Gold-catalyzed cyclization and cycloaddition in natural product synthesis.

Covering: 2016 to mid 2023Transition metal catalysis, known for its remarkable capacity to expedite the assembly of molecular complexity from readily available starting materials in a single operation, occupies a central position in contemporary chemical synthesis. Within this landscape, gold-catalyzed reactions present a novel and versatile paradigm, offering robust frameworks for accessing diverse structural motifs. In this review, we highlighted a curated selection of publications in the past 8 years, focusing on the deployment of homogeneous gold catalysis in the ring-forming step for the total synthesis of natural products. These investigations are categorized based on the specific ring formations they engender, accentuating the prevailing gold-catalyzed methodologies applied to surmount intricate challenges in natural products synthesis.

A genome-wide CRISPR screening uncovers that TOB1 acts as a key host factor for FMDV infection via both IFN and EGFR mediated pathways.

The interaction between foot-and-mouth disease virus (FMDV) and the host is extremely important for virus infection, but there are few researches on it, which is not conducive to vaccine development and FMD control. In this study, we designed a porcine genome-scale CRISPR/Cas9 knockout library containing 93,859 single guide RNAs targeting 16,886 protein-coding genes, 25 long ncRNAs, and 463 microRNAs. Using this library, several previously unreported genes required for FMDV infection are highly enriched post-FMDV selection in IBRS-2 cells. Follow-up studies confirmed the dependency of FMDV on these genes, and we identified a functional role for one of the FMDV-related host genes: TOB1 (Transducer of ERBB2.1). TOB1-knockout significantly inhibits FMDV infection by positively regulating the expression of RIG-I and MDA5. We further found that TOB1-knockout led to more accumulation of mRNA transcripts of transcription factor CEBPA, and thus its protein, which further enhanced transcription of RIG-I and MDA5 genes. In addition, TOB1-knockout was shown to inhibit FMDV adsorption and internalization mediated by EGFR/ERBB2 pathway. Finally, the FMDV lethal challenge on TOB1-knockout mice confirmed that the deletion of TOB1 inhibited FMDV infection in vivo. These results identify TOB1 as a key host factor involved in FMDV infection in pigs.

Manipulation of cross-linking in PEDOT:PSS hydrogels for biointerfacing.

Conducting hydrogels can be used to fabricate bioelectronic devices that are soft for improved cell- and tissue-interfacing. Those based on conjugated polymers, such as poly(3,4-ethylene-dioxythiophene):polystyrene sulfonate (PEDOT:PSS), can be made simply with solution-based processing techniques, yet the influence of fabrication variables on final gel properties is not fully understood. In this study, we investigated if PEDOT:PSS cross-linking could be manipulated by changing the concentration of a gelling agent, ionic liquid, in the hydrogel precursor mixture. Rheology and gelation kinetics of precursor mixtures were investigated, and aqueous stability, swelling, conductivity, stiffness, and cytocompatibility of formed hydrogels were characterized. Increasing ionic liquid concentration was found to increase cross-linking as measured by decreased swelling, decreased non-network fraction, increased stiffness, and increased conductivity. Such manipulation of IL concentration thus afforded control of final gel properties and was utilized in further investigations of biointerfacing. When cross-linked sufficiently, PEDOT:PSS hydrogels were stable in sterile cell culture conditions for at least 28 days. Additionally, hydrogels supported a viable and proliferating population of human dermal fibroblasts for at least two weeks. Collectively, these characterizations of stability and cytocompatibility illustrate that these PEDOT:PSS hydrogels have significant promise for biointerfacing applications that require soft materials for direct interaction with cells.

A charge transfer framework that describes supramolecular interactions governing structure and properties of 2D perovskites.

The elucidation of structure-to-function relationships for two-dimensional (2D) hybrid perovskites remains a primary challenge for engineering efficient perovskite-based devices. By combining insights from theory and experiment, we describe the introduction of bifunctional ligands that are capable of making strong hydrogen bonds within the organic bilayer. We find that stronger intermolecular interactions draw charge away from the perovskite layers, and we have formulated a simple and intuitive computational descriptor, the charge separation descriptor (CSD), that accurately describes the relationship between the Pb-I-Pb angle, band gap, and in-plane charge transport with the strength of these interactions. A higher CSD value correlates to less distortion of the Pb-I-Pb angle, a reduced band gap, and higher in-plane mobility of the perovskite. These improved material properties result in improved device characteristics of the resulting solar cells.

Hot-Casting-Assisted Liquid Additive Engineering for Efficient and Stable Perovskite Solar Cells.

High-performance inorganic-organic lead halide perovskite solar cells (PSCs) are often fabricated with a liquid additive such as dimethyl sulfoxide (DMSO), which retards crystallization and reduces roughness and pinholes in the perovskite layers. However, DMSO can be trapped during perovskite film formation and induce voids and undesired reaction byproducts upon later processing steps. Here, it is shown that the amount of residual DMSO can be reduced in as-spin-coated films significantly through use of preheated substrates, or a so-called hot-casting method. Hot casting increases the perovskite film thickness given the same concentration of solutions, which allows for reducing the perovskite solution concentration. By reducing the amount of DMSO in proportion to the concentration of perovskite precursors and using hot casting, it is possible to fabricate perovskite layers with improved perovskite-substrate interfaces by suppressing the formation of byproducts, which increase trap density and accelerate degradation of the perovskite layers. The best-performing PSCs exhibit a power conversion efficiency (PCE) of 23.4% (23.0% stabilized efficiency) under simulated solar illumination. Furthermore, encapsulated devices show considerably reduced post-burn-in decay, retaining 75% and 90% of their initial and post-burn-in efficiencies after 3000 h of operation with maximum power point tracking (MPPT) under high power of ultraviolet (UV)-containing continuous light exposure.

Accelerated aging of all-inorganic, interface-stabilized perovskite solar cells.

To understand degradation routes and improve the stability of perovskite solar cells (PSCs), accelerated aging tests are needed. Here, we use elevated temperatures (up to 110°C) to quantify the accelerated degradation of encapsulated CsPbI3 PSCs under constant illumination. Incorporating a two-dimensional (2D) Cs2PbI2Cl2 capping layer between the perovskite active layer and hole-transport layer stabilizes the interface while increasing power conversion efficiency of the all-inorganic PSCs from 14.9 to 17.4%. Devices with this 2D capping layer did not degrade at 35°C and required >2100 hours at 110°C under constant illumination to degrade by 20% of their initial efficiency. Degradation acceleration factors based on the observed Arrhenius temperature dependence predict intrinsic lifetimes of 51,000 ± 7000 hours (>5 years) operating continuously at 35°C.

Integrated near-infrared spectral sensing.

Spectral sensing is increasingly used in applications ranging from industrial process monitoring to agriculture. Sensing is usually performed by measuring reflected or transmitted light with a spectrometer and processing the resulting spectra. However, realizing compact and mass-manufacturable spectrometers is a major challenge, particularly in the infrared spectral region where chemical information is most prominent. Here we propose a different approach to spectral sensing which dramatically simplifies the requirements on the hardware and allows the monolithic integration of the sensors. We use an array of resonant-cavity-enhanced photodetectors, each featuring a distinct spectral response in the 850-1700 nm wavelength range. We show that prediction models can be built directly using the responses of the photodetectors, despite the presence of multiple broad peaks, releasing the need for spectral reconstruction. The large etendue and responsivity allow us to demonstrate the application of an integrated near-infrared spectral sensor in relevant problems, namely milk and plastic sensing. Our results open the way to spectral sensors with minimal size, cost and complexity for industrial and consumer applications.

Advancing 2D Perovskites for Efficient and Stable Solar Cells: Challenges and Opportunities.

Perovskite solar cells (PSCs) have rapidly emerged as one of the hottest topics in the photovoltaics community owing to their high power-conversion efficiencies (PCE), and the promise to be produced at low cost. Among various PSCs, typical 3D perovskite-based solar cells deliver high PCE but they suffer from severe instability, which restricts their practical applications. In contrast to 3D perovskites, 2D perovskites that incorporate larger, less volatile, and generally more hydrophobic organic cations exhibit much improved thermal, chemical, and environmental stability. 2D perovskites can have different roles within a solar cell, either as the primary light absorber (2D PSCs), or as a capping layer atop a 3D perovskite absorbing layer (2D/3D PSCs). Tradeoffs between PCE and stability exist in both types of PSCs-2D PSCs are more stable but exhibit lower efficiency while 2D/3D PSCs deliver exciting efficiency but show relatively poor stability. To address this PCE/stability tradeoff, the challenges both the 2D and 2D/3D PSCs face are identified and select works the community has undertaken to overcome them are highlighted in this review. It is ended with several recommendations on how to further improve PSCs so their performance and stability can be commensurate with application requirements.

Design and experiment of array Rayleigh wave-EMAT for plane stress measurement.

The Rayleigh wave excited by the electromagnetic acoustic transducer (EMAT) is an effective selection for surface plane stress measurement. However, the propagation velocity of Rayleigh wave on the metal surface is easily affected by the original rolling process. Besides, the direction of the plane stress state is usually unknown, which means that the propagation velocity cannot be expressed linearly by the stress. As a result, the traditional measurement model of one transmitter and one receiver can only realize the decouple of plane stress components by rotating method, which not only brings position error but also low measurement efficiency. Therefore, this paper focuses on a novel Rayleigh wave-EMAT for plane stress ultrasonic measurement. Firstly, the Rayleigh wave measurement model is established based on the acoustoelastic equation and displacement expression. Furthermore, an array Rayleigh wave-EMATintegrating three transmitters and three receivers is designed. Finally, the typical plane stress state of 5052 aluminum alloy plate after friction stir welding (FSW) is measured. The experimental results show good agreement compared with the hole-drilling method, which verifies the effectiveness of proposed method and designed EMAT.

Accessing Highly Oriented Two-Dimensional Perovskite Films via Solvent-Vapor Annealing for Efficient and Stable Solar Cells.

Accessing vertical orientation of two-dimensional (2D) perovskite films is key to achieving high-performance solar cells with these materials. Herein, we report on solvent-vapor annealing (SVA) as a general postdeposition strategy to induce strong vertical orientation across broad classes of 2D perovskite films. We do not observe any local compositional drifts that would result in impure phases during SVA. Instead, our experiments point to solvent vapor plasticizing 2D perovskite films and facilitating their surface-induced reorientation and concomitant grain growth, which enhance out-of-plane charge transport. Solar cells with SVA 2D perovskites exhibit superior efficiency and stability compared to their untreated analogs. With a certified efficiency of (18.00 ± 0.30) %, our SVA (BDA)(Cs0.1FA0.9)4Pb5I16 solar cell boasts the highest efficiency among all solar cells with 2D perovskites (n ≤ 5) reported so far.

Author Correction: Integrated nano-optomechanical displacement sensor with ultrawide optical bandwidth.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Revisiting the Pig IGHC Gene Locus in Different Breeds Uncovers Nine Distinct IGHG Genes.

IgG subclass diversification is common in placental mammals. It has been well documented in humans and mice that different IgG subclasses, with diversified functions, synergistically regulate humoral immunity. However, our knowledge on the genomic and functional diversification of IgG subclasses in the pig, a mammalian species with high agricultural and biomedical importance, is incomplete. Using bacterial artificial chromosome sequencing and newly assembled genomes generated by the PacBio sequencing approach, we characterized and mapped the IgH C region gene locus in three indigenous Chinese breeds (Erhualian, Xiang, and Luchuan) and compared them to that of Duroc. Our data revealed that IGHG genes in Chinese pigs differ from the Duroc, whereas the IGHM, IGHD, IGHA, and IGHE genes were all single copy and highly conserved in the pig breeds examined. Most striking were differences in numbers of IGHG genes: there are seven genes in Erhualian pigs, six in the Duroc, but only five in Xiang pigs. Phylogenetic analysis suggested that all reported porcine IGHG genes could be classified into nine subclasses: IGHG1, IGHG2a, IGHG2b, IGHG2c, IGHG3, IGHG4, IGHG5a, IGHG5b, and IGHG5c. Using sequence information, we developed a mouse mAb specific for IgG3. This study offers a starting point to investigate the structure-function relationship of IgG subclasses in pigs.

Customized hydrogel substrates for serum-free expansion of functional hMSCs.

We describe a screening approach to identify customized substrates for serum-free human mesenchymal stromal cell (hMSC) culture. In particular, we combine a biomaterials screening approach with design of experiments (DOE) and multivariate analysis (MVA) to understand the effects of substrate stiffness, substrate adhesivity, and media composition on hMSC behavior in vitro. This approach enabled identification of poly(ethylene glycol)-based and integrin binding hydrogel substrate compositions that supported functional hMSC expansion in multiple serum-containing and serum-free media, as well as the expansion of MSCs from multiple, distinct sources. The identified substrates were compatible with standard thaw, seed, and harvest protocols. Finally, we used MVA on the screening data to reveal the importance of serum and substrate stiffness on hMSC expansion, highlighting the need for customized cell culture substrates in optimal hMSC biomanufacturing processes.

Integrated nano-optomechanical displacement sensor with ultrawide optical bandwidth.

Optical read-out of motion is widely used in sensing applications. Recent developments in micro- and nano-optomechanical systems have given rise to on-chip mechanical sensing platforms, potentially leading to compact and integrated optical motion sensors. However, these systems typically exploit narrow spectral resonances and therefore require tuneable lasers with narrow linewidth and low spectral noise, which makes the integration of the read-out extremely challenging. Here, we report a step towards the practical application of nanomechanical sensors, by presenting a sensor with ultrawide (∼80 nm) optical bandwidth. It is based on a nanomechanical, three-dimensional directional coupler with integrated dual-channel waveguide photodiodes, and displays small displacement imprecision of only 45 fm/Hz1/2 as well as large dynamic range (>30 nm). The broad optical bandwidth releases the need for a tuneable laser and the on-chip photocurrent read-out replaces the external detector, opening the way to fully-integrated nanomechanical sensors.

Extending the Photovoltaic Response of Perovskite Solar Cells into the Near-Infrared with a Narrow-Bandgap Organic Semiconductor.

Typical lead-based perovskites solar cells show an onset of photogeneration around 800 nm, leaving plenty of spectral loss in the near-infrared (NIR). Extending light absorption beyond 800 nm into the NIR should increase photocurrent generation and further improve photovoltaic efficiency of perovskite solar cells (PSCs). Here, a simple and facile approach is reported to incorporate a NIR-chromophore that is also a Lewis-base into perovskite absorbers to broaden their photoresponse and increase their photovoltaic efficiency. Compared with pristine PSCs without such an organic chromophore, these solar cells generate photocurrent in the NIR beyond the band edge of the perovskite active layer alone. Given the Lewis-basic nature of the organic semiconductor, its addition to the photoactive layer also effectively passivates perovskite defects. These films thus exhibit significantly reduced trap densities, enhanced hole and electron mobilities, and suppressed illumination-induced ion migration. As a consequence, perovskite solar cells with organic chromophore exhibit an enhanced efficiency of 21.6%, and substantively improved operational stability under continuous one-sun illumination. The results demonstrate the potential generalizability of directly incorporating a multifunctional organic semiconductor that both extends light absorption and passivates surface traps in perovskite active layers to yield highly efficient and stable NIR-harvesting PSCs.

Nano-opto-electro-mechanical switch based on a four-waveguide directional coupler.

Optical switches connect optical circuits, and route optical signals in networks. Nano-electromechanical systems can in principle enable compact and power-effective switches that can be integrated in photonic circuits. We proposed an optical switch based on four coupled waveguides arranged in three-dimensional configuration. The switching operation is controlled by a cantilever displacement of only 55 nm. Simulations show that our proposed device requires a low switching voltage down to 3V and can operate at frequencies in the MHz range. Our results also pave the way towards novel optical components that electromechanically manipulate light in both the horizontal and the vertical direction in photonic circuits.

Polarization-dependent enhanced photoluminescence and polarization-independent emission rate of quantum dots on gold elliptical nanodisc arrays.

We have fabricated gold (Au) elliptical nanodisc (ND) arrays via three-beam interference lithography and electron beam deposition of gold. The enhanced photoluminescence intensity and emission rate of quantum dots (QDs) near to the Au elliptical NDs have been studied by tuning the nearest distance between quantum dots and Au elliptical NDs. We found that the photoluminescence intensity is polarization-dependent with the degree of polarization being equal to that of the light extinction of the Au elliptical NDs, while the emission rate is polarization-independent. This is resulted from the plasmon-coupled emission via the coupling between the QD dipole and the plasmon nano-antenna. Our experiments fully confirm the evidence of the plasmophore concept proposed recently in the interaction of the QDs with metal nanoparticles.

Dislocated double-layer metal gratings: an efficient unidirectional coupler.

We propose theoretically and demonstrate experimentally a dislocated double-layer metal grating structure, which operates as a unidirectional coupler capable of launching surface plasmon polaritons in a desired direction under normal illumination. The structure consists of a slanted dielectric grating sandwiched between two gold gratings. The upper gold grating has a nonzero lateral relative displacement with respect to the lower one. Numerical simulations show that a grating structure with 7 periods can convert 49% of normally incident light into surface plasmons with a contrast ratio of 78 between the powers of the surface plasmons launched in two opposite directions. We explain the unidirectional coupling phenomenon by the dislocation-induced interference of the diffracted waves from the upper and lower gold gratings. Furthermore, we developed a simple and cost-effective technique to fabricate the structure via tilted two-beam interference lithography and subsequent shadow deposition of gold. The experimental results demonstrate a coupling efficiency of 36% and a contrast ratio of 43. The relatively simple periodic nature of our structure lends itself to large-scale low-cost fabrication and simple theoretical analysis. Also, unlike the previous unidirectional couplers based on aperiodic structures, the design parameters of our unidirectional coupler can be determined analytically. Therefore, this structure can be an important component for surface-plasmon-based nanophotonic circuits by providing an efficient interface between free-space and surface plasmon waves.

Plasmonic gold mushroom arrays with refractive index sensing figures of merit approaching the theoretical limit.

Localized surface plasmon resonance (LSPR)-based sensing has found wide applications in medical diagnosis, food safety regulation and environmental monitoring. Compared with commercial propagating surface plasmon resonance (PSPR)-based sensors, LSPR ones are simple, cost-effective and suitable for measuring local refractive index changes. However, the figure of merit (FOM) values of LSPR sensors are generally 1-2 orders of magnitude smaller than those of PSPR ones, preventing the widespread use of LSPR sensors. Here we describe an array of submicrometer gold mushrooms with a FOM reaching ~108, which is comparable to the theoretically predicted upper limit for standard PSPR sensors. Such a high FOM arises from the interference between Wood's anomaly and the LSPRs. We further demonstrate the array as a biosensor for detecting cytochrome c and alpha-fetoprotein, with their detection limits down to 200 pM and 15 ng ml(-1), respectively, suggesting that the array is a promising candidate for label-free biomedical sensing.

Mitochondrial DNA genetic polymorphism in thirteen rice cytoplasmic male sterile lines.

KEY MESSAGE: Thirteen rice CMS lines derived from different cytoplasms were classified into eight groups by PCR amplification on mtDNA. The orf79 gene, which causes Boro II CMS, possibly results in Dian1-CMS. Thirteen rice cytoplasmic male sterile (CMS) lines derived from different cytoplasms are widely used for hybrid rice breeding. Based on 27 loci on mitochondrial DNA, including single nucleotide polymorphisms and segmental sequence variations between typical indica and japonica as well as high-polymorphism segmental sequence variations and single nucleotide polymorphisms among rice CMS lines, the 13 rice CMS lines were classified into eight groups: (I) wild-abortive CMS, Indonesian Shuitiangu CMS, K-CMS, Gang CMS, D-CMS and dwarf abortive CMS; (II) Maxie-CMS; (III) Honglian CMS; (IV) Boro II CMS; (V) Dian1-CMS; (VI) Liao-CMS; (VII) Lead CMS; and (VIII) Chinese wild rice CMS. According to their pollen abortion phenotypes, groups I and II (including 7 CMS lines) were classified as sporophytic CMS lines, the cytoplasmic genetic relationships among which were very close. They could have originated from similar, or even the same, cytoplasm donors. Groups III-VIII (including 6 CMS lines) were categorized as gametophytic CMS lines, the cytoplasms of which differed from one another, with some having relatively far genetic relationships. Dian1-CMS was found to harbor the orf79 gene, which causes Boro II CMS, whereas Liao-CMS had an orf79 structure that does not result in Lead CMS. Therefore, we speculated that orf79 is associated with Dian1-CMS but not with Liao-CMS. The atp6-orf79 structure related to sterility was also found to experience multiple evolutionary turnovers. All sporophytic CMS lines were indica-like. Except the Honglian CMS line, which was indica-like, all gametophytic CMS lines were japonica-like.