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Issues concerning the photoexcitation of two bichromophoric molecules consisting of diphenylpolyene and anthracene moieties connected by two fused norborynyl bridges are discussed. Photoexcitation was found to cause the production of both the anthracene and polyene cation radicals.

Bismuth telluride-based materials have been widely used in commercial thermoelectric applications due to their excellent thermoelectric performance in the near-room-temperature range, yet further improvement of their thermoelectric properties is still necessary. Moreover, the narrow band gap of these materials results in a bipolar effect at elevated temperatures, which causes severe degradation of the thermoelectric performance. In this work, the commercial Bi 0.4 Sb 1.6 Te 3 was alloyed with AgSbTe 2 by using high-energy ball milling method combined with spark plasma sintering. It was found that ball milling can effectively reduce the lattice thermal conductivity of the samples. The alloying of AgSbTe 2 leads to a gradual increase in hole carrier concentration, resulting in an enhanced electrical conductivity and optimized power factor. Additionally, the bipolar effect is also weakened due to the increased hole carrier concentration. Furthermore, the substitution of Ag in the Bi/Sb sublattice causes further reduction in the lattice thermal conductivity. Ultimately, the sample alloyed with 0.15 wt % AgSbTe 2 demonstrates its best thermoelectric performance with a maximum zT of 1.35 at 393 K, showing a 20.5% improvement compared to the commercial sample. Besides, its average zT reaches a high value of 1.25 between 303 and 483 K, with a 27.6% improvement compared to that of the commercial sample.

Cell-like particles represent a category of synthetic particles designed to emulate the structures or functions of natural cells. Herein, we present the assembly of cell-like poly(ethylene glycol) (PEG) particles with different stiffnesses and shapes via replication of animal cells and investigate the impact of particle stiffness on their biological behaviors. As a proof of concept, we fabricate red blood cell-like and spherical PEG particles with varying cross-linking densities. A systematic exploration of their properties, encompassing morphology, stiffness, deformability, and biodistribution, reveal the vital influence of particle stiffness on in vivo fate, elucidating its role in governing the traversal of capillaries and the dynamic interactions with phagocytic cells.

The propagation pattern of pressure drawdown effectively reflects the recoverable reserves range around the gas well and serves as a crucial basis for development strategies. However, it is not easy to detect the pressure propagation boundary near the producing well, especially in low-permeability reservoirs where the drainage radius is small. Physical simulation experiments can serve as a crucial method as the whole pressure profile and gas rate can be obtained in real time. Using long core plugs with permeabilities of 2.300 mD, 0.486 mD, and 0.046 mD, physical simulation experiments were carried out under varying initial water saturation (Swi) conditions of 0%, 20%, 40%, and 55% to observe the dynamic variations in pressure profiles of the core plugs during pressure depletion. Based on the material balance equation and pressure profile characteristics of the core plugs, a method for evaluating recoverable reserves within a well-spacing radius through laboratory experiments was proposed and performed. Mechanism analysis was conducted based on mercury injection tests, and suggestions for enhancing gas recovery were presented. Research findings indicate that lower permeability, higher initial water saturation, and higher abandonment gas rates result in reduced reserve utilization range and degree. Under abandoned gas rate conditions, for type I and II rocks, the pore radius is primarily distributed between 0.1 and 1 μm, the pressure drawdown can reach the well-spacing radius of 600 m, and the ultimate recovery efficiencies are more than 70.6%. For type III rocks, the pore radius mainly falls below 0.1 μm, the drainage radius is smaller than 10 m with Swi greater than 40%, and the ultimate recovery is below 10%. This paper provides an experimental method for recoverable reserves evaluation while formulating gas reservoir development strategies before well testing., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In this work, a series of Cu 2 Se/ x wt % porous carbon (PC) ( x = 0, 0.2, 0.4, 0.6, 0.8, 1) composite materials were synthesized by ball milling and spark plasma sintering (SPS). The highly ordered porous carbon was synthesized by a hydrothermal method using mesoporous silica (SBA-15) as the template. X-ray diffraction results show that the incorporation of porous carbon induces a phase transition of Cu 2 Se from the β phase to the α phase. Meanwhile, the addition of porous carbon reduces the carrier concentration from 2.7 × 10 21 to 2.45 × 10 20 cm -3 by 1 order of magnitude. The decrease of the carrier concentration leads to the reduction of electrical conductivity and the increase of the Seebeck coefficient, which results in the enhancement of the power factor. On the other hand, the incorporation of porous carbon into Cu 2 Se increases the porosity of the composites and also introduces more interfaces between the two materials, which is evidenced by positron annihilation lifetime measurements. Both pores and interfaces greatly enhance phonon scattering, leading to extremely low lattice thermal conductivity. In addition, the decrease of electrical conductivity also causes a sufficient reduction in electronic thermal conductivity. Due to the above synergistic effects, the thermoelectric performance of the Cu 2 Se/PC composite is significantly enhanced with a maximum ZT value of 0.92 at 403 K in the Cu 2 Se/1 wt % PC composite, which is close to that of the Bi 2 Te 3 -based materials. Our work shows that α-Cu 2 Se has great potential for near-room-temperature thermoelectric materials.

Accurate detection of biomarkers in whole blood is an important aspect of diagnostic testing but remains a challenge due to various interferences. However, using a self-calibrating two-signal strategy offers a solution that can overcome interference caused by experimental and environmental factors. Here, we proposed a novel microswimmer {methylene blue (MB)@ZIF-90@aptamer-HER2/3,3',5,5'-tetramethylbenzidine (TMB)@ZIF-90@aptamer-ER}-dual-signal (electrochemical and fluorescence) homogeneous sensor based on functionalized ZIF nanomaterials for one-step simultaneous detection of human epidermal growth factor receptor-2 (HER2) and estrogen receptor (ER) in whole blood. The proposed one-step ZIF-90 synthesis encapsulates TMB and MB with dual-signal properties. HER2 and ER aptamers adsorbed on MB@ZIF-90/TMB@ZIF-90 function as the gate switches. The microswimmer targets the HER2 and ER with adenosine triphosphate (ATP)-driven motion. When targets are present, aptamers dissociate and reduce the microswimmer's surface negative charge. The microswimmer undergoes attack and decomposition by swimming ATP due to the strong coordination force between ATP and Zn 2+ , leading to the release of MB and TMB. The negative charges on the surface of indium tin oxide enrich MB and TMB with positive charges, thereby increasing the intensities of electrochemical and fluorescence signals. The detection process was completed within 40 min, and the detection limits for ER and HER2 were 8.1 and 5.7 fg/mL respectively, with a linear range of 0.25-20 pg/mL.

Ubiquitination genes are key components of plant responses to biotic stress. GmPUB20A , a ubiquitination gene, plays a negative role in soybean resistance to soybean cyst nematode (SCN). In this study, we employed high-throughput sequencing to investigate transcriptional changes in GmPUB20A overexpressing and RNA-interfering transgenic hairy roots. Totally, 7661 differentially expressed genes (DEGs) were identified. Gene Ontology (GO) enrichment and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analyses revealed that DEGs were significantly enriched in disease resistance and signal transduction pathways. In addition, silencing Glyma.15G021600 and Glyma.09G284700 by siRNA, the total number of nematodes was decreased by 33.48% and 27.47% than control plants, respectively. Further, GUS activity and reactive oxygen species (ROS) assays revealed that GmPUB20A , Glyma.15G021600 , and Glyma.09G284700 respond to SCN parasitism and interfere with the accumulation of ROS in plant roots, respectively. Collectively, our study provides insights into the molecular mechanism of GmPUB20A in soybean resistance to SCN.

Synergetic optimization of the electrical and thermal transport performance of GeTe has been achieved through Sb doping in this work, resulting in a high thermoelectric figure of merit ZT of 2.2 at 723 K. Positron annihilation measurements provided clear evidence that Sb doping in GeTe can effectively suppress the Ge vacancies, and the decrease of vacancy concentration coincides well with the change of hole carrier concentration after Sb doping. The decreased scattering by hole carriers and vacancies causes notable increase in carrier mobility. Despite this, the density of states effective mass is not enhanced by Sb doping, a maximum power factor of 4562 μW m -1 K -2 at 723 K is obtained for Ge 0.94 Sb 0.06 Te with an optimized carrier concentration of ∼3.65 × 10 20 cm -3 . Meanwhile, the electronic thermal conductivity κ e is reduced because of the decreased electrical conductivity σ with the increase of the Sb doping amount. In addition, the lattice thermal conductivity κ L is also suppressed due to multiple phonon scattering mechanism, such as the large mass and strain fluctuations by the substitution of Sb for Ge atoms, and also the unique microstructure including grain boundary, nano-pore, and dislocation in the samples. In conclusion, a maximum ZT of 2.2 is gained at 723 K, which contributes to preferable TE property for GeTe-based materials.

As a liquid-like material, CuAgSe has high carrier mobility and ultralow lattice thermal conductivity. It undergoes an n-p conduction-type transition during β- to α-phase transition with increasing temperature. Moreover, optimization of the thermoelectric performance of CuAgSe is rather difficult, owing to the two-carrier conduction in this material. In this work, we reported the free tuning of the conduction type and thermoelectric performance of CuAgSe by manipulating the cation vacancies. Positron annihilation measurements reveal that the increase in CuAg content can effectively suppress the cation vacancies and reduce the hole carrier concentration, resulting in n-type conduction at high temperatures. Doping with Zn at the Cu sublattice in the CuAg-excessive CuAgSe can further decrease the number of vacancies, leading to a significant decrease in hole carrier concentration. Furthermore, the reduction of vacancies leads to weakening of carrier scattering. As a result, carrier mobility is also enhanced, thus improving the thermoelectric performance of n-type CuAgSe. On the other hand, high-performance p-type CuAgSe can be achieved by decreasing the CuAg content to introduce more cation vacancies. Ultimately, both n-type and p-type CuAgSe with superb thermoelectric performance are obtained, with a zT max of 0.84 in Cu 1.01 Ag 1.02 Se (n-type) and 1.05 in (CuAg) 0.01 Se (n-type) and 1.05 in (CuAg) 0.96 of 0.77 and 0.94 between 470 and 630 K for n-type and p-type, respectively.zT of 0.77 and 0.94 between 470 and 630 K for n-type and p-type, respectively.

Low thermal conductivity is crucial for obtaining a promising thermoelectric (TE) performance in semiconductors. In this work, the TE properties of Cu 4 TiS 4 and Cu 4 TiSe 4 were theoretically investigated by carrying out first-principles calculations and solving Boltzmann transport equations. The calculated results reveal a lower sound velocity in Cu 4 TiSe 4 compared to that in Cu 4 TiS 4 , which is due to the weaker chemical bonds in the crystal orbital Hamilton population (COHP) and also the larger atomic mass in Cu 4 TiSe 4 . In addition, the strong lattice anharmonicity in Cu 4 TiSe 4 enhances phonon-phonon scattering, which shortens the phonon relaxation time. All of these factors lead to an extremely low lattice thermal conductivity (κ L ) of 0.11 W m -1 K -1 at room temperature in Cu 4 TiSe 4 compared with that of 0.58 W m -1 K -1 in Cu 4 TiS 4 . Owing to the suitable band gaps of Cu 4 TiS 4 and Cu 4 TiSe 4 , they also exhibit great electrical transport properties. As a result, the optimal ZT values for p (n)-type Cu 4 TiSe 4 are up to 2.55 (2.88) and 5.04 (5.68) at 300 and 800 K, respectively. For p (n)-type Cu 4 TiS 4 , due to its low κ L , the ZT can also reach high values over 2 at 800 K. The superior thermoelectric performance in Cu 4 TiSe 4 demonstrates its great potential for applications in thermoelectric conversion.

The ability to efficiently detect trace disease biomarkers in whole blood remains an enormous challenge. Researchers have paid more attention to the homogeneous electrochemical ratio biosensor due to its self-calibration capability and improved detection accuracy. However, proportional homogeneous electrochemical sensing is difficult to achieve and typically requires functional modification of the electrode or the preparation of complex materials. Herein, a dual-signal ratiometric aptamer homogeneous electrochemical microswimming detection device with active capture capability and one-step detection of human epidermal growth factor receptor-2 (HER2) is proposed. The homogeneous electrochemical biosensor is fabricated based on a functionalized nanocomposite double-stranded DNA({single-stranded DNA-ferrocene (Fc)-aptamer})@Co-UiO-66 with catalase properties and adsorptive properties to electroactive toluidine blue (TB) molecules. Encapsulation of Co-UiO-66 material with dsDNA (ssDNA-Fc-Apt) containing HER2 aptamer as a gate switch inhibited its ability to adsorb TB molecules. This functionalized Co-UiO-66 material can catalyze hydrogen peroxide. Using hydrogen peroxide as a fuel, it breaks down to release oxygen bubbles, creating a propulsion force that drives dsDNA(ssDNA-Fc-Apt)@Co-UiO-66 target HER2 through whole blood. When the surface dsDNA (ssDNA-Fc-Apt)@Co-UiO-66 recognizes HER2, a strand displacement reaction occurs, and the ssDNA-Fc is released into solution. The HER2 aptamer is coiled because it targets HER2, and the ability to adsorb TB molecules is restored due to the exposed surface of Co-UiO-66. A certain negative voltage is applied to the ITO electrode, and due to the electrostatic attraction, the TB molecules and ssDNA-Fc are adsorbed and enriched on the surface of the electrode by electrostatic attraction, which produces two strong and oppositely changing electrochemical signals, and the electrochemical signals depend on the HER2 concentration. It can sensitively detect HER2 biomarkers in only 40 min with the detection range of 0.0001-10 ng/mL and detection limits as low as 10 fg/mL. The electrochemical microswimmer for the detection of trace disease biomarkers involves a one-step process of capture, signal change, and detection.

Herein, we develop a hemin-functionalized microfluidic chip with dual-electric signal outputs for accurate determination of uric acid (UA). Hemin is designed as the catalyst, which could trigger a built-in reference signal. Carbon nanotube (CNT) and alkalinized titanium carbide (alk-Ti 3 C 2 T x ) are used as attachment substrates to strengthen the signal. Benefiting from the synergistic action of hemin, CNT, and alk-Ti 3 C 2 T x , the hybrid functionalized sensor shows prominent electrochemical capacity, desirable catalytic activity, and unique built-in signal ability. Through density functional theory calculations, the structure-reactivity relationship and possible signal output mechanism are deeply investigated. The functionalized sensor is further integrated into a microfluidic chip to prepare a portable electrochemical sensing platform, in which multiple sample processing steps including primary filtration, target enrichment, and reliable analysis can be conducted step-by-step. Based on the abovementioned designs, the developed functionalized microfluidic platform presents desirable performance in UA determination with a detection limit of 0.41 μM. Furthermore, it is capable of accurately detecting UA in urine samples, providing a promising idea for biomolecule monitoring.

Phosphatidylserine (PS) has been widely used in the fields of food and medicine, among others, owing to its unique chemical structure and health benefits. However, the phospholipase D (PLD)-mediated enzymatic production of PS remains a challenge due to the low transphosphatidylation activity of PLD. Therefore, in the present study, we designed a maltose-binding protein (MBP) tag and a PLD co-expression method to achieve the expression of soluble PLD in Escherichia coli . A "reconstruct substrate pocket" strategy was then proposed based on the catalytic mechanism and molecular dynamics simulation, expanding the substrate pocket and manipulating the coordination of l-Ser within the active site. The best mutant ( Sr MBP PLD Mu6 ) exhibited a 2.04-fold higher transphosphatidylation/hydrolysis ratio than the wild-type Furthermore, under optimal conditions, Mu 6 produced 58.6 g/L PS with 77.2% conversion, within 12 h on a 3 L scale, which demonstrates the potential of the proposed method for industrial application.

By using first-principles calculations, the sensing properties of pristine and transition metal (TM) atoms (Ti, V, and Co) embedded germanium selenide (GeSe) monolayer toward small gas molecules (H 2 , NH 3 , CO, O 2 , SO 2 , NO, and NO 2 ) were investigated. The adsorption energies, electronic structure, optical properties, and recovery time of the adsorption systems were calculated and analyzed in detail. The results indicate that TM doped GeSe has stronger interaction with gas molecules compared with the pristine GeSe monolayer. Especially for Ti- and V-GeSe monolayer, the absolute value of adsorption energies are up to 2 eV for O 2 , NO, and NO 2 . The doping with TM atoms also changes the charge transfer and electronic structures of adsorption systems. Combined with the result of the calculated optical properties and recovery time, it can be concluded that Ti-GeSe monolayer has great potential for NH 3 detection, while Co-GeSe monolayer can be very promising SO 2 gas sensors.

In this study, a series of Cu 2+ x - y In y Se (-0.3 ≤ x ≤ 0.2 and 0 ≤ y ≤ 0.05) samples were prepared by melting and the spark plasma sintering method. X-ray diffraction measurements indicate that the Cu-deficient samples ( x = -0.3 y = 0 and x = -0.2 y = 0) prefer to form the cubic phase (β-Cu 2 Se). Adding excessive Cu or introducing In atoms into the Cu 2 Se matrix triggers a phase transition from the β to α phase. Positron lifetime measurements confirm the reduction in Cu vacancy concentration by adding excessive Cu or introducing In atoms into Cu 2 Se, which causes a dramatic decrease in carrier concentration from 1.59 × 10 21 to 5.0 × 10 19 cm -3 at room temperature. The samples with In contents of 0.01 and 0.03 show a high power factor of about 1 mW m -1 K -2 at room temperature due to the optimization of the carrier concentration. Meanwhile, the excess Cu content and doping of In atoms also favor the formation of nanopores. These pores have strong interaction with phonons, leading to remarkable reduction in lattice thermal conductivity. Finally, a high ZT value of about 1.44 is achieved at 873 K in the Cu 1.99 In 0.01 Se ( x = 0 and y = 0.01) sample, which is about twice that of the Cu-deficient sample (Cu 1.7 Se). Our work provides a viable insight into tuning vacancy defects to improve efficiently the electrical and thermal transport performance for copper-based thermoelectric materials.

In this work, the thermoelectric performance of a typical small-molecule organic semiconductor rubrene under different hydrostatic pressures was studied by first-principles calculation and molecular dynamics simulation. The ZT value of rubrene can reach 1.6 at 400 K due to an unprecedented increase in hole mobility under hydrostatic pressure. The underlying mechanism is ascribed to the suppression of low-frequency phonons (which weakens electron-phonon scattering) and the increase in the intermolecular electronic coupling. The effect of uniaxial stress has also been investigated to confirm this conclusion. Our results provide meaningful insights to understand the relationship between thermoelectric properties and hydrostatic pressure in organic semiconductors.

It is well known that extracellular matrix stiffness can affect cell fate and change dynamically during many biological processes. Existing experimental means for in situ matrix stiffness modulation often alters its structure, which could induce additional undesirable effects on cells. Inspired by the phenomenon of depth sensing by cells, we introduce here core-shell microfibers with a thin collagen core for cell growth and an alginate shell that can be dynamically stiffened to deliver mechanical stimuli. This allows for the maintenance of biochemical properties and structure of the surrounding microenvironment, while dynamically modulating the effective modulus "felt" by cells. We show that simple addition of Sr 2+ in media can easily increase the stiffness of initially Ca 2+ cross-linked alginate shells. Thus, despite the low stiffness of collagen cores (<5 kPa), the effective modulus of the matrix "felt" by cells are substantially higher, which promotes osteogenesis differentiation of human mesenchymal stem cells. We show this effect is more prominent in the stiffening microfiber compared to a static microfiber control. This approach provides a versatile platform to independently and dynamically modulate cellular microenvironments with desirable biochemical, physical, and mechanical stimuli without an unintended interplay of effects, facilitating investigations of a wide range of dynamic cellular processes.

In this paper, we report a series of x polycrystalline AgCuTe 1- x Se samples with high thermoelectric performance. X-ray photoelectron spectroscopy data suggest the observation of Ag + , Cu + , Te 2- , and Se 2- states of Ag, Cu, Te, and Se. Meanwhile, the carrier concentration of the obtained p-type samples changes from 9.12 × 10 18 to 0.86 × 10 18 cm -3 as their carrier mobility varies from 698.55 to 410.12 cm 2 ·V -1 ·s -1 at 300 K. Compared with undoped AgCuTe, an ultralow thermal conductivity is realized in AgCuTe 1- x Se x due to the enhanced phonon scattering. Ultimately, a maximum figure of merit (ZT) of ∼1.45 at 573 K and a high average ZT above 1.0 at temperatures ranging from room temperature to 773 K can be achieved in AgCuTe 0.9 Se 0.1 , which increases by 186% compared to that of the undoped AgCuTe (0.82 at 573 K). This work provides a viable insight toward understanding the effect of the Se atom on the lattice structure and thermoelectric properties of AgCuTe and other transition-metal dichalcogenides.

In this paper, 2 atom % Al-doped ZnO (AZO) was prepared by the co-precipitation method together with sparking plasma sintering (SPS) treatment. The as-synthesized AZO powders show the morphology of hollow hexagonal towers, which result in a high porosity of 50.6% in the bulk sample consolidated by SPS sintering at 400 °C, and the porosity decreases gradually with increasing sintering temperature up to 1000 °C. Positron annihilation measurements reveal that even after sintering at 1000 °C, there are still a considerable number of small pores. A high electrical conductivity of 3 × 10 5 S m -1 is achieved at room temperature for the AZO sample sintered at 1000 °C, while the absolute values of Seebeck coefficient keep at relatively high values between 59 and 144 μV K -1 in the measurement temperature range of 27-500 °C, leading to a high power factor of 3.4 × 10 -3 W m -1 K -2 . On the other hand, the pores in AZO act as strong phonon scattering centers, and an extremely low thermal conductivity of 1.5 W m -1 K -1 measured at room temperature is obtained for AZO sintered at 400 °C. Due to the residual pores in the 1000 °C-sintered sample, the thermal conductivity is still relatively low. As a result, a maximum ZT of 0.275 measured at 500 °C is obtained in this sample, which is the highest ZT reported for ZnO around this temperature.

Photonic detection with narrow spectrum selectivity is very important to eliminate the signal from obtrusive light, which can improve the anti-interference ability of the infrared imaging system. While the self-driving effect inherent to the p-n junction is very attractive in optic-electronic integration, the application of the p-n junction in narrow-band photodetectors is limited by the usual broad absorption range. In this work, a self-powered filterless narrowband near-infrared photodetector based on CuGaTe 2 /silicon p-n junction was reported. The as-fabricated photodetector exhibited typical narrow-band response which shall be ascribed to the slightly smaller band gap of Si than CuGaTe 2 and the restricted photocurrent generation region in the p-n heterojunction by optimizing CuGaTe 2 thickness. It is observed that when the thickness of CuGaTe 2 film is 143 nm, the device exhibits a response peak centered around 1050 nm with a full-width at half-maximum of ∼118 nm. Further device analysis reveals a specific detectivity of ∼10 12 Jones and a responsivity of 114 mA/W under 1064 nm illumination at zero bias. It was also found that an image system based on the narrowband CuGaTe 2 /Si photodetector showed high noise immunity for its spectral selective characteristics.

Few-layered InSe nanosheets were fabricated by the simple liquid-phase exfoliation method. The morphology and crystal structure features of InSe nanosheet sample were characterized comprehensively. The photoluminescence (PL) spectrum indicated that the liquid-phase exfoliated InSe nanosheets contained variously layered nanoflakes, where eight layers nanosheets dominate. In addition, the first-principle simulation was carried out to describe the electron density of states (DOS) and the electronic band structures. Moreover, the few-layered InSe nanosheets performed excellent nonlinear absorption properties in a broad spectral band. As an application, the stable passively Q-switched (PQS) lasers with few-layered InSe nanosheets saturable absorbers (SAs) were realized with the operating wavelengths at 1.06, 1.34, and 1.91 μm. The shortest pulse durations were 599, 520, and 210 ns, respectively. Our results confirmed that the few-layered InSe nanosheets could be an excellent candidate for pulsed lasers in wide spectral bands.

A series of amorphous melamine-based polymer networks synthesized by Schiff base chemistry (SNW) were successfully prepared by varying the strut length. The pore structure was analyzed by gas adsorption and positron annihilation methods. Positron lifetime measurements indicate the existence of ultramicropores and also larger mesopores in the SNW materials. The sizes of micropores and mesopores are almost the same in these samples, which are about 0.7 and 16.5 nm, respectively. The relative number of micropores increases in the order of SNW-1 < SNW-2 < SNW-3, while the number of mesopores increases in the reverse order. N 2 adsorption/desorption measurements also reveal micropores and mesopores in these materials. However, it gives an underestimation of the micropore volume. Benefiting from the abundant nitrogen content and high microporosity, the SNW materials exhibit exceptionally high CO 2 capture ability, which reaches a maximum value of 18.3 wt % in SNW-3 at 273 K and 1 bar, followed by SNW-2 and SNW-1. This order is exactly the same as the order of micropore volume revealed by positron annihilation measurement, suggesting that micropores play a crucial role in the CO 2 uptake. Our results show that positron can provide more precise information about the structure of micropores and thus can offer an accurate prediction for the adsorption capacity of complex porous materials.

An unexpected cascade transformation of aminonaphthoquinones with N-substituents bearing a p-methoxybenzyl ether into bridged-ring-fused naphthalenone derivatives is reported. This cascade transformation was initiated by a catalytic amount of Zn(OTf) 2 and involved with subsequent functional group migration and cyclization. The process proceeded through the cleavage of two bonds and the formation of three new bonds in one pot and was proven to be efficient and tolerant to various substituents.

A unified and concise approach to the synthesis of nine curvularin-type metabolites and two analogues has been developed with few steps and high yields. Among them, sumalactones A-D were synthesized for the first time. The key steps in this approach included esterification, Friedel-Crafts acylation, and ring-closing metathesis (or cross metathesis).

The preparation of graphene aerogel by hydrothermal or chemical reduction has been one of the hot topics of research. But in the process of assembly, the random weak connection of GO flakes leads to irreversible deformation under compression, and the mechanical stability of aerogel based on graphene is one of its drawbacks that is hard to overcome. Here, a novel method to prepare graphene aerogel with high mechanical stability was proposed via combining surface support brought by metallic-CNT networks and interfacial cross-linking of GO sheets achieved by nanoparticle selective absorption. Thoroughly dispersed metallic-CNTs absorbed on the basal plane of GO flakes formed continuous network structures, which not only improve the mechanical performance of flakes but also provide steric effects to impel the adsorption of metallic oxide magnetic nanoparticles concentrated on the edge of GO flakes, thereby guaranteeing the interfacial connection of adjacent rGO flakes by nanoparticle cross-linking. Meanwhile, the surface and interface reinforce approach can greatly improve the electrical conductivity and mechanical stability of composites. Owing to the light weight, abundant interface, high electrical conductivity, combined with the superparamagnetic properties brought by the magnetic nanoparticles, composite aerogel with high mechanical stability and excellent microwave absorption was achieved, of which the effective absorption bandwidth of the aerogel is 4.4-18 GHz and the maximum value can reach -49 dB. This approach could not only be used to prepare microwave absorption materials with light weight and high performance but also be meaningful to enlarge the construction and application of carbon-based materials.

Artificial structural colors based on short-range-ordered amorphous photonic structures (APSs) have attracted great scientific and industrial interest in recent years. However, the previously reported methods of self-assembling colloidal nanoparticles lack fine control of the APS coating and fixation on substrates and poorly realize three-dimensional (3D) conformal coatings for objects with irregular or highly curved surfaces. In this paper, atomization deposition of silica colloidal nanoparticles with poly(vinyl alcohol) as the additive is proposed to solve the above problems. By finely controlling the thicknesses of APS coatings, additive mixing of noniridescent structural colors is easily realized. Based on the intrinsic omnidirectional feature of atomization, a one-step 3D homogeneous conformal coating is also readily realized on various irregular or highly curved surfaces, including papers, resins, metal plates, ceramics, and flexible silk fabrics. The vivid coatings on silk fabrics by atomization deposition possess robust mechanical properties, which are confirmed by rubbing and laundering tests, showing great potential in developing an environmentally friendly coloring technique in the textile industry.

Molecular dynamics simulation studies were employed to investigate the microscopic behaviors of CH 4 and CO 2 molecules in slit-nanopores (SNPs) with various surfaces and different compositions. Three kinds of SNPs were constructed by a pair-wise combination of graphene, silica, and the calcite surface. The grand canonical Monte Carlo and molecular dynamics simulation methods were used to investigate the adsorption and self-diffusion of the gases in the nanopores. It is found that in all three cases, the CH 4 molecules prefer to adsorb onto the graphene surface, whereas the CO 2 molecules prefer to adsorb onto the calcite surface. The adsorption intensity of gases adsorbed onto various surfaces, the adsorption distances, along with the details of adsorption orientations of CH 4 and CO 2 molecules on various surfaces are calculated. The surface characteristics, such as surface roughness and charge distribution, are analyzed to help understand the microscopic adsorption behaviors of the gases on the specific surface. It was found that competitive adsorptions of CO 2 over CH 4 broadly occurred, especially in the SNPs containing calcite, because of the strong adsorption interactions between the CO 2 molecules and the calcite surface. This work provides the microbehaviors of CH 4 and CO 2 in SNPs with various surfaces in different compositions to provide useful guidance for better understanding about the microstate of gases in complex nanoporous shale formation and to give out useful guidance for enhancing shale gas recovery by injecting CO 2 ., Competing Interests: The authors declare no competing financial interest.

A concise total synthesis of aetheramide A in an overall yield of 4.7% with a longest linear sequence of 15 steps is described. This synthetic strategy features macrocyclization via an intramolecular trapping of acylketene generated from dioxinone precursor, and stereoselective late-stage methylation of β-ketoamide. Aetheramide B could be synthesized via the ester migration of aetheramide A.

The insertion of arynes into P-O bonds for the preparation of o-hydroxy-substituted arylphosphine oxides, -phosphinates, and -phosphonates is described. This novel reaction leads to the simultaneous formation of C-P and C-O bonds in one step with good yields and regioselectivities under mild and transition-metal-free conditions. The easy follow-up transformations of the resulting o-hydroxyl group extend these reactions to the facile construction of other ortho-substituted arylphosphorus compounds.

The concise total syntheses of the potent HIV inhibitors aetheramides A and B (IC50 values of 15 and 18 nM), as well as three pairs of their stereoisomers, were achieved, which allowed the complete stereochemical assignment of aetheramides for the first time. With a longest linear sequence of 15 steps, the convergent, fully stereocontrolled route provided aetheramides A and B in 5.3% and 3.6% yields, respectively. The synthetic strategy features efficient Stille coupling for macrocyclization, asymmetric aldol reactions to establish the ambiguous stereochemistries at C-17 and C-26, and implementation of mild conditions to avoid the epimerization of the sensitive polyketide moiety and the migration of the labile lactone.

Organic electronics have gained widespread attention due to their flexibility, lightness, and low-cost potential. It is attractive due to the possibility of large-scale roll-to-roll processing. However, organic electronics require additional development before they can be made commercially available and fully integrated into everyday life. To achieve feasibility for commercial use, these devices must be biocompatible and flexible while maintaining high performance. In this study, biocompatible silk fibroin (SF) was integrated with a mesh of silver nanowires (AgNWs) to build up flexible organic solar cells with maximum power conversion efficiency of up to 6.62%. The AgNW/SF substrate exhibits a conductivity of ∼11.0 Ω/sq and transmittance of ∼80% in the visible light range. These substrates retained their conductivity, even after being bent and unbent 200 times; this surprising ability was attributed to its embedded structure and the properties of the specific SF materials used. To contrast, indium tin oxide on synthetic plastic substrate lost its conductivity after the much less rigid bending. These lightweight and silk-based organic solar cells pave the way for future biocompatible interfaces between wearable electronics and human skin.

The RNA induced silencing complex (RISC) contains at its core the endonuclease Argonaute (Ago) that allows for guide strand (GS)-mediated sequence-specific cleavage of the target mRNA. Functionalization of the sugar/phosphodiester backbone of the GS, which is in direct contact with Ago, presents a logical opportunity to affect RISC's activity. A systematic evaluation of modified nucleosides requires the synthesis of phosphoramidites corresponding to all four canonical bases (A, U, C, and G) and their sequential evaluation at each position along the 21-nucleotide-long GS. With the use of a platform approach, the sequential replacement of canonical bases with inosine greatly simplifies the problem and defines a new activity baseline toward which the corresponding sugar-modified inosines are compared. This approach was validated using 2'-O-benzyl modification, which demonstrated that positions 5, 8, 15, and 19 can accommodate this large group. Application of this high-throughput methodology now allows for hypothesis-driven rational design of highly potent, immunologically silent and stable siRNAs suitable for therapeutic applications.

The trans-4-hydroxynonenal (HNE)-derived exocyclic 1, N(2)-dG adduct with (6S,8R,11S) stereochemistry forms interstrand N(2)-dG-N(2)-dG cross-links in the 5'-CpG-3' DNA sequence context, but the corresponding adduct possessing (6R,8S,11R) stereochemistry does not. Both exist primarily as diastereomeric cyclic hemiacetals when placed into duplex DNA [Huang, H., Wang, H., Qi, N., Kozekova, A., Rizzo, C. J., and Stone, M. P. (2008) J. Am. Chem. Soc. 130, 10898-10906]. To explore the structural basis for this difference, the HNE-derived diastereomeric (6S,8R,11S) and (6R,8S,11R) cyclic hemiacetals were examined with respect to conformation when incorporated into 5'-d(GCTAGC XAGTCC)-3' x 5'-d(GGACTCGCTAGC)-3', containing the 5'-CpX-3' sequence [X = (6S,8R,11S)- or (6R,8S,11R)-HNE-dG]. At neutral pH, both adducts exhibited minimal structural perturbations to the DNA duplex that were localized to the site of the adduction at X(7) x C(18) and its neighboring base pair, A(8) x T(17). Both the (6S,8R,11S) and (6R,8S,11R) cyclic hemiacetals were located within the minor groove of the duplex. However, the respective orientations of the two cyclic hemiacetals within the minor groove were dependent upon (6S) versus (6R) stereochemistry. The (6S,8R,11S) cyclic hemiacetal was oriented in the 5'-direction, while the (6R,8S,11R) cyclic hemiacetal was oriented in the 3'-direction. These cyclic hemiacetals effectively mask the reactive aldehydes necessary for initiation of interstrand cross-link formation. From the refined structures of the two cyclic hemiacetals, the conformations of the corresponding diastereomeric aldehydes were predicted, using molecular mechanics calculations. Potential energy minimizations of the duplexes containing the two diastereomeric aldehydes predicted that the (6S,8R,11S) aldehyde was oriented in the 5'-direction while the (6R,8S,11R) aldehyde was oriented in the 3'-direction. These stereochemical differences in orientation suggest a kinetic basis that explains, in part, why the (6S,8R,11S) stereoisomer forms interchain cross-links in the 5'-CpG-3' sequence whereas the (6R,8S,11R) stereoisomer does not.

trans-4-Hydroxynonenal (HNE) is a peroxidation product of omega-6 polyunsaturated fatty acids. The Michael addition of deoxyguanosine to HNE yields four diastereomeric exocyclic 1,N(2)-dG adducts. The corresponding acrolein- and crotonaldehyde-derived exocyclic 1,N(2)-dG adducts undergo ring-opening to N(2)-dG aldehydes, placing the aldehyde functionalities into the minor groove of DNA. The acrolein- and the 6R-crotonaldehyde-derived exocyclic 1,N(2)-dG adducts form interstrand N(2)-dG:N(2)-dG cross-links in the 5'-CpG-3' sequence context. Only the HNE-derived exocyclic 1,N(2)-dG adduct of (6S,8R,11S) stereochemistry forms interstrand N(2)-dG:N(2)-dG cross-links in the 5'-CpG-3' sequence context. Moreover, as compared to the exocyclic 1,N(2)-dG adducts of acrolein and crotonaldehyde, the cross-linking reaction is slow (Wang, H.; Kozekov, I. D.; Harris, T. M.; Rizzo, C. J. J. Am. Chem. Soc. 2003, 125, 5687-5700). Accordingly, the chemistry of the HNE-derived exocyclic 1,N(2)-dG adduct of (6S,8R,11S) stereochemistry has been compared with that of the (6R,8S,11R) adduct, when incorporated into 5'-d(GCTAGCXAGTCC)-3'.5'-d(GGACTCGCTAGC)-3', containing the 5'-CpG-3' sequence (X = HNE-dG). When placed complementary to dC in this duplex, both adducts open to the corresponding N(2)-dG aldehydic rearrangement products, suggesting that the formation of the interstrand cross-link by the exocyclic 1,N(2)-dG adduct of (6S,8R,11S) stereochemistry, and the lack of cross-link formation by the exocyclic 1,N(2)-dG adduct of (6R,8S,11R) stereochemistry, is not attributable to inability to undergo ring-opening to the aldehydes in duplex DNA. Instead, these aldehydic rearrangement products exist in equilibrium with stereoisomeric cyclic hemiacetals. The latter are the predominant species present at equilibrium. The trans configuration of the HNE H6 and H8 protons is preferred. The presence of these cyclic hemiacetals in duplex DNA is significant as they mask the aldehyde species necessary for interstrand cross-link formation.