Metal-free ß,γ-C(sp3)-H difunctionalization of propanols: DMP-initiated asymmetric spirocyclopropanation.

A DMP-initiated metal-free effective ß,γ-asymmetric spirocyclopropanation of propanols strategy using oxidative iminium activation is described. This process has been realized by a synergistic amine-catalyzed one-pot cascade oxidation-Michael addition cyclopropanation for "one-pot" access to various spirocyclopropyl propionaldehydes/propanols from diverse 3-arylpropanols and α-brominated active methylene compounds under mild conditions and with high enantioselectivity (ee up to >99%).

Ti-Catalyzed Formal [2π + 2σ] Cycloadditions of Bicyclo[1.1.0]butanes with 2-Azadienes to Access Aminobicyclo[2.1.1]hexanes.

Saturated bicyclic amines are increasingly targeted to the pharmaceutical industry as sp3-rich bioisosteres of anilines. Numerous strategies have been established for the preparation of bridgehead aminobicyclics. However, methods to assemble the bridge-amino hydrocarbon skeleton, which serves as a meta-substituted arene bioisostere, are limited. Herein, a general approach to access 2-aminobicyclo[2.1.1]hexanes (aminoBCHs) by titanium-catalyzed formal [2π + 2σ] cycloaddition of bicyclo[1.1.0]butanes and 2-azadienes was developed. Simple derivatization of aminoBCHs leads to various medicinally and agrochemically important analogues.

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.

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%.

Highly Conductive Inkjet-Printed PEDOT:PSS Film under Cyclic Stretching.

Inkjet-printed conductive polymer PEDOT:PSS films have provided a new developing direction for realizing the stretchable transparent electrodes in optoelectronic devices. However, their conductivity and stretchability are limited as the presence of insulating PSS chains, rigid PEDOT conjugated backbone, and stronger inter-chain interactions in the pristine polymer, respectively. Here, we report a PEDOT:PSS film with preferable electrical and mechanical performances by inkjet-printing the formulated printable ink containing PEDOT:PSS, formamide (FA), d-sorbitol (SOR), sodium dodecyl benzene sulfonate (DBSS), and ethylene glycol (EG). The inkjet-printed uniform PEDOT:PSS film exhibits a high conductivity of 1050 S/cm and sheet resistance of less than 145 Ω/sq on both rigid and flexible substrates. Moreover, the resistance can remain stable after 200 cycles of stretching at 55% strain. The film also presents good stability during repetitive stretching-releasing cycles. The significantly enhanced conductivity of the film lies on the conformational transition of the backbone by secondary doping and post-treatment with FA as well as removing the excess PSS components after phase separation between PEDOT and PSS. Meanwhile, SOR serves as a plasticizer to break the original hydrogen bonds between PSSH chains and provides larger free volume for polymer chain extension, which gives the PEDOT:PSS film the ability to tolerant cyclic tension. This is one of the optimal performances currently reported for inkjet-printed stretchable PEDOT:PSS films. The inkjet-printed PEDOT:PSS film with high conductivity, stretching properties, as well as good biocompatibility exhibits promising prospects as anodes on optoelectronic devices.

Effects of different processing techniques of broken rice on processing quality of pellet feed, nutrient digestibility, and gut microbiota of weaned piglets.

The present study was conducted to assess the effect of different processing techniques of broken rice on processing quality of pellet feed, growth performance, nutrient digestibility, blood biochemical parameters, and fecal microbiota of weaned piglets. A total of 400 crossbred piglets (Duroc × Landrace × Yorkshire) with a mean initial body weight (BW) of 7.24 ±â€…0.52 kg were used in a 28-d experiment. Piglets were randomly distributed to one of 4 treatment and 10 replicate pens per treatment, with 10 piglets per pen. The dietary treatments were as follows: CON, corn as the main cereal type in the dietary; BR, 70% of the corn replaced by broken rice; ETBR, 70% of the corn replaced by extruded broken rice; EPBR, 70% of the corn replaced by expanded broken rice. Extruded broken rice and expanded broken rice supplementation significantly (P < 0.05) increased hardness, pellet durability index, crispness, and starch gelatinization degree. Extruded broken rice and expanded broken rice generated a higher (P < 0.05) average daily feed intake, increased (P < 0.05) average daily gain, decreased (P < 0.05) feed conversion ratio, and lowered (P < 0.05) the diarrhea rate. Piglets fed extruded broken rice displayed high apparent total tract digestibility levels of dry matter (P < 0.05), gross energy (P < 0.05), crude protein (P < 0.05), and organic matter (P < 0.05). In addition, extruded broken rice and expanded broken rice supplementation had increased Lactobacillus and Bifidobacterium levels in gut, whereas a lower abundance of the potential pathogens Clostridium_sensu_strictio_1 and Streptococcus was observed. Dietary supplementation of extruded broken rice and expanded broken rice failed to show significant effects on blood biochemical parameters. Combined, 70% corn substituted with broken rice failed to show significant effects. Collectively, extruded broken rice and expanded broken rice supplementation had positively enhanced the pellet quality, growth performance, nutrient digestibility, and gut microbiota of weaned piglets.

Weaned piglets represent a critical phase in animal husbandry, and with the rising demand for meat, the consumption of animal feed has surged. Corn, a vital constituent of animal feed, has been consumed at an accelerated pace. In this regard, the use of broken rice as an alternative to corn is a feasible solution. Nevertheless, due to the incomplete development of piglets' bodies, higher quality feed is necessary. The processing technique applied to the feed has a significant impact on its effectiveness. Thus, we experimented to assess the effect of different processing techniques on the feed efficiency of weaning piglets, substituting corn with broken rice, extruded broken rice, and expanded broken rice. The study results revealed that the application of extruded and expanded broken rice improved the feed pellet quality, growth performance, nutrient digestibility, and gut microbiota of weaned piglets. Furthermore, extruded broken rice exhibited a superior feeding effect compared to expanded broken rice.

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%.

Improving the Molecular Packing Order and Vertical Phase Separation of the P3HT:O-IDTBR Blend by Extending the Crystallization Period of O-IDTBR.

The morphology with strong molecular packing order and gradient vertical composition distribution associated with efficient charge transport and collection is critical to achieve high performance in nonfullerene solar cells. However, the rapid solidification process of the active layer upon the fast removal of solvent usually results in a kinetically trapped state with undesired morphology. Herein, we proposed a strategy to extend the crystal growth time of the acceptor via a high-boiling-point additive that selectively dissolved the acceptor. This was enabled by adding dibenzyl ether (DBE) to the poly(3-hexylthiophene) (P3HT):O-IDTBR blend in chlorobenzene (CB) solution. The combination of the kinetic study by time-resolved ultraviolet-visible (UV-vis) absorption spectra and detailed morphological characterization allows us to correlate the crystallization kinetics with the microstructural transition. The results show that the crystal growth time of O-IDTBR increases from 3 to 60 s upon the addition of 0.75% DBE, leading to further evolution of the molecular order of O-IDTBR during the DBE-dominated drying period. Meanwhile, O-IDTBR has more time to migrate toward the substrate owing to the larger surface energy. In addition, the onset of the crystallization process of P3HT is brought forward from 8 to 6 s due to the reduced solvent quality, which favors P3HT to crystallize into a fibril network. As a result, an optimized morphology that features the enhanced molecular packing order of P3HT and O-IDTBR as well as the vertical compositional gradient of O-IDTBR is obtained. Devices based on the optimized blend show more balanced charge transport and suppressed bimolecular recombination, giving rise to an improved power conversion efficiency (PCE) from 4.29 ± 0.04 to 7.30 ± 0.12%.

Effect of pre-gelatinization on α-amylase-catalyzed hydrolysis of corn starch under moderate electric field.

This study aimed to explore the roles of starch structure in α-amylase-catalyzed hydrolysis under moderate electric field (MEF). Corn starch was gelatinized by controlling the temperature procedure of rapid viscos-analysis, and then the pre-gelatinized starch (3.0 g) was treated by MEF (2.5 and 5 V/cm) in the presence of α-amylase (1.5 mL). Only a slight hydrolysis occurred for native starch, showing minor increases in reducing sugar content (RSC, ∼0.19 mg/mL), slight changes in granular and semicrystalline structure, and decreases in thermostability (the maximum decomposition temperature (Tmax) decreased from 322 to 300 °C). The densely-packed semicrystalline within starch granules was destroyed by pre-gelatinization, thus enhancing the hydrolysis and further decreasing the thermostability, presenting RSC values of 0.63-0.92 mg/mL and Tmax of 291-292 °C. Moreover, some special crystals were formed by IEF-induced orientation of hydrolyzed starch chains. Overall, these results confirmed that the semicrystalline structure of starch dominated in MEF-assisted hydrolysis, which could provide guidance for the application of electro-based techniques in starch modification.

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%.

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.

Asymmetric α-spirocyclopropanation of oxindoles and benzofuranones via dynamic kinetic resolution.

Chiral benzo five-membered heterocyclic spirocyclopropanes are an important class of parent core structures with pharmacological activity. A novel organocatalytic one-pot cascade ether oxidation iminium-ion activation strategy for the asymmetric spirocyclopropylation of benzofuran-2-ones and indolin-2-ones from allyl tert-butyl ethers/ pent-2,4-dienyl ethyl ethers with excellent enantioselectivity (ee% up to > 99) and diastereoselectivity(dr.% up to 91:9) has been developed. This process involves the successful dynamic kinetic resolution of racemic 3-bromobenzofuran-2-ones or 3-bromoindolin-2-ones. Its synthetic application will provide a new aminocatalytic cascade tool for the efficient synthesis of complex molecules.

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.

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.

To Reveal the Importance of the Crystallization Sequence on Micro-Morphological Structures of All-Crystalline Polymer Blends by In Situ Investigation.

In crystalline/crystalline polymer blend systems, complex competition and coupling of crystallization and morphology usually happen due to the different crystal nucleation and growth processes of polymers, making the morphology and crystallization behavior difficult to control. Herein, we probe the crystallization sequence during the film formation process (crystallize simultaneously, component A crystallizes prior to B or inverse) to illustrate the micro-morphology evolution process in poly(3-hexylthiophene) (P3HT) and poly[[N,N-bis(2-octyldodecyl)-napthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]- alt-5, 5'-(2,2'-bithiophene)] (N2200) blend using in situ UV-vis absorption spectra and in situ two-dimensional grazing incidence X-ray diffraction (2D GIXRD). When P3HT and N2200 crystallize simultaneously, a large-sized morphology structure is formed. When strengthening the solution aggregation of P3HT by increasing the solvent-polymer interaction, P3HT crystallizes prior to N2200. A P3HT-based micro-morphology structure is obtained. As the molecular weight of N2200 increases to a critical value (72.0 kDa), the crystallization of N2200 dominates the film formation process. A N2200-based micro-morphology is formed guided by N2200 domains. The results confirm that the crystallization sequence is one of the most important factors to determine the micro-morphology structure in all-crystalline polymer blends.

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.

Efficient Nonhalogenated Solvent-Processed Ternary All-Polymer Solar Cells with a Favorable Morphology Enabled by Two Well-Compatible Donors.

The rational design of the morphology of ternary all-polymer solar cells (all-PSCs) having broadened photon harvesting is crucial to achieve high device performance. However, multicomponent blends often illustrated an unfavorable morphology such as large-sized phase separation due to their complicated interaction. Herein, we proposed to solve these problems by employing two donors with good miscibility (J51 and PTB7-Th), which also have similar compatibility with the acceptor (N2200). The resultant ternary blend films of J51:PTB7-Th:N2200 feature a uniform phase separation morphology due to the reduced competitive effect of intermolecular interactions. As an additional polymer donor, PTB7-Th could not only enhance the absorption of the binary blend but also act as a crystallization regulator to boost the face-on orientation in ternary blends. Accordingly, the J51:PTB7-Th:N2200 ternary blends exhibited improved sunlight absorption and higher and well-balanced carrier mobility accompanied by enhanced carrier extraction. With the nonhalogenated cyclopentyl methyl ether as the processing solvent, the ternary all-PSCs showed outstanding power conversion efficiency (PCE) higher than 9% when varying the PTB7-Th weight ratio in donors from 20 to 50%. Due to the PTB7-Th content holding a 30% weight ratio in donors, the ternary all-PSCs demonstrated the optimal PCE of 9.60%, which perform better than those of binary all-PSCs (PCE = 7.58 or 5.63%).

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.