermixed fractions. The incorporation of type (II) SAs resulted in a greater yield of dissociated polarons, and the final device efficiency increased from 0.02% to 1.65%. On the contrary, for finely mixed F-DTS:EP-PDI systems, type (I) SAs were considerably more effective because of the fact that the required pure crystalline phases were readily induced by the unfavorable interactions. The charge transport pathways optimized by type (I) SAs improved device efficiency from 0.18% to 2.82%. Hence, by processing selective SAs, the fraction of intermixed and pure crystalline phases for PDI-based non-fullerene OSCs can be well regulated; therefore, the final performance for both systems can be significantly improved.

Cooperative effects of solvent and polymer acceptor co-additives in P3HT:PDI solar cells: simultaneous optimization in lateral and vertical phase separation.

In this work, solvent chloronaphthalene (CN) and polymer acceptor an alternating copolymer of perylene diimide and carbazole (PCPDI) were utilized as co-additives to optimize the nanoscale phase-separated morphology and photovoltaic properties of bulk-heterojunction (BHJ) polymer solar cells based on the poly(3-hexyl thiophene) (P3HT)/N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (EP-PDI) system. The domain size of EP-PDI molecules together with that of P3HT distinctly decreased by adding a 0.75 vol% CN additive. The optimized lateral phase separation increased the donor-acceptor interfacial area and facilitated the exciton dissociation process, leading to 5-fold enhancement of short-circuit current (JSC). Furthermore, when PCPDI was employed as a co-additive, acceptor materials (including PCPDI and EP-PDI) were prone to aggregation towards the top surface of blend films, improving vertical phase separation of active layers. PCPDI incorporation, which improved the percolation pathways for electron carriers, suppressed the crystallinity of P3HT distinctly. Thus, much more balanced charge transport was achieved by PCPDI addition, which resulted in almost 1-fold enhancement of open-circuit voltage (VOC) by reducing nongeminate recombination. As a consequence, cooperative effects of CN and PCPDI additives improved the nanoscale phase-separated morphology in lateral and vertical directions simultaneously, achieving the enhancement in both VOC and JSC.

Binding capacity and co-migration potential of Pb(II), Cu(II), and Cd(II) on colloids in road runoff.

To evaluate the co-migration potential between heavy metal ions and road runoff colloids, the influence of contact time, temperature, initial concentration of metal ions, pH, humic acid (HA), and polymetallic coexistence on the binding capacity of heavy metals onto runoff colloids were investigated. The adsorption of heavy metals by runoff colloids was extremely rapid, approximately 80% of the equilibrium adsorption capacity was achieved in the first 30 min. The binding capacity exhibited an increasing trend with the initial concentration of metal ions increasing, and the maximum adsorption capacities of Pb(II), Cu(II), and Cd(II) achieved 159.13, 56.06, and 78.35 mg/g at 298 K, respectively. The adsorption capacity of Cu(II) and Cd(II) by runoff colloids increased with temperature increasing, while it displayed a converse trend for Pb(II). Neutral pH facilitated the combination of metal ions and runoff colloids. The presence of humic acid increased the binding capacity of Pb(II), Cu(II), and Cd(II) onto runoff colloids by 72.19, 63.31, and 13.83mg/g, respectively. Compared to the monometallic systems, the binding capacity of Pb(II), Cu(II), and Cd(II) by runoff colloids decreased by 18.44%, 22.35%, and 56.06% in polymetallic systems, respectively. Pb(II) bounded with colloids in the road runoff should be controlled preferentially to avoid their migrations to aquatic environments.