3D Conjugated Hole Transporting Materials for Efficient and Stable Perovskite Solar Cells and Modules.

The orthogonal structure of the widely used hole transporting material (HTM) Spiro-OMeTAD imparts isotropic conductivity and excellent film-forming capability. However, inherently weak intra- and inter-molecular π-π interactions result in low intrinsic hole mobility. Herein, a novel arylamine derivative, termed FTPE-ST, with a twist conjugated dibenzo[g,p]chrysene core and coplanar 3,4-ethylenedioxythiophene (EDOT) as extended donor units, was designed to enhance intra- and inter-molecular π-π interactions, without compromising on solubility. The 3D configuration provides the material multi-direction charge transport as well as excellent solubility even in 2-methylanisole (2-MA), and its large conjugated delocalization backbone endows the HTM with a high hole mobility (7.2 × 10-4 cm2V-1s-1). Moreover, the sulfur donors in the EDOT units coordinate to lead ions on the perovskite surface, leading to stronger interfacial interactions and the suppression of defects at the perovskite/HTM interface. As a result, perovskite solar cells (PSCs) employing FTPE-ST as the HTM achieve a champion power conversion efficiency (PCE) of 25.21% with excellent long-time stability, which is one of the highest PCEs for non-spiro HTMs in n-i-p PSCs. In addition, the excellent film-forming capacity of the HTM enables the fabrication of FTPE-ST-based large-scale PSCs (1.0 cm2) and modules (29.0 cm2), which achieve PCEs of 24.21% (certificated 24.17%) and 21.27%, respectively. This article is protected by copyright. All rights reserved.

A Multifunctional Dye Molecule as the Interfacial Layer for Perovskite Solar Cells.

In perovskite solar cells (PSCs), defects in the interface and mismatched energy levels can damage the device performance. Improving the interface quality is an effective way to achieve efficient and stable PSCs. In this work, a multifunctional dye molecule, named ThPCyAc, was designed and synthesized to be introduced in the perovskite/HTM interface. On one hand, various functional groups on the acceptor unit can act as Lewis base to reduce defect density and suppress nonradiative combinations. On the other hand, the stepwise energy-level alignment caused by ThPCyAc decreases the accumulation of interface carriers for facilitating charge extraction and transmission. Therefore, based on the ThPCyAc molecule, the devices exhibit elevated open-circuit voltage and fill factor, resulting in the best power conversion efficiency (PCE) of 23.16%, outperforming the control sample lacking the interface layer (PCE = 21.49%). Excitingly, when attempting to apply it as a self-assembled layer in inverted devices, ThPCyAc still exhibits attractive behavior. It is worth noting that these results indicate that dye molecules have great potential in developing multifunctional interface materials to obtain higher-performance PSCs.

Dopant-Free Pyrene-Based Hole Transporting Material Enables Efficient and Stable Perovskite Solar Cells.

Dopant-free hole transporting materials (HTMs) is significant to the stability of perovskite solar cells (PSCs). Here, we developed a novel star-shape arylamine HTM, termed Py-DB, with a pyrene core and carbon-carbon double bonds as the bridge units. Compared to the reference HTM (termed Py-C), the extension of the planar conjugation backbone endows Py-DB with typical intermolecular π-π stacking interactions and excellent solubility, resulting in improved hole mobility and film morphology. In addition, the lower HOMO energy level of the Py-DB HTM provides efficient hole extraction with reduced energy loss at the perovskite/HTM interface. Consequently, an impressive power conversion efficiency (PCE) of 24.33 % was achieved for dopant-free Py-DB-based PSCs, which is the highest PCE for dopant-free small molecular HTMs in n-i-p configured PSCs. The dopant-free Py-DB-based device also exhibits improved long-term stability, retaining over 90 % of its initial efficiency after 1000 h exposure to 25 % humidity at 60 °C. These findings provide valuable insights and approaches for the further development of dopant-free HTMs for efficient and reliable PSCs.

Microbial mechanisms regulate soil organic carbon mineralization under carbon with varying levels of nitrogen addition in the above-treeline ecosystem.

Climate change is leading to the upward migration of treelines in mountainous regions, resulting in changes to the carbon and nitrogen inputs in soils. The impact of these alterations on the microbial mineralization of the existing soil organic carbon (SOC) pool remains uncertain, making it challenging to anticipate their effects on the carbon balance. To enhance our prediction and understanding of native SOC mineralization in Himalayan regions resulting from treeline shifts, a study was conducted to quantify soil priming effects (PEs) at high elevations above the treeline ecosystem. In laboratory incubation, soils were treated with a combination of 13C-glucose and varying nitrogen rates, along with carbon-only treatments and control groups without any amendments. The addition of carbon with varying nitrogen addition rates exhibited diverse PEs on native SOC. A highly positive PE was observed under low nitrogen input due to a high carbon/nitrogen imbalance and increased L-leucine aminopeptidase (LAP) activity, coupled with low nitrogen availability and carbon use efficiency (CUE). In contrast, a positive PE declined following high nitrogen input due to a low carbon/nitrogen imbalance and LAP activity, coupled with high nitrogen availability and CUE. These findings support the concept that multiple mechanisms (i.e., microbial nitrogen mining and microbial metabolic efficiency) exist that regulate SOC mineralization under the addition of carbon with varying nitrogen rates. Thus, an increase in nitrogen availability fulfils microbial nitrogen demand, reduces the microbial carbon/nitrogen imbalance, decreases enzyme activity that requires nitrogen and enhances microbial metabolic efficiency. Consequently, this mechanism reduces the positive PE, thereby serving as a potential tool for stabilizing native SOC in above-treeline ecosystems.

Design Strategies for Aqueous Zinc Metal Batteries with High Zinc Utilization: From Metal Anodes to Anode-Free Structures.

Aqueous zinc metal batteries (AZMBs) are promising candidates for next-generation energy storage due to the excellent safety, environmental friendliness, natural abundance, high theoretical specific capacity, and low redox potential of zinc (Zn) metal. However, several issues such as dendrite formation, hydrogen evolution, corrosion, and passivation of Zn metal anodes cause irreversible loss of the active materials. To solve these issues, researchers often use large amounts of excess Zn to ensure a continuous supply of active materials for Zn anodes. This leads to the ultralow utilization of Zn anodes and squanders the high energy density of AZMBs. Herein, the design strategies for AZMBs with high Zn utilization are discussed in depth, from utilizing thinner Zn foils to constructing anode-free structures with theoretical Zn utilization of 100%, which provides comprehensive guidelines for further research. Representative methods for calculating the depth of discharge of Zn anodes with different structures are first summarized. The reasonable modification strategies of Zn foil anodes, current collectors with pre-deposited Zn, and anode-free aqueous Zn metal batteries (AF-AZMBs) to improve Zn utilization are then detailed. In particular, the working mechanism of AF-AZMBs is systematically introduced. Finally, the challenges and perspectives for constructing high-utilization Zn anodes are presented.

Topological analysis of functional connectivity in Parkinson's disease.

Parkinson's disease (PD) is a clinically heterogeneous disorder, which mainly affects patients' motor and non-motor function. Functional connectivity was preliminary explored and studied through resting state functional magnetic resonance imaging (rsfMRI). Through the topological analysis of 54 PD scans and 31 age-matched normal controls (NC) in the Neurocon dataset, leveraging on rsfMRI data, the brain functional connection and the Vietoris-Rips (VR) complex were constructed. The barcodes of the complex were calculated to reflect the changes of functional connectivity neural circuits (FCNC) in brain network. The 0-dimensional Betti number ß0 means the number of connected branches in VR complex. The average number of connected branches in PD group was greater than that in NC group when the threshold δ ≤ 0.7. Two-sample Mann-Whitney U test and false discovery rate (FDR) correction were used for statistical analysis to investigate the FCNC changes between PD and NC groups. In PD group, under threshold of 0.7, the number of FCNC involved was significantly differences and these brain regions include the Cuneus_R, Lingual_R, Fusiform_R and Heschl_R. There are also significant differences in brain regions in the Frontal_Inf_Orb_R and Pallidum_R, when the threshold increased to 0.8 and 0.9 (p < 0.05). In addition, when the length of FCNC was medium, there was a significant statistical difference between the PD group and the NC group in the Neurocon dataset and the Parkinson's Progression Markers Initiative (PPMI) dataset. Topological analysis based on rsfMRI data may provide comprehensive information about the changes of FCNC and may provide an alternative for clinical differential diagnosis.

High-Throughput Sequencing Reveals a Dynamic Bacterial Linkage between the Captive White Rhinoceros and Its Environment.

Soil is an essential part of the animal habitat and has a large diversity of microbiota, while the animal body was colonized by a complex bacterial community; so far, the relationship between the animal host microbial community and the soil microbial ecosystem remains largely unknown. In this study, 15 white rhinoceros from three different captive grounds were selected and the bacterial community of the gut, skin, and environment of these rhinoceros were analyzed by 16S rRNA sequencing technology. Our results showed that Firmicutes and Bacteroidota were the predominant phyla in the gut microbiome, whereas skin and environment samples share similar microbiome profiles and are dominated by the phyla of Actinobacteriota, Chloroflexi, and Proteobacteria. Although the bacterial composition of the gut differs from that of the skin and environment, the Venn diagrams showed that there were 22 phyla and 186 genera shared by all the gut, skin, and environmental microbes in white rhinoceroses. Further cooccurrence network analysis indicated a bacterial linkage based on a complex interaction was established by the bacterial communities from the three different niches. In addition, beta diversity and bacterial composition analysis showed that both the captive ground and host ages induced shifts in the microbial composition of white rhinoceroses, which suggested that the bacterial linkage between the captive white rhinoceros and its environment is dynamic. Overall, our data contribute to a better understanding of the bacterial community of the captive white rhinoceros, especially for the relationship between the environment and animal bacterial communities. IMPORTANCE The white rhinoceros is one of the world's most endangered mammals. The microbial population plays a key role in animal health and welfare; however, studies regarding the microbial communities of the white rhinoceros are relatively limited. As the white rhinoceros has a common behavior of mud baths and thus is in direct contact with the environment, a relationship between the animal microbial community and the soil microbial ecosystem appears possible, but it remains unclear. Here, we described the characteristics and interaction of bacterial communities of the white rhinoceros in three different niches, including gut, skin, and environment. We also analyzed the effects of captive ground and age on the composition of the bacterial community. Our findings highlighted the relationship among the three niches and may have important implications for the conservation and management of this threatened species.

Spin-orbit charge-transfer intersystem crossing in heavy-atom-free orthogonal covalent boron-dipyrromethene heterodimers.

Boron-dipyrromethene (BODIPY) derivatives are prospective organic-based triplet photosensitizers. Since the triplet generation yield of the parent BODIPY is low, heavy atoms are widely used to improve the triplet yield. However, the dimerization of BODIPYs can also significantly improve their ability to produce triplets. Through a comparative study of the triplet formation dynamics of two heavy-atom-free orthogonal covalent BODIPY heterodimers that differ in their dihedral angles, we have demonstrated that the mechanism of spin-orbit charge-transfer intersystem crossing (SOCT-ISC) promotes the triplet generation of BODIPY heterodimers in solution. Different from the general understanding of SOCT-ISC, the heterodimer with a smaller dihedral angle and low structural rigidity showed better triplet generation due to (a) the stronger inter-chromophoric interaction in the heterodimer, which promoted the formation of a solvent-stabilized charge-transfer (CT) state, (b) the more favorable energy level alignment with sizeable spin-orbit coupling strength, and (c) the balance between the stabilized singlet CT state and limited direct charge recombination to the ground state in a weakly polar solvent. The complete spectral characterization of the triplet formation dynamics clarified the SOCT-ISC mechanism and important factors affecting the triplet generation in BODIPY heterodimers.

Highly Efficient and Stable FAPbI3 Perovskite Solar Cells and Modules Based on Exposure of the (011) Facet.

Perovskite crystal facets greatly impact the performance and stability of their corresponding photovoltaic devices. Compared to the (001) facet, the (011) facet yields better photoelectric properties, including higher conductivity and enhanced charge carrier mobility. Thus, achieving (011) facet-exposed films is a promising way to improve device performance. However, the growth of (011) facets is energetically unfavorable in FAPbI3 perovskites due to the influence of methylammonium chloride additive. Here, 1-butyl-4-methylpyridinium chloride ([4MBP]Cl) was used to expose (011) facets. The [4MBP]+ cation selectively decreases the surface energy of the (011) facet enabling the growth of the (011) plane. The [4MBP]+ cation causes the perovskite nuclei to rotate by 45° such that (011) crystal facets stack along the out-of-plane direction. The (011) facet has excellent charge transport properties and can achieve better-matched energy level alignment. In addition, [4MBP]Cl increases the activation energy barrier for ion migration, suppressing decomposition of the perovskite. As a result, a small-size device (0.06 cm2) and a module (29.0 cm2) based on exposure of the (011) facet achieved power conversion efficiencies of 25.24% and 21.12%, respectively.

Extending the π-Conjugated System in Spiro-Type Hole Transport Material Enhances the Efficiency and Stability of Perovskite Solar Modules.

Hole transport materials (HTMs) are a key component of perovskite solar cells (PSCs). The small molecular 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl)-amine-9,9'-spirobifluorene (spiro-OMeTAD, termed "Spiro") is the most successful HTM used in PSCs, but its versatility is imperfect. To improve its performance, we developed a novel spiro-type HTM (termed "DP") by substituting four anisole units on Spiro with 4-methoxybiphenyl moieties. By extending the π-conjugation of Spiro in this way, the HOMO level of the HTM matches well with the perovskite valence band, enhancing hole mobility and increasing the glass transition temperature. DP-based PSC achieves high power conversion efficiencies (PCEs) of 25.24 % for small-area (0.06 cm2 ) devices and 21.86 % for modules (designated area of 27.56 cm2 ), along with the certified efficiency of 21.78 % on a designated area of 27.86 cm2 . The encapsulated DP-based devices maintain 95.1 % of the initial performance under ISOS-L-1 conditions after 2560 hours and 87 % at the ISOS-L-3 conditions over 600 hours.

Ultrafast Charge Separation Driven by Torsional Motion in Orthogonal Boron Dipyrromethene Dimer.

In this work, the photoinduced charge separation (CS) via symmetry breaking in an orthogonal meso-ß-linked boron dipyrromethene (BODIPY) dimer was investigated by polarized transient absorption spectroscopy. The time constant about 0.76 ps of the CS reaction determined in dimethyl sulfoxide is much faster than the solvation dynamics. The observed transient anisotropy of the BODIPY anion band implies that both hole and electron transfers occur with similar probabilities. The bidirectional charge transfer processes suggest that the locally excited state is weakly coupled to the polar solvent, and the solvation coupled excited-state structural relaxation within the BODIPY monomeric unit is rather limited. In combination with the electronic excitation analysis based on time-dependent density-functional theory calculations, we deduced that the CS in the orthogonal BODIPY dimer is enabled via the torsional motion associated with covalently connected BODIPY units, promoting the electronic coupling, and irrelevant to the dynamic solvent relaxation.

Photophyical and photosensitizing properties of BODIPYs substantially changed by alkyl- and phenyl-amino groups on meso carbon.

meso-RNH (R = C3H7, C4H9, PhCH2, H, and Ph) substituted BODIPY compounds have been prepared to examine their photophysical properties and photosensitizing abilities. We have measured the UV-vis absorption, steady state and time resolved fluorescence, excited triplet state formation using laser flash photolysis, singlet oxygen generation ability using chemical trapping method. The results show that the presence of meso-RNH leads to large blue shift of absorption and emission wavelength, remarkable decrease in fluorescence quantum yield and lifetime values, and significant increase in singlet oxygen formation quantum yield. Quantum chemical calculation also reveals the photoinduced charge transfer (PCT) mechanism. We conclude that property changes are due to: 1) S0 and S1 geometry, 2) ground state structural isomerization, and 3) intramolecular PCT. These results and mechanisms are helpful for designing new functional materials.

Event-Triggered Communication-Based Control for Strict-Feedback Nonlinear Systems.

In this article, we shall investigate the event-triggered communication control problem for strict-feedback nonlinear systems with measurement outputs. First, two event-triggered communication schemes are designed. Based on both event-triggered schemes, the measurement output and control input signals are only transmitted at triggering time instants, which saves communication costs from the sensor to the controller and from the controller to the actuator. Meanwhile, Zeno behavior can be excluded under the proposed triggering schemes. Second, since the full-state information is not available to the controller, by developing an observer, the system state is estimated and a controller based on estimated state information is designed. Due to the irregular sampling of information communication and state estimation error affects each other, the parameters of the state observer, the controller, and the event-triggering mechanism should be jointly designed. It is proved that the closed-loop system state converges to the origin. Finally, a simulation example verifies the validity of the obtained theoretical result.

Developmental stage variation in the gut microbiome of South China tigers.

South China tigers (Panthera tigris amoyensis, SC) are the most threatened tiger subspecies in the world. All the living SCs are captive in zoos or reserves and depend on artificial feeding. The composition of the gut microbiome plays an important role in sustaining the health of the host. A comprehensive understanding of the composition and development of the microbial community of SC is helpful to improve the feeding of captive SC. In this study, we collected 47 fecal samples, 37 of which were from SC of three developmental stages, 5 from adult Amur tigers (Am), and 5 from adult Bengal tigers (Bg), which were all housed in the same zoo. We investigated the diversity, richness, and composition of the bacterial microbiomes and we found that the gut microbiome of SC is strongly affected by host aging. The composition of the gut microbiome of juvenile SC experienced dramatic changes from 5 months old to 1 year old, and it showed much less difference when compared to the samples of 1 year old and the subadult. No significant differences were observed between the samples of subadult and the adult groups. The predominant phylum of 5-month-old SC is Fusobacteriota (33.99%) when the juvenile tigers were older than 5 months, and Firmicutes, but not Fusobacteriota, became the predominant phylum of bacteria in their gut. The gut microbiome of SC, Am, and Bg is possibly affected by their genetic variation; however, the core microbiome of these three subspecies is the same. Our data suggest that the gut microbiome of SC undergoes a developmental progression: a developmental phase (cub), a transitional phase (subadult), and a stable phase (adult). These results expand our understanding of the role of age in the development of the gut microbiome of SC.

A N-Ethylcarbazole-Terminated Spiro-Type Hole-Transporting Material for Efficient and Stable Perovskite Solar Cells.

The development of stable and efficient hole-transporting materials (HTMs) is critical for the commercialization of perovskite solar cells (PSCs). Herein, a novel spiro-type HTM was designed and synthesized where N-ethylcarbazole-terminated groups fully substituted the methoxy group of spiro-OMeTAD, named spiro-carbazole. The developed molecule exhibited a lower highest occupied molecular orbital level, higher hole mobility, and extremely high glass transition temperature (Tg =196 °C) compared with spiro-OMeTAD. PSCs with the developed molecule exhibited a champion power conversion efficiency (PCE) of 22.01 %, which surpassed traditional spiro-OMeTAD (21.12 %). Importantly, the spiro-carbazole-based device had dramatically better thermal, humid, and long-term stability than spiro-OMeTAD.

Evaluation of fertilization capability of frozen-thawed completely immotile spermatozoa collected from a white bengal tiger after interspecific ICSI with bovine oocytes.

The objective of this study was to evaluate the fertilization capability of White Bengal Tiger frozen-thawed completely immotile spermatozoa after interspecific intracytoplasmic sperm injection (ICSI) with bovine oocytes. The fertilization status of presumptive zygotes was assessed 18 h after ICSI by immunofluorescence staining and confocal microscopy. The fertilization rate was 34.8% (8/23), as confirmed by the extrusion of two polar bodies, or male and female pronuclei formation. For unfertilized oocytes (65.2%, 15/23), one activated oocyte had an activated spermatozoon but most were unactivated oocytes with unactivated spermatozoa (1/15, 6.7% vs 10/15, 66.7%, respectively, p < 0.05). These results showed that White Bengal Tiger frozen-thawed completely immotile spermatozoa retained the capacity to fertilize bovine oocytes after interspecific ICSI. This is the first report of in vitro produced zygotes using tiger immotile sperm with bovine oocytes by interspecific ICSI technique, which provides an efficient and feasible method for preservation and utilization of endangered feline animals.

Event-Triggered-Based Distributed Consensus Tracking for Nonlinear Multiagent Systems With Quantization.

In this article, an observer-based adaptive neural network (NN) event-triggered distributed consensus tracking problem is investigated for nonlinear multiagent systems with quantization. In the first place, the limited capacity of the communication channel between agents is considered. The event-trigger mechanism and dynamic uniform quantizers are set up to reduce information transmission. The next NN is utilized to handle the unknown nonlinear functions. Finally, in order to estimate the unmeasurable states, an NN-based state observer is designed for each agent by using a dynamic gain function. To settle the difficulty caused by the coupling effects of event-triggered conditions and the scaling function in dynamic uniform quantizers and observers, a distributed control protocol with estimated information of its neighbors is designed, which ensures distributed consensus tracking of the nonlinear multiagent systems without incurring the Zeno behavior. The effectiveness of the control protocol is illustrated by a simulation example.

Comparative analyses of copy number variations between swamp and river buffalo.

Domestic buffalo is an important livestock in the tropical and sub-tropical region, including two types: swamp and river buffalo. The swamp buffalo is mainly used as draft animal, while the river buffalo is raised for milk production. In this study, based on the new high-quality buffalo reference genome UOA_WB_1, we firstly investigated the copy number variants in buffalo using whole-genome Illumina sequencing. A total of 3,734 CNV regions (CNVRs) were detected in 106 buffalo population with a total length of 23,429,066 bp, corresponding to ∼ 0.88% of the water buffalo genome (UOA_WB_1). Our results revealed a clear population differentiation in CNV between swamp and river buffalo. In addition, a total of 667 highly differentiated CNVRs (covering 886 genes) were detected between river and swamp buffalo population. We detected a set of CNVR-overlapping genes associated with exercise, immunity, nerve, and milk trait which exhibited different copy numbers between swamp and river buffalo population. This study provides valuable genome variation resources for buffalo and would contribute to understanding the genetic differences between swamp and river buffalo.

Single-crystalline TiO2 nanoparticles for stable and efficient perovskite modules.

Despite the remarkable progress in power conversion efficiency of perovskite solar cells, going from individual small-size devices into large-area modules while preserving their commercial competitiveness compared with other thin-film solar cells remains a challenge. Major obstacles include reduction of both the resistive losses and intrinsic defects in the electron transport layers and the reliable fabrication of high-quality large-area perovskite films. Here we report a facile solvothermal method to synthesize single-crystalline TiO2 rhombohedral nanoparticles with exposed (001) facets. Owing to their low lattice mismatch and high affinity with the perovskite absorber, their high electron mobility and their lower density of defects, single-crystalline TiO2 nanoparticle-based small-size devices achieve an efficiency of 24.05% and a fill factor of 84.7%. The devices maintain about 90% of their initial performance after continuous operation for 1,400 h. We have fabricated large-area modules and obtained a certified efficiency of 22.72% with an active area of nearly 24 cm2, which represents the highest-efficiency modules with the lowest loss in efficiency when scaling up.

Distributed Nash equilibrium seeking strategy with incomplete information.

In this paper, two kinds of distributed Nash equilibrium seeking strategies based on Kalman filter are proposed in non-cooperative games with incomplete information. In the discrete-time system with process and measurement noises, each player, selfish and only considering its own profit, utilizes the gradient method to maximize the benefit. Since the payoff function is related to all players' states, Kalman filter and leader-following consensus are used to estimate the states in the network. Furthermore, considering the trade-off between strategy precision of Nash equilibrium and communication rate, another Nash equilibrium seeking method is proposed by introducing an event-based scheduler. The convergence of both Nash equilibrium seeking strategies is analyzed based on Lyapunov method. It is proved that both strategies are bounded in the mean square sense. Simulation examples are given to verify the efficiency.