Engineering High-Performance Hypergolic Propellant by Synergistic Contribution of Metal-Organic Framework Shell and Aluminum Core.

Hypergolicity is a highly desired characteristic for hybrid rocket engine-based fuels because it eliminates the need for a separate ignition system. Introducing hypergolic additives into conventional fuels through physical mixing is a feasible approach, but achieving highly reliable hypergolic ignition and energy release remains a major challenge. Here, the construction of core-shell Al@metal organic framework (MOF) heterostructures is reported as high-performance solid hypergolic propellants. Upon contact with the liquid oxidizer the uniformly distributed hypergolic MOF (Ag-MOF) shell can induce the ignition of hypergolic-inert fuel Al, resulting in Al combustion. Such a synthetic strategy is demonstrated to be favorable in hotspot generation and heat transfer relative to a simple physical mixture of Al/Ag-MOF, thus producing shorter ignition delay times and more efficient combustion. Thermal reactivity study indicated that the functionalization of the Ag-MOF shell changes the energy release process of the inner Al, which is accompanied by a thermite reaction. The synergistic effect of implantation of hypergolic MOF and high energy Al contributes to high specific impulses of 230-270 s over a wide range of oxidizer-to-fuel ratios.

Probing the Electron Accepting Ability of Phosphaphenalenes.

Phosphaphenalenes, extended π conjugates with the incorporation of phosphorus, are attractive avenues towards molecular materials for the applications in organic electronics, but their electron accepting ability have not been investigated. Herein we present systematic studies on the reductive behavior of a representative phosphaphenalene and its oxide by chemical and electrochemical methods. The chemical reduction of the phosphaphenalene by alkali metals reveals the facile P-C bond cleavage to form phosphaphenalenide anion, which functions as a transfer block for structure modification on the phosphorus atom. In contrast, the pentavalent P-oxide reacts with one or two equivalents of elemental sodium to form stable radical anion and dianion salts, respectively.

Synthesis, Photophysical and Electrochemical Properties of Spiro-Phosphonium Compounds.

A series of spiro-phosphonium compounds have been synthesized by copper-mediated coupling reaction of phosphacyclic compounds with alkynes. Their photophysical properties are tuned by varying substituents and exhibit different luminescent colors from blue to green, and finally, yellow. The fluorescence quantum efficiency of diethyl spiro-xanthenebenzophosphole 3aa in solid and liquid states reached 31% and 76%, respectively. Diphenyl spiro-xanthenebenzophosphole 3ad displayed relatively low cytotoxicity toward lung cancer cells A549 and was able to effectively penetrate the cell membrane and maintain strong staining. Moreover, density functional theory (DFT) and time-dependent DFT calculations have been performed to explore the origin of their photophysical properties.

Towards tetrasubstituted furans through rearrangement and cyclodimerization of acetylenic ketones.

Cyclodimerization of readily accessible acetylenic ketones facilitated by a phosphane-borane complex under basic conditions is achieved. This methodology allows one-pot synthesis of phosphorus-involved tetrasubstituted furans via the construction of a C-P bond and a furan ring within a single procedure. A plausible reaction mechanism is proposed.

A comparative study of satellite altimetry-based and DEM-based methods for estimating lake water volume changes.

This study compared two different methods, the satellite altimetry-based and DEM (digital elevation model)-based, for estimating lake water volume changes. We focused on 34 lakes in China as the testing sites to compare the two methods for lake water volume changes from 2005 to 2020. The satellite altimetry-based method used water levels provided by the DAHITI (Database for Hydrological Time Series of Inland Waters) data and surface areas derived from Landsat imagery. The DEM-based method used the SRTM DEM data in combination with Landsat-derived lake extents. Our results showed a high degree of consistency in lake water volume changes estimated between the two methods (R2 > 0.90), but each method has its limitations. In terms of temporal coverage, the satellite altimetry-based method with the DAHITI data is limited by missing water level data in certain periods. The performance of the DEM-based method in extracting lake shore boundaries in regions with flat terrains (slope <1.5°) is not satisfactory. The DEM-based method has complete regional applicability (100%) in the Tibetan Plateau (TP) Lake Region, yet its effectiveness drops significantly in the Xinjiang and Eastern China Plain Lake Regions, with applicability rates of 50 and 40%, respectively.

BF3-Promoted Ring Expansion of Iminylphosphiranes and Acylphosphiranes for Divergent Access to 1,2-Azaphospholidines and 1,2-Dihydrophosphetes.

Ring expansion of strained small rings provides an efficient method for the synthesis of various high-value carbocycles and heterocycles. Here we report BF3·Et2O as both an activating reagent and fluorine source, enabling ring expansion of phosphirane and P-F bond formation. Treatment of 1-iminylphosphirane complexes with BF3·Et2O resulted in 1,2-azaphospholidines, while the reaction of 1-acylphosphirane complexes with BF3·Et2O afforded 1,2-dihydrophosphetes. The reaction path was tuned by the nucleophilicity of the N and O atoms toward the intermediate phosphenium cation.

Spatial-temporal differentiation and influencing factors of carbon emission trajectory in Chinese cities - A case study of 247 prefecture-level cities.

Cities, where human energy activities and greenhouse gas emissions are concentrated, contribute significantly to alleviating the impacts of global climate change. Utilizing the China Carbon Emissions Accounting Database (CEADs) to provide carbon dioxide emission inventories for urban areas in China at the prefecture level, this study closely examines the historical evolution trajectories of carbon emissions across 247 urban units from 2005 to 2019. The logarithmic cubic function model was employed to simulate these trajectories, evaluating urban emission peaks and classifying the different carbon emission trajectories. Further, the Geographical and Temporal Weighted Regression model was employed to explore spatiotemporal traits and essential variables that impact the variations in carbon emissions among four identified trajectory types. Our results showed that Chinese urban carbon emission trajectories can be classified into four categories: a) peaking emissions, b) fluctuating growth, c) continuous growth, and d) passive decline. Specifically, 43 cities, primarily in North China, proactively attained their emission peak post-2010, driven by the reduction in secondary industry and energy intensity. 90 cities, largely industrial hubs in the southeast coast and inland, reached an emission plateau around 2015, exhibiting fluctuating growth due to dependencies on secondary industries. 101 cities, predominantly located in western and central regions, demonstrated a clear upward trend in carbon emissions, propelled by rapid urbanization and heavy industry-oriented economic development. Lastly, 13 cities, typically in the northeastern and southwestern regions, experienced a passive decline in carbon emissions, attributable to resource depletion or economic downturns. It is evident that China's city-level carbon peaking has demonstrated some effectiveness, yet considerable progress is still required.

Preparation of a novel cadmium-containing coordination polymer and catalytic application in the synthesis of N-alkylated aminoquinoline derivatives via the borrowing hydrogen approach.

Herein, we report an efficient and straightforward approach for the synthesis of N-alkylated aminoquinoline derivatives by recyclable Cd-containing coordination polymer-catalyzed reactions of aminoquinolines with primary alcohols via the borrowing hydrogen strategy. In this work, a new type of coordination polymer [Cd(CIA)(phen)2(H2O)]n was successfully designed and fabricated. The molecular structure was corroborated by single-crystal X-ray diffraction and fully characterized by PXRD, FT-IR, TGA, and XPS. Importantly, this polymer revealed high catalytic activity for the N-alkylation reaction of 2-aminoquinoline and 8-aminoquinoline with inexpensive and low-toxicity alcohols as alkylating agents in excellent yields up to 95%. Interestingly, the present synthetic protocol was successfully applied for the gram-level synthesis of several biologically active compounds. In addition, several control reactions were carried out to investigate the possible mechanisms of this transformation. Finally, recycling experiments indicated that the cadmium coordination polymer showed good recovery performance for borrowing hydrogen reactions.

Three-dimensional ecological drought identification and evaluation method considering eco-physiological status of terrestrial ecosystems.

Ecological drought is a complex process in terrestrial ecosystems where vegetation's eco-physiological functions are impaired due to water stress. However, there is currently a lack of long-term assessment of ecological drought from an eco-physiological perspective. In this study, the standardized ecological drought index (SESNDI) was developed using actual evaporation, root soil moisture, and kernel normalized difference vegetation index via the Euclidean distance method, reflecting ecosystem physiology, water supply capacity, and vegetation status. Solar-induced chlorophyll fluorescence validated SESNDI by reflecting vegetation photosynthesis. Using China as an example, severely impacted by climate change and ecological restoration, ecological drought's spatio-temporal variation and propagation characteristics was evaluated using clustering algorithms. The results demonstrated that (1) SESNDI showed superior performance over several other drought indices. (2) During 1982-2020, ecological drought was prevalent from 1990 to 2010, especially in the central and northeastern regions. (3) Compared to 1982-2000, the median duration and affected area of ecological drought events during 2001-2020 reduced by four months and 1.51 × 105 km2, respectively, while the median intensity increased by 0.06. (4) Decreased precipitation and increased temperature were the primary factors contributing to the frequent occurrence of ecological drought in China from 1990 to 2010. This study offers a crucial methodology for evaluating ecological drought, serving as a reference for developing effective terrestrial restoration strategies.

The first discovery of Polypedatesteraiensis (Dubois, 1987) (Rhacophoridae, Anura) in China.

Background: The genus of Polypedates Tschudi, 1838 currently comprises 25 recognised species with four of these species reported in Yunnan, China. Dubois (1987) speculated the distribution of P.teraiensis in China; however, there was no study carried out to confirm its distribution in the region. New information: We herein describe P.teraiensis as a new national record, based on a specimen collected from Yunnan border region. Phylogenetically, our sequence clustered with the sequences of recognised P.teraiensis specimens from Bangladesh, Myanmar and India. The uncorrected pairwise distances between the specimens from China and other P.teraiensis localities was small, ranging from 0.0-0.7%, based on 16S rRNA gene. Therefore, we report P.teraiensis as a new species record for China.