Volatile Perovskite Precursor Ink Enables Window Printing of Phase-Pure FAPbI3 Perovskite Solar Cells and Modules in Ambient Atmosphere.

Despite the great success of perovskite photovoltaics in terms of device efficiency and stability using laboratory-scale spin-coating methods, the demand for high-throughput and cost-effective solutions remains unresolved and rarely reported because of the complicated nature of perovskite crystallization. In this work, we propose a stable precursor ink design strategy to control the solvent volatilization and perovskite crystallization to enable the wide speed window printing (0.3 to 18.0 m/min) of phase-pure FAPbI3 perovskite solar cells (pero-SCs) in ambient atmosphere. The FAPbI3 perovskite precursor ink uses volatile acetonitrile (ACN) as the main solvent with DMF and DMSO as coordination additives is beneficial to improve the ink stability, inhibit the coffee rings, and the complicated intermediate FAPbI3 phases, delivering high-quality pin-hole free and phase-pure FAPbI3 perovskite films with large-scale uniformity. Ultimately, small-area FAPbI3 pero-SCs (0.062 cm2 ) and large-area modules (15.64 cm2 ) achieved remarkable efficiencies of 24.32 % and 21.90 %, respectively, whereas the PCE of the devices can be maintained at 23.76 % when the printing speed increases to 18.0 m/min. Specifically, the unencapsulated device exhibits superior operational stability with T90 >1350 h. This work represents a step towards the scalable, cost-effective manufacturing of perovskite photovoltaics with both high performance and high throughput.

Iodonium Initiators: Paving the Air-free Oxidation of Spiro-OMeTAD for Efficient and Stable Perovskite Solar Cells.

To date, perovskite solar cells (pero-SCs) with doped 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD) hole transporting layers (HTLs) have shown the highest recorded power conversion efficiencies (PCEs). However, their commercialization is still impeded by poor device stability owing to the hygroscopic lithium bis(trifluoromethanesulfonyl)imide and volatile 4-tert-butylpyridine dopants as well as time-consuming oxidation in air. In this study, we explored a series of single-component iodonium initiators with strong oxidability and different electron delocalization properties to precisely manipulate the oxidation states of Spiro-OMeTAD without air assistance, and the oxidation mechanism was clearly understood. Iodine (III) in the diphenyliodonium cation (IP+ ) can accept a single electron from Spiro-OMeTAD and forms Spiro-OMeTAD⋅+ owing to its strong oxidability. Moreover, because of the coordination of the strongly delocalized TFSI- with Spiro-OMeTAD⋅+ in a stable radical complex, the resulting hole mobility was 30 times higher than that of pristine Spiro-OMeTAD. In addition, the IP-TFSI initiator facilitated the growth of a homogeneous and pinhole-free Spiro-OMeTAD film. The pero-SCs based on this oxidizing HTL showed excellent efficiencies of 25.16 % (certified: 24.85 % for 0.062-cm2 ) and 20.71 % for a 15.03-cm2 module as well as remarkable overall stability.

Amalgamation of DNAzymes and Nanozymes in a Coronazyme.

Artificial enzymes such as nanozymes and DNAzymes are economical and stable alternatives to natural enzymes. By coating Au nanoparticles (AuNPs) with a DNA corona (AuNP@DNA), we amalgamated nanozymes and DNAzymes into a new artificial enzyme with catalytic efficiency 5 times higher than AuNP nanozymes, 10 times higher than other nanozymes, and significantly greater than most of the DNAzymes on the same oxidation reaction. The AuNP@DNA demonstrates excellent specificity as its reactivity on a reduction reaction does not change with respect to pristine AuNP. Single-molecule fluorescence and force spectroscopies and density functional theory (DFT) simulations indicate a long-range oxidation reaction initiated by radical production on the AuNP surface, followed by radical transport to the DNA corona, where the binding and turnover of substrates take place. The AuNP@DNA is named coronazyme because of its natural enzyme mimicking capability through the well-orchestrated structures and synergetic functions. By incorporating different nanocores and corona materials beyond DNAs, we anticipate that the coronazymes represent generic enzyme mimics to carry out versatile reactions in harsh environments.

Mechanistic Insight into Acceptorless Dehydrogenation of Methanol to Syngas Catalyzed by MACHO-Type Ruthenium and Manganese Complexes: A DFT Study.

The acceptorless dehydrogenation of methanol to produce carbon monoxide (CO) and dihydrogen (H2) mediated by MACHO-type 1-Ru and 1-Mn complexes was theoretically investigated via density functional theory calculations. The 1-Ru-catalyzed process involves the formation of active species 4-Ru through a methanol-bridged H2 release pathway. Methanol dehydrogenation by 4-Ru yields formaldehyde and 1-Ru, followed by H2 release to regenerate 4-Ru (rate-determining step, ΔG‡ = 32.5 kcal/mol). Formaldehyde further reacts with methanol via nucleophilic attack of the MeO- ligand in the Ru complex (ΔG‡ = 9.6 kcal/mol), which is more favorable than the traditional methanol-to-formaldehyde nucleophilic attack (ΔG‡ = 33.8 kcal/mol) due to the higher nucleophilicity of MeO-. CO is ultimately produced through the methyl formate decarbonylation reaction. Accelerated H2 release in the early reaction stage compared to CO results from the initial methanol dehydrogenation and condensation of formaldehyde with methanol. In contrast, CO generation occurs later via methyl formate decarbonylation. The 1-Mn-catalyzed reaction has reduced efficiency compared to 1-Ru for the higher Gibbs energy barrier (ΔG‡ = 34.1 kcal/mol) of the rate-determining step. Excess NaOtBu promotes the reaction of CO and methanol, forming methyl formate, significantly reducing the CO/H2 ratio as the catalyst amount decreases. These findings deepen our understanding of the methanol-to-syngas transformation and can drive progress in this field.

Improving landscape connectivity through habitat restoration: application for Asian elephant conservation in Xishuangbanna Prefecture, China.

Habitat restoration is an effective method for improving landscape connectivity, which can reduce habitat fragmentation. Maintaining landscape connectivity could promote connections between habitat, which is extremely essential to preserve gene flow and population viability. This study proposes a methodological framework to analyze landscape connectivity for Asian elephant habitat conservation, aiming to provide practical options for reducing habitat fragmentation and improving habitat connectivity. Our approach involved combining a species distribution model using MaxEnt and landscape functional connectivity models using graph theory to assess the impact on connectivity improvement via farmland/plantation restoration as habitat. The results showed that: (1) there were 119 suitable habitat patches of Asian elephant covering a total area of 1952.41 km2 . (2) The connectivity between habitats improved significantly after vegetation restoration and the gain first decreased and then increased with the increase of dispersal distance. (3) The first few new habitat patches that were identified played an important role in improving connectivity, and the variation rate of connectivity gradually leveled off as the number of new habitats increased. (4) Prioritization of the 25 best new habitat patches increased connectivity from 0.54% to 5.59% as the dispersal distance increased and mainly was located between two Asian elephant distribution regions and two components. Establishment of new habitat patches was effective for improving or restoring connectivity. Our findings can be used as guidance for improving the studied fragmented Asian elephant habitats, and they can also be used as a reference for the habitat restoration of other endangered species heavily affected by habitat fragmentation.

Heart rate patterns of captive Asian elephant (Elephas maximus) in their natural habitat at Wild Elephant Valley, Xishuangbanna of China.

There are few studies on the changes of heart rate of the Asian elephant (Elephas maximus), one of the largest tropical terrestrial mammals, with its self-factors and external environment. By measuring the heart rate of 35 Asian elephants, ranging in age from 4 months to 52 years, using a non-invasive electrocardiogram sensor in their natural habitat at Wild Elephant Valley, Xishuangbanna of China, we found factors that significantly influenced the HR were season, phase of the day, age, body weight, and the interaction between some of the above factors. We also observed that Asian elephants had lower resting heart rate in the morning of hot season than the cold and mild season, and the differences were significant, but the heart rate increased to similar levels in the afternoon regardless of the season. HR also decreased with age in all seasons and phases of the day. However, there was no significant effect of sex. This study reveals the adaptability of Asian elephant to tropical environment, and provides a basic reference for heart rate of Asian elephant under various natural conditions.

Programmable Y-Shaped Probes with Proximity Bivalent Recognition for Rapid Electrochemiluminescence Response of Acute Myocardial Infarction.

Herein, an exogenous luminophore-free and disposable electrochemiluminescence (ECL) biosensor was established for rapid response of acute myocardial infarction (AMI) using programmable Y-shaped probes (Y-probes) with proximity bivalent recognition. Specifically, the indium tin oxide thin film coated glass electrode (ITO) was modified with urchin-like porous TiO2 microspheres (pTiO2 MSs), which could achieve strong and stable ECL in S2O82- solution due to the dual promoting effect of the coreaction accelerator pTiO2 MSs, exhibiting 2.7-fold higher ECL intensity in comparison with that of bare ITO. Moreover, the Y-probes as bivalent recognition elements containing two kinds of cardiac troponin I (cTnI, a biomarker of AMI) aptamers and a linker labeled with ferrocene (L-Fc) were designed to export a "signal off" mode. When the target cTnI was in the proximity of the Y-probes, the L-Fc was separated from the electrode surface due to the proximity recognition of cTnI and its aptamers, achieving the highly effective recovery of ECL, which allowed for a much more rapid detection of cTnI than the sandwich-type immunoassay. As a proof of concept, an exogenous luminophore-free and disposable ECL platform for rapid and sensitive monitoring of cTnI was obtained and displayed a desired linear range from 100 fg mL-1 to 100 ng mL-1 with a limit of detection (LOD) of 30.1 fg mL-1, which can be ingeniously expanded as a portable home tester with ECL biosensors developments.

Elephant Endotheliotropic Herpesvirus 1, 4 and 5 in China: Occurrence in Multiple Sample Types and Implications for Wild and Captive Population Surveillance.

Elephant endotheliotropic herpesviruses (EEHVs) are important causes of death in both captive and wild Asian elephants (Elephas maximus). Nothing is known about the prevalence of EEHVs in wild or domestic elephants in China. To determine if EEHVs are present in elephants in China, 126 wild elephants from three populations and 202 captive individuals from zoos (n = 155) and the Wild Elephant Valley (n = 47) were screened using semi-nested polymerase chain reaction assays with EEHV-redundant and EEHV1/4/5-specific primers. EEHV1B and EEHV4 were detected in samples from both wild (EEHV1B:8/126; EEHV4:2/126) and captive (EEHV1B:5/155; EEHV4:9/155) elephants, while EEHV1A (six cases) and EEHV5 (one case) were only present in the captive elephants from the Wild Elephant Valley. EEHV1 was detected in blood and trunk and oral swabs; EEHV4 was detected in trunk and oral swabs as well as feces; EEHV5 was found in trunk and oral swabs. No significant age or sex association with EEHV1A, EEHV1B, or EEHV5 positivity was observed. An age association with EEHV4 positivity was found, with all unweaned elephants being EEHV4 positive, but an association with the sex of the elephant was not observed. These findings represent the first documentation of EEHV presence in captive and wild elephants in China. These findings also document EEHV1B and EEHV4 shedding in feces and demonstrate the utility of fecal screening as a tool for investigating EEHV4 infection in wild populations of elephants. It is recommended that EEHV testing be included in surveillance programs for captive and wild elephants in China.

The Pd(0) and Pd(ii) cocatalyzed isomerization of alkynyl epoxides to furans: a mechanistic investigation using DFT calculations.

The conversion of alkynyl epoxides to furans is an unusual tandem catalytic process in which two different oxidation states of palladium are employed. In this study, we used density functional theory calculations to establish the mechanistic details of the catalytic cycles for all the individual processes in this conversion. The results showed that the use of Pd(0) or Pd(ii) alone as the catalyst leads to high reaction barriers. This finding is consistent with experimental observations of low furan yields and the need for high temperatures in the presence of either catalyst alone. However, a combination of Pd(0) and Pd(ii) lowers the reaction barriers considerably. Our key finding is that the reaction pathway involves epoxide ring opening catalyzed by Pd(0), followed by tautomerization of an enol to generate an allenyl ketone in conjunction with Pd(0), with a subsequent Pd(ii)-catalyzed cyclization to yield the furan.

Raging elephants: effects of human disturbance on physiological stress and reproductive potential in wild Asian elephants.

Human disturbance has become a widespread threat to wildlife viability. The Asian elephant (Elephas maximus), an endangered and disturbance-prone species, is under severe threat from habitat loss and fragmentation, human-elephant conflict and poaching. Establishing connections between human disturbance, stress responses and reproduction is crucial for assessing the long-term survivability of a species and will provide critical information for conservation management. The current study investigated the effects of human disturbance on population-level stress responses and stress-related effects on reproductive potential of wild Asian elephants in Xishuangbanna Dai Autonomous Prefecture, China. We used a radioimmunoassay to measure the concentration of fecal cortisol and estradiol in 257 samples collected from five local populations at 15 sites over 4 years. Human disturbance in Xishuangbanna was quantified based on the Ecological-Niche Factor Analysis model. We found that fecal cortisol concentrations were strongly positively correlated with the degree of human disturbance and increased markedly with the expansion of tea plantations. Percentage of non-stressed individuals in a population was higher depending on the extend of undisturbed area in their home ranges. Fecal estradiol concentrations decreased significantly with increasing stress levels. Our results suggest that human disturbance poses environmental challenges to wild Asian elephant populations, and chronic exposure to human disturbance could lead to population decline. The study demonstrates the efficacy of non-invasive endocrine monitoring for further informing management decisions and developing conservation strategies.

Conflict between conservation and development: cash forest encroachment in Asian elephant distributions.

Over the last 4 decades, China has undergone major economic development, resulting in considerable impacts on its wildlife populations and habitats. It is essential to quantify the conflict between development and conservation to assist with policy-making because forestry policies and market trends affected indirectly the distribution of Asian elephants. Here, we mapped the historical distribution of elephants versus human land use. Elephant distributions appear to occur in unbroken natural forests only. However, over the 40-year period, the distribution ranges have become smaller and fragmented, with natural forest area also declining by 16%. The monoculture of cash trees is encroaching on natural forests. Over the past 10 years, rubber plantations have become concentrated in the south, with extensive natural forests and scattered rubber farms being converted to tea plantations, due to changes in governmental policies and product prices. Through mapping the spatial changes in the distribution of rubber and tea plantations, our study is expected to help local managers to incorporate the needs of endangered elephants through creating space when planning plantations, especially in Xishuangbanna and the south part of Pu'er. In conclusion, restoring elephant habitat and establishing ecological corridors are critical for the survival of elephants in this region.

Asian elephants in China: estimating population size and evaluating habitat suitability.

We monitored the last remaining Asian elephant populations in China over the past decade. Using DNA tools and repeat genotyping, we estimated the population sizes from 654 dung samples collected from various areas. Combined with morphological individual identifications from over 6,300 elephant photographs taken in the wild, we estimated that the total Asian elephant population size in China is between 221 and 245. Population genetic structure and diversity were examined using a 556-bp fragment of mitochondrial DNA, and 24 unique haplotypes were detected from DNA analysis of 178 individuals. A phylogenetic analysis revealed two highly divergent clades of Asian elephants, α and ß, present in Chinese populations. Four populations (Mengla, Shangyong, Mengyang, and Pu'Er) carried mtDNA from the α clade, and only one population (Nangunhe) carried mtDNA belonging to the ß clade. Moreover, high genetic divergence was observed between the Nangunhe population and the other four populations; however, genetic diversity among the five populations was low, possibly due to limited gene flow because of habitat fragmentation. The expansion of rubber plantations, crop cultivation, and villages along rivers and roads had caused extensive degradation of natural forest in these areas. This had resulted in the loss and fragmentation of elephant habitats and had formed artificial barriers that inhibited elephant migration. Using Geographic Information System, Global Positioning System, and Remote Sensing technology, we found that the area occupied by rubber plantations, tea farms, and urban settlements had dramatically increased over the past 40 years, resulting in the loss and fragmentation of elephant habitats and forming artificial barriers that inhibit elephant migration. The restoration of ecological corridors to facilitate gene exchange among isolated elephant populations and the establishment of cross-boundary protected areas between China and Laos to secure their natural habitats are critical for the survival of Asian elephants in this region.

Prevalence of cerebral palsy in children aged 1 - 6 in Guangxi, China.

OBJECTIVE: To study the prevalence of cerebral palsy (here in after referred to CP) in children aged 1 - 6 in Guangxi, China, and its epidemiologic characteristics and relevant risk factors. METHODS: Investigations on the prevalence and etiology of CP in children at ages of 1 - 6 were conducted in Nanning, Hengxian and Qinzhou of Guangxi from June to December in 1998, with a cluster sampling. RESULTS: Totally, 150 806 children aged 1 - 6 were investigated in Nanning, Hengxian and Qinzhou of Guangxi, with 89 418 boys and 61 388 girls. Among them, 193 children were diagnosed as CP, with a prevalence rate of 1.28 per thousand, higher in boys (136 cases, 1.52 per thousand ) than in girls (57 cases, 0.93 per thousand ), with statistical significance (chi(2) = 9.536 7, P = 0.02). Logistic regression analysis showed that risk factors for CP were children who could not cry after birth (neonatal asphyxia), Apgar score less than eight, delivery at lower level of maternity hospital, number of mother's gravidity, no prenatal checks for mothers, and taking antipyretics and preserved food with salt during pregnancy. CONCLUSIONS: Prevalence of CP in children of Guangxi was at a lower level in comparison with that in other areas at home and abroad, which, maybe, was related with the lower neonatal survival and higher infant mortality.

[Tree species diversity of tropical montane rain forest in Xishuangbanna, Yunnan].

Tropical montane rain forest (TMR), one of the main forest vegetation types in Xishuangbanna of Yunnan Province, occurs horizontally in the north (TMRF I) and vertically in the south (TMRF II). In order to understand its tree species diversity in different zones, six fixed plots (50 m x 50 m) at different sites in Xishuangbanna were established, two (plots 1 and 2) for TMRF I, and four (plots 3, 4, 5 and 6) for TMRF II. Grid method (10 m x 10 m) was used to record all the individuals with DBH greater than 2.0 cm in each plot, and tree species richness and diversity characteristics along DBH class, as well as changing trend of tree species diversity with increasing sampling area were analyzed. The results showed that the tree stem and species richness in the six plots both declined constantly along the DBH class gradient. For the communities of TMRF I (altitude was 850 1000 m), all indices had no clear trend with the gradient, while for the communities of TMRF II (altitude 1 200 - 2000 m), Shannon-Wiener and Simpson indices declined constantly with gradient, but Pielou's evenness index had the opposite trend. In smaller DBH classes (> or =2 cm, > or =5 cm and > or =10 cm), the tree species richness, diversity, and evenness of the communities of TMRF II were obviously higher than those of the communities of TMRF I, but there was no difference between the communities of TMRF I and TMRF II in larger DBH classes (> or = 20.0 cm, > or =30.0 cm and > or =50.0 cm) . With sampling area increased, the tree species richness, Shannon-Wiener index, Simpson index and Pielou's evenness index of the six plots all had the trend to be smooth when the sampling area increased to 2 000 m2.