Heat-Set Supramolecular Hydrogelation by Regulating the Hydrophilic-Lipophilic Balance for a Tunable Circularly Polarized Luminescent Switch.

Heat-set supramolecular gels exhibited totally opposite phase behaviors of dissolution upon cooling and gelation on heating. They are commonly discovered by chance and their rational design remains a great challenge. Herein, a rational design strategy is proposed to realize heat-set supramolecular hydrogelation through regulation of the hydrophilic-lipophilic balance of the system. A newly synthesized amphiphile hydrogelator with pyrene embedded in its lipophilic terminal can self-assemble into a hydrogel through a heating and cooling cycle. However, the host-guest complex of the gelator and hydrophilic γ-cyclodextrin (γ-CyD) results in a sol at room temperature. Thus, heat-set hydrogelation is realized from the sol state in a controllable manner. Heat-set gelation mechanism is revealed by exploring critical heat-set supramolecular gelation and the related findings provide a general strategy for developing new functional molecular gels with tunable hydrophilic-lipophilic balance.

Self-Assembly of Amphiphilic PDI and NDI Derivatives with Opposite Thermoresponsive Fluorescent Behaviors in Aqueous Solution.

This work presents a study of the thermally induced aggregation of perylene diimide (PDI) and naphthalene diimide (NDI) derivatives modified with oligo ethylene glycol (OEG) chains in aqueous solution. Water-soluble and flexible OEG side chains were introduced into the π-core of glutamate-modified NDI and PDI structures, and the aggregation process was modulated by heating or cooling in water. Interestingly, a rare opposite temperature response of fluorescent behavior from the two amphiphilic chromophores was revealed, in which the PDI exhibited fluorescent enhancement, while fluorescent quenching upon temperature increase was observed from the NDI assembly. The mechanism of thermally induced aggregation is clearly explained by studies with various spectroscopic techniques including UV-visible, fluorescence, 1H NMR, 2D NMR spectroscopy, and SEM observation as well as control experiments operated in DMSO solution. It is found that although similar J-aggregates were formed by both amphiphilic chromophores in aqueous solution, the temperature response of the aggregates to temperature was opposite. The degree of PDI aggregation decreased, while that of NDI increased upon temperature rising. This research paves a valuable way for understanding the complicated supramolecular behaviors of amphiphilic chromophores.

Identification of a combined hypoxia and lactate metabolism prognostic signature in lung adenocarcinoma : Author.

BACKGROUND: In the tumor microenvironment (TME), a bidirectional relationship exists between hypoxia and lactate metabolism, with each component exerting a reciprocal influence on the other, forming an inextricable link. The aim of the present investigation was to develop a prognostic model by amalgamating genes associated with hypoxia and lactate metabolism. This model is intended to serve as a tool for predicting patient outcomes, including survival rates, the status of the immune microenvironment, and responsiveness to therapy in patients with lung adenocarcinoma (LUAD). METHODS: Transcriptomic sequencing data and patient clinical information specific to LUAD were obtained from comprehensive repositories of The Cancer Genome Atlas (TCGA) and Gene Expression Omnibus (GEO). A compendium of genes implicated in hypoxia and lactate metabolism was assembled from an array of accessible datasets. Univariate and multivariate Cox regression analyses were employed. Additional investigative procedures, including tumor mutational load (TMB), microsatellite instability (MSI), functional enrichment assessments and the ESTIMATE, CIBERSORT, and TIDE algorithms, were used to evaluate drug sensitivity and predict the efficacy of immune-based therapies. RESULTS: A novel prognostic signature comprising five lactate and hypoxia-related genes (LHRGs), PKFP, SLC2A1, BCAN, CDKN3, and ANLN, was established. This model demonstrated that LUAD patients with elevated LHRG-related risk scores exhibited significantly reduced survival rates. Both univariate and multivariate Cox analyses confirmed that the risk score was a robust prognostic indicator of overall survival. Immunophenotyping revealed increased infiltration of memory CD4 + T cells, dendritic cells and NK cells in patients classified within the high-risk category compared to their low-risk counterparts. Higher probability of mutations in lung adenocarcinoma driver genes in high-risk groups, and the MSI was associated with the risk-score. Functional enrichment analyses indicated a predominance of cell cycle-related pathways in the high-risk group, whereas metabolic pathways were more prevalent in the low-risk group. Moreover, drug sensitivity analyses revealed increased sensitivity to a variety of drugs in the high-risk group, especially inhibitors of the PI3K-AKT, EGFR, and ELK pathways. CONCLUSIONS: This prognostic model integrates lactate metabolism and hypoxia parameters, offering predictive insights regarding survival, immune cell infiltration and functionality, as well as therapeutic responsiveness in LUAD patients. This model may facilitate personalized treatment strategies, tailoring interventions to the unique molecular profile of each patient's disease.

Industrial-Scale Hard Carbon Designed to Regulate Electrochemical Polarization for Fast Sodium Storage.

Given the merits of abundant resource, low cost and high electrochemical activity, hard carbons have been regarded as one of the most commercializable anode material for sodium-ion batteries (SIBs). However, poor rate capability is one of the main obstacles that severely hinder its further development. In addition, the relationships between preparation method, material structure and electrochemical performance have not been clearly elaborated. Herein, a simple but effective strategy is proposed to accurately construct the multiple structural features in hard carbon via adjusting the components of precursors. Through detailed physical characterization of the hard carbons derived from different regulation steps, and further combined with in-situ Raman and galvanostatic intermittent titration technique (GITT) analysis, the network of multiple relationships between preparation method, microstructure, sodium storage behavior and electrochemical performance have been successfully established. Simultaneously, exceptional rate capability about 108.8 mAh g-1 at 8 A g-1 have been achieved from RHC sample with high reversible capacity and desirable initial Coulombic efficiency (ICE). Additionally, the practical applications can be extended to cylindrical battery with excellent cycle behaviors. Such facile approach can provide guidance for large-scale production of high-performance hard carbons and provides the possibility of building practical SIBs with high energy density and durability.

Defect-Healing Induced Monoclinic Iron-Based Prussian Blue Analogs as High-Performance Cathode Materials for Sodium-Ion Batteries.

Prussian blue analogs (PBAs) have attracted wide interest as a class of ideal cathodes for rechargeable sodium-ion batteries due to their low cost, high theoretical capacity, and facile synthesis. Herein, a series of highly crystalline Fe-based PBAs (FeHCF) cubes, where HCF stands for the hexacyanoferrate, is synthesized via a one-step pyrophosphate-assisted co-precipitation method. By applying this proposed facile crystallization-controlled method to slow down the crystallization process and suppress the defect content of the crystal framework of the PBAs, the as-prepared materials demonstrate high crystallization and a sodium-rich induced rhombohedral phase. As a result, the as prepared FeHCF can deliver a high specific capacity of up to 152.0 mA h g-1 (achieving ≈90% of its theoretical value) and an excellent rate capability with a high-capacity retention ratio of 88% at 10 C, which makes it one of the most competitive candidates among the cathodes reported regarding both capacity and rate performance. A highly reversible three-phase-transition sodium-ion storage mechanism has been revealed via multiple in situ techniques. Furthermore, the full cells fabricated with as-prepared cathode and commercial hard carbon anode exhibit excellent compatibility which shows great prospects for application in the large-scale energy storage systems.

Amplified Single-Atom U-O Interfacial Effect Originated from U 5f-O 2p Hybridization over UOx/GO for Enhanced Nitrogen Reduction Reaction.

Uranium-based catalysts have been regarded as promising candidates for N2 fixation owing to the low-valent uranium metal active sites possessing the ability to enhance the electron back-donating to the π* antibonding orbitals of N2 for N≡N dissociation. Herein, we report a directional half-wave rectified alternating current electrochemical method to confine oxygen-rich uranium precursors over ultrathin 2D GO nanosheets. The as-prepared uranium catalysts exhibit a considerable Faradaic efficiency of 12.7% for NH3 and the NH3 yield rate of 18.7 µg h-1 mg-1 for N2 electroreduction. Operando XAS and isotope-labeling FTIR further unravel the preferred nitrogen adsorption reaction intermediate N-(2Oax-1 U-4Oeq) and confirm the key *N2Hy intermediate species derived from the fed N2 gas. Theoretical simulations demonstrate that the U-O atomic interface originated from U 5f-O 2p orbital hybridization can accumulate partial charge from GO, which can facilitate the N≡N dissociation and lower the thermodynamic energy barrier of the first hydrogenation step.

[Research progress in gut-skin axis and its association with traditional Chinese medicine theory].

Currently, the gut-organ axis has become a hot research topic. As increasing attention has been paid to the role of gut microbiota in the health of organs, the complex and integrated dialogue mechanism between the gastrointestinal tract and the associated microbiota has been demonstrated in more and more studies. Skin as the largest organ in the human body serves as the primary barrier protecting the human body from damage. The proposal of the gut-skin axis has established a bidirectional link between the gut and the skin. The disturbance of gut microbiota can lead to the occurrence of skin diseases, the mechanism of which is complex and may involve multiple pathways in immunity, metabolism, and internal secretion. According to the theory of traditional Chinese medicine(TCM), the connection between the intestine and the skin can be established through the lung, and the interior disorders will definitely cause symptoms on the exterior. This paper reviews the research progress in the gut-skin axis and its correlation with TCM theory and provides ideas and a basis for cli-nical treatment and drug development of skin and intestinal diseases.

Three-dimensional self-powered DNA walking machine based on catalyzed hairpin assembly energy transfer strategy.

Herein, catalyzed hairpin assembly is implemented as an automated strategy, which can respond in living cells to detect specific target DNA. Using the principle of catalyzed hairpin assembly (CHA), the auxiliary chain connects the fuel and starting chain to form a triple-stranded DNA to complete such a single system. Hundreds of single systems are modified on gold nanoparticles as DNA orbitals. Through the specific recognition of base complementation, the target DNA can realize the automatic walking of the three-dimensional fluorescence machine. This is a novel walking nanomachine that has a simple structure and can independently exist in cells to achieve automatic operation.

Synthesis, Herbicidal Activity and Toxicity Evaluation of Secondary Ammonium Salts from Turpentine Oil for Sustainable Weed Control.

Three series of secondary ammonium chloride from turpentine were synthesized and evaluated as botanical herbicides. The preemergence herbicidal activities against ryegrass (Loliun multiflorum) and barnyard grass (Echinochloa crus-galli) were investigated using water as the only solvent. Their toxicity was evaluated by cytotoxicity assays. Preliminary results demonstrated that the herbicidal performance of the prepared salts was similar or much higher than that of corresponding secondary amines and even commercial herbicide glyphosate. Promisingly, compound 14e containing a cyclohexyl-substituted p-menthene skeleton with an IC50 value of 0.0014 mM against root growth of ryegrass showed 39-fold higher herbicidal activity than glyphosate. Besides, this compound was found to be nontoxic to human and animal cells, indicating the potential application as a water-soluble herbicide for ryegrass control.

Molecular Epidemiology of Carbapenem-Resistant Klebsiella pneumoniae in a Tertiary Hospital in Northern China.

Background: In recent years, carbapenem-resistant Klebsiella pneumoniae (CRKP) has emerged rapidly in China with the abuse and overuse of antibiotics, and infections caused by CRKP pose a serious threat to global public health safety. The present study aimed to explore the epidemiological characteristics of CRKP isolates in Northern China and to elucidate their drug resistance mechanisms. Methods: 45 CRKP strains were consecutively collected at a teaching hospital from March 1st, 2018 to June 30th, 2018. Antimicrobial susceptibility was determined by the VITEK2 compact system and microbroth dilution method. Polymerase chain reaction (PCR) and sequencing were used to analyze multilocus sequence typing (MLST), drug resistance determinants, and plasmid types. The transfer of resistance genes was determined by conjugation. All statistical analysis was performed using SPSS 22.0 software. Results: All 45 isolates showed multidrug resistance (MDR). MLST analysis showed ST11 (48.9%, 22/45) was the most frequent type. All of the 45 CRKP isolates contained carbapenemase genes, extended-spectrum ß-lactamase (ESBL) genes, and plasmid-mediated quinolone resistance (PMQR) genes. For carbapenemase genes, KPC-2 (93.3%, 42/45) was the main genotype, and followed by GES (37.8%, 17/45) and NDM-1 (11.1%, 5/45). Plasmid typing analysis showed that IncFII and IncFIB were the most prevalent plasmids. The carbapenem resistance rate of K.pneumoniae was 11.4% and ICU was the main CRKP infection source. Conclusions: ST11 is the most frequent sequence type and KPC-2 is the predominant carbapenemase of CRKP strains in Northern China. KPC-2-ST11 are representative clonal lineages.

Overexpression of CENPF is associated with progression and poor prognosis of lung adenocarcinoma.

Background and aim: The molecular signatures of lung adenocarcinoma (LUAD) are not well understood. Centromere protein F (CENPF) has been shown to promote oncogenesis in many cancers; however, its role in LUAD has not been illustrated. We explored the role of CENPF in LUAD. Methods: CENPF expression level was investigated in public online database firstly, the prognosis of CENPF in LUAD were also assessed by Kaplan-Meier analysis. Then quantitative reverse transcription-polymerase chain reaction (qRT-PCR) was performed using 13 matched pairs of clinical LUAD tissue samples. Subsequently, the impact of CENPF expression on cell proliferation, cell cycle, apoptosis, colony formation was investigated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT), flow cytometric analysis and colony formation assay, respectively. Finally, experimental xenograft lung cancer model of nude mice armpit of right forelimb to determine the effect of CENPF on LUAD tumorigenesis. Results: CENPF mRNA expression was significantly elevated in LUAD tissues compared with adjacent non-tumor lung tissues in Gene Expression Profiling Interactive Analysis (GEPIA) (P < 0.001). Up-regulated CENPF was remarkably positively associated with pathological stage, relapse free survival (RFS) as well as overall survival (OS) of LUAD patients. Besides, CENPF knockdown greatly suppressed A549 cell proliferation, induced S phase arrest, promoted apoptosis and decreased colony numbers of LUAD cells. Furthermore, knockdown of CENPF significantly inhibited the tumor growth of the LUAD cells in an experimental xenograft lung cancer model of nude mice armpit of right forelimb. Conclusion: Taken together, these results demonstrated that CENPF may serve as a potential biomarker of prognostic relevance and a potential therapeutic target for LUAD.

Design and synthesis of tetrahydropyridopyrimidine derivatives as dual GPR119 and DPP-4 modulators.

Based on the approach of merged pharmacophores of GPR119 agonists and DPP-4 inhibitors, a series of tetrahydropyridopyrimidine compounds were designed as dual GPR119 and DPP-4 modulators with hypoglycemic activity. Seven fragments extracted from DPP-4 inhibitors were hybridized with the scaffold of tetrahydropyridopyrimidine. Among them, compound 51 displayed most potent GPR119 agonistic activity (EC50 = 8.7 nM) and good inhibition rate of 74.5% against DPP-4 at 10 µM. Furthermore, the blood glucose AUC0-2h of 51 was reduced to 19.5% in the oral glucose tolerance test (oGTT) at the dose of 30 mg/kg in C57BL/6N mice, which was more potent than that of vildagliptin (16.4%) at the same dose. The docking study of compound 51 with DPP-4 indicated GPR119 agonists could inhibit DPP-4 to serve as dual GPR119 and DPP-4 modulators.

Molecular docking and QSAR analyses of aromatic heterocycle thiosemicarbazone analogues for finding novel tyrosinase inhibitors.

A collection of 36 thiosemicarbazone analogues possessed a broad span of tyrosinase inhibitory activities was designed and obtained. Robust and reliable CoMFA and CoMSIA models were gained to predict the structure-activity relationship and the new modifier direction. Inhibitory activities of the compounds were found to greatly depend upon molecular shape, size, and charge. The sterically bulky group at the C-4 position of the thiophene ring contributed a high capacity for biological activity. Some bulky substituents at the C1-position and C12-position, and electron-negative groups at the C3-position, helped to improve the activity of these analogues. The molecular docking results provided visual evidence for QSAR analysis and detailed information about binding mode, affinity, and the principal mechanism between the ligands and tyrosinase. Based on these, a prospective structure modification and optimization of the most potent compound, T32, was suggested for further research.

TGIF2 is a potential biomarker for diagnosis and prognosis of glioma.

Background: TGFB-induced factor homeobox 2 (TGIF2), a member of the Three-Amino-acid-Loop-Extension (TALE) superfamily, has been implicated in various malignant tumors. However, its prognostic significance in glioma, impact on tumor immune infiltration, and underlying mechanisms in glioma development remain elusive. Methods: The expression of TGIF2 in various human normal tissues, normal brain tissues, and gliomas was investigated using HPA, TCGA, GTEx, and GEO databases. The study employed several approaches, including Kaplan-Meier analysis, ROC analysis, logistic regression, Cox regression, GO analysis, KEGG analysis, and GSEA, to explore the relationship between TGIF2 expression and clinicopathologic features, prognostic value, and potential biological functions in glioma patients. The impact of TGIF2 on tumor immune infiltration was assessed through Estimate, ssGSEA, and Spearman analysis. Genes coexpressed with TGIF2 were identified, and the protein-protein interaction (PPI) network of these coexpressed genes were constructed using the STRING database and Cytoscape software. Hub genes were identified using CytoHubba plugin, and their clinical predictive value was explored. Furthermore, in vitro experiments were performed by knocking down and knocking out TGIF2 using siRNA and CRISPR/Cas9 gene editing, and the role of TGIF2 in glioma cell invasion and migration was analyzed using transwell assay, scratch wound-healing assay, RT-qPCR, and Western blot. Results: TGIF2 mRNA was found to be upregulated in 21 cancers, including glioma. High expression of TGIF2 was associated with malignant phenotypes and poor prognosis in glioma patients, indicating its potential as an independent prognostic factor. Furthermore, elevated TGIF2 expression positively correlated with cell cycle regulation, DNA synthesis and repair, extracellular matrix (ECM) components, immune response, and several signaling pathways that promote tumor progression. TGIF2 showed correlations with Th2 cells, macrophages, and various immunoregulatory genes. The hub genes coexpressed with TGIF2 demonstrated significant predictive value. Additionally, in vitro experiments revealed that knockdown and knockout of TGIF2 inhibited glioma cell invasion, migration and suppressed the epithelial-mesenchymal transition (EMT) phenotype. Conclusion: TGIF2 emerges as a potential biomarker for glioma, possibly linked to tumor immune infiltration and EMT.

Versatile Nitrogen-Centered Organic Redox-Active Materials for Alkali Metal-Ion Batteries.

Versatile nitrogen-centered organic redox-active molecules have gained significant attention in alkali metal-ion batteries (AMIBs) due to their low cost, low toxicity, and ease of preparation. Specially, their multiple reaction categories (anion/cation insertion types of reaction) and higher operating voltage, when compared to traditional conjugated carbonyl materials, underscore their promising prospects. However, the high solubility of nitrogen-centered redox active materials in organic electrolyte and their low electronic conductivity contribute to inferior cycling performance, sluggish reaction kinetics, and limited rate capability. This review provides a detailed overview of nitrogen-centered redox-active materials, encompassing their redox chemistry, solutions to overcome shortcomings, characterization of charge storage mechanisms, and recent progress. Additionally, prospects and directions are proposed for future investigations. It is anticipated that this review will stimulate further exploration of underlying mechanisms and interface chemistry through in situ characterization techniques, thereby promoting the practical application of nitrogen-centered redox-active materials in AMIBs.

A potential therapeutic agent for the treatment of hyperuricemia and gout: 3,4-Dihydroxy-5-nitrobenzaldehyde phenylthiosemicarbazide.

Uric acid, the metabolic product of purines, relies on xanthine oxidase (XOD) for production. XOD is a target for the development of drugs for hyperuricemia (HUA) and gout. Currently, treatment options remain limited for gout patients. 3, 4-Dihydroxy-5-nitrobenzaldehyde (DHNB) is a derivative of the natural product protocatechualdehyde with good biological activity. In this work, we identify a DHNB thiosemicarbazide class of compounds that targets XOD. 3,4-Dihydroxy-5-nitrobenzaldehyde phenylthiosemicarbazone can effectively inhibit XOD activity (IC50 value: 0.0437 µM) and exhibits a mixed inhibitory effect. In a mouse model of acute hyperuricemia, a moderate dose (10 mg/kg.w) of 3,4-dihydroxy-5-nitrobenzaldehyde phenylthiosemicarbazide effectively controlled the serum uric acid content and significantly inhibited serum XOD activity. In addition, 3,4-Dihydroxy-5-nitrobenzaldehyde phenylthiosemicarbazide showed favorable safety profiles, and mice treated with the target compound did not show any symptoms of general toxicity following a single dose of 500 mg/kg. In the allopurinol group, 50 % of the mice died. These results provide a structural framework and mechanism of XOD inhibition that may facilitate the design of hyperuricemia and gout treatments.

In Situ Metal-Oxygen-Hydrogen Modified B-Tio2 @Co2 P-X S-Scheme Heterojunction Effectively Enhanced Charge Separation for Photo-assisted Uranium Reduction.

Photo-assisted uranium reduction from uranium mine wastewater is expected to overcome the competition between impurity ions and U(VI) in the traditional process. Here, B-TiO2 @Co2 P-X S-scheme heterojunction with metal-oxygen-hydrogen (M-O-H) is developed insitu modification for photo-assisted U(VI) (hexavalent uranium) reduction. Relying on the DFT calculation and Hard-Soft-Acid-Base (HSAB) theory, the introduction of metal-oxygen-hydrogen (M-O-H, hard base) metallic bonds in the B-TiO2 @Co2 P-X is found to enhance the hydrophilicity and the capture capability for uranyl ion (hard acid). Accordingly, B-TiO2 @Co2 P-500 hybrid nanosheets exhibit excellent U(VI) reduction ability (>98%) in the presence of competing ions. By self-consistent energy band calculations and in-situ KPFM spectral analysis, the formation of the internal electric field between B-TiO2 and Co2 P at the heterojunction is proven, offering a strong driving force and atomic transportation highway for accelerating the S-scheme charge carriers directed migration and promoting the photocatalytic reduction of uranium. This work provides a valuable route to explore the functionally modified photocatalyst with high-efficiency photoelectron separation for U(VI) reduction.

Identification and field verification of the aggregation pheromone components produced by male Holotrichia parallela Motschulsky (Coleoptera: Scarabaeidae).

BACKGROUND: The chafer beetle, Holotrichia parallela, causes damage to numerous economically significant crops worldwide. Adult beetles exhibit aggregation behavior likely mediated by a male-produced pheromone. Advancements in biological research technology have facilitated the identification of insect aggregation pheromones and promoted their applications as bait for trapping and monitoring pests. Currently, only a few active components of aggregation pheromones from Holotrichia species have been identified. However, the specific components of aggregation pheromones produced by H. parallela remain unknown. RESULT: In this study, we initially observed from Y-tube olfactometer assays that both male and female H. parallela were significantly attracted to volatiles emitted by males, but not to those from females. We then collected hindgut crude extracts of male adults and carried out gas chromatography-mass spectrometry analysis to identify potential aggregation pheromone components. Pentadecyl acetate, cis-13-docosenol, and behenic acid were identified as male-specific compounds in comparison to female extracts, serving as components of the aggregation pheromone in H. parallela. We further evaluated their attractiveness to H. parallea in both laboratory and field experiments. In laboratory settings, pentadecyl acetate, cis-13-docosenol, and behenic acid evoked significant responses to both males and females at specific concentrations, as evidenced by both electroantennography tests and behavioral bioassays. Under field conditions, traps baited with these three compounds captured significantly more H. parallela adults compared to control traps. CONCLUSION: In this study, we found that pentadecyl acetate, cis-13-docosenol, and behenic acid are specifically present in male H. parallela, serving as aggregation pheromones. Both laboratory and field-trapping experiments suggest their potential as monitoring and controlling tools against H. parallela adults. © 2024 Society of Chemical Industry.

Influences of elevational gradient on flower size and number of Gentiana lawrencei var. farreri.

Plants can adapt to environmental changes by adjusting their functional traits and biomass allocation. The size and number of flowers are functional traits related to plant reproduction. Life history theory predicts that there is a trade-off between flower size and number, and the trade-off can potentially explain the adaptability of plants. Elevation gradients in mountains provide a unique opportunity to test how plants will respond to climate change. In this study, we tried to better explain the adaptability of the alpine plant Gentiana lawrencei var. farreri in response to climate change. We measured the flower size and number, individual size, and reproductive allocation of G. lawrencei var. farreri during the flowering period along an elevation gradient from 3200 to 4000 m, and explored their relationships using linear mixed-effect models and the structural equation model. We found that with elevation increasing, individual size and flower number decreased and flower size increased, while reproductive allocation remained unchanged. Individual size positively affected flower number, but was not related to flower size; reproductive allocation positively affected flower size, but was not related to flower number; there is a clear trade-off between flower size and number. We also found that elevation decreased flower number indirectly via directly reducing individual size. In sum, this study suggests that G. lawrencei var. farreri can adapt to alpine environments by the synergies or trade-offs among individual size, reproductive allocation, flower size, and flower number. This study increases our understanding of the adaptation mechanisms of alpine plants to climate change in alpine environments.

Alkyl backbone variations in common ß-diketiminate ligands and applications to N-heterocyclic silylene chemistry.

We report the extension of the common ß-diketimine proligand class, RArnacnacH (HC(RCNAr)2H), where R is an alkyl group such as Et or iPr, plus Ph, and Ar is a sterically demanding aryl substituent such as Dip = 2,6-diispropylphenyl, Dep = 2,6-diethylphenyl, Mes = 2,4,6-trimethylphenyl or mesityl, Xyl = 2,6-dimethylphenyl, via one-pot condensation procedures. When a condensation reaction is carried out using the chemical dehydrating agent PPSE (polyphosphoric acid trimethylsilylester), ß-diketiminate phosphorus(V) products such as (iPrMesnacnac)PO2 can also be obtained, which can be converted to the respective proligand iPrMesnacnacH via alkaline hydrolysis. The RArnacnacH proligands can be converted to their alkali metal complexes with common methods and we have found that deprotonation of iPrDipnacnacH is significantly more sluggish than that of related ß-diketimines with smaller backbone alkyl groups. The basicity of the RArnacnac- anions can play a role in the success of their salt metathesis chemistry and we have prepared and structurally characterised the EtDipnacnac-derived silicon(II) compounds (EtDipnacnac)SiBr and (EtDipnacnac')Si, where EtDipnacnac' is the deprotonated variant MeCHC(NDip)CHC(NDip)Et.