65% cover is the sustainable vegetation threshold on the Loess Plateau.

Global temperatures will continue to increase in the future. The ∼640,000-km2 Loess Plateau (LP) is a typical arid and semi-arid region in China. Similar regions cover ∼41% of the Earth, and its soils are some of the most severely eroded anywhere in the world. It is very important to understand the vegetation change and its ecological threshold under climate change on the LP for the sustainable development in the Yellow River Basin. However, little is known about how vegetation on the LP will respond to climate change and what is the sustainable threshold level of vegetation cover on the LP. Here we show that the temperature on the LP has risen 0.27 °C per decade over the past 50 years, a rate that is 30% higher than the average warming rate across China. During historical times, vegetation change was regulated by environmental factors and anthropogenic activities. Vegetation coverage was about 53% on the LP from the Xia Dynasty to the Spring and Autumn and Warring States period. Over the past 70 years, however, the environment has gradually improved and the vegetation cover had increased to ∼65% by 2021. We forecast future changes of vegetation cover on the LP in 2030s, in 2050s and in 2070s using SDM (Species Distribution Model) under Low-emission scenarios, Medium-emission scenarios and High-emission scenarios. An average value of vegetation cover under the three emission scenarios will be 64.67%, 62.70% and 61.47%, respectively. According to the historical record and SDM forecasts, the threshold level of vegetation cover on the LP is estimated to be 53-65%. Currently, vegetation cover on the LP has increased to the upper limit of the threshold value (∼65%). We conclude that the risk of ecosystem collapse on the LP will increase with further temperature increases once the vegetated area and density exceed the threshold value. It is urgent to adopt sustainable strategies such as stopping expanding vegetation area and scientifically optimizing the vegetation structure on the LP to improve the ecological sustainability of the Yellow River Basin.

Calixarene-Based Supramolecular Sensor Array for Pesticide Discrimination.

The identification and detection of pesticides is crucial to protecting both the environment and human health. However, it can be challenging to conveniently and rapidly differentiate between different types of pesticides. We developed a supramolecular fluorescent sensor array, in which calixarenes with broad-spectrum encapsulation capacity served as recognition receptors. The sensor array exhibits distinct fluorescence change patterns for seven tested pesticides, encompassing herbicides, insecticides, and fungicides. With a reaction time of just three minutes, the sensor array proves to be a rapid and efficient tool for the discrimination of pesticides. Furthermore, this supramolecular sensing approach can be easily extended to enable real-time and on-site visual detection of varying concentrations of imazalil using a smartphone with a color scanning application. This work not only provides a simple and effective method for pesticide identification and quantification, but also offers a versatile and advantageous platform for the recognition of other analytes in relevant fields.

A general supramolecular adjuvant for pesticides based on host-guest recognition.

BACKGROUND: Pesticides are indispensable in agriculture and can effectively improve the yields and quality of crops. Due to their weak water solubility, most pesticides need to be dissolved by adding solubilizing adjuvants. In this work, based on molecular recognition of the macrocyclic host, we developed a novel supramolecular adjuvant, called sulfonated azocalix[4]arene (SAC4A), which significantly improves the water solubility of pesticides. RESULTS: SAC4A presents multiple advantages, including high water solubility, strong binding affinity, universality, and simple preparation. SAC4A showed an average binding constant value of 1.66 × 105 M-1 for 25 pesticides. Phase solubility results indicated that SAC4A increased the water solubility of pesticides by 80-1310 times. The herbicidal, fungicidal, and insecticidal activities of supramolecular formulations were found to be superior to those of technical pesticides, and the herbicidal effects were even better than those of commercial formulations. CONCLUSION: Overall results revealed the potential of SAC4A to improve the solubility and effectiveness of pesticides, providing a new development idea for the application of adjuvants in agriculture. © 2023 Society of Chemical Industry.

A facile way to construct sensor array library via supramolecular chemistry for discriminating complex systems.

Differential sensing, which discriminates analytes via pattern recognition by sensor arrays, plays an important role in our understanding of many chemical and biological systems. However, it remains challenging to develop new methods to build a sensor unit library without incurring a high workload of synthesis. Herein, we propose a supramolecular approach to construct a sensor unit library by taking full advantage of recognition and assembly. Ten sensor arrays are developed by replacing the building block combinations, adjusting the ratio between system components, and changing the environment. Using proteins as model analytes, we examine the discriminative abilities of these supramolecular sensor arrays. Then the practical applicability for discriminating complex analytes is further demonstrated using honey as an example. This sensor array construction strategy is simple, tunable, and capable of developing many sensor units with as few syntheses as possible.

Construction of Complex Macromulticyclic Peptides via Stitching with Formaldehyde and Guanidine.

There is a growing interest in constructing multicyclic peptide structures to expand the chemical space of peptides. Conventional strategies for constructing large peptide structures are limited by the typical reliance on the inflexible coupling between premade templates equipped with fixed reactive handles and peptide substrates via cysteine anchors. Herein, we report the development of a facile three-component condensation reaction of primary alkyl amine, formaldehyde, and guanidine for construction of complex macromulticyclic peptides with novel topologies via lysine anchors. Moreover, the reaction sequences can be orchestrated in different anchor combinations and spatial arrangements to generate various macrocyclic structures crosslinked by distinct fused tetrahydrotriazine linkages. The macrocyclization reactions are selective, efficient, versatile, and workable in both organic and aqueous media. Thus, the condensation reaction provides a smart tool for stitching native peptides in situ using simple methylene threads and guanidine joints in a flexible and programmable manner.

Is Current Research on How Climate Change Impacts Global Food Security Really Objective?

Global food insecurity is becoming more severe under the threat of rising global carbon dioxide concentrations, increasing population, and shrinking farmlands and their degeneration. We acquired the ISI Web of Science platform for over 31 years (1988-2018) to review the research on how climate change impacts global food security, and then performed cluster analysis and research hotspot analysis with VosViewer software. We found there were two drawbacks that exist in the current research. Firstly, current field research data were defective because they were collected from various facilities and were hard to integrate. The other drawback is the representativeness of field research site selection as most studies were carried out in developed countries and very few in developing countries. Therefore, more attention should be paid to developing countries, especially some African and Asian countries. At the same time, new modified mathematical models should be utilized to process and integrate the data from various facilities and regions. Finally, we suggested that governments and organizations across the world should be united to wrestle with the impact of climate change on food security.

Supramolecular imaging of spermine in cancer cells.

As an important biomarker, the overexpressed spermine has been widely investigated for cancer diagnosis and treatment. However, bioimaging of spermine in living cells is still a formidable challenge. Herein, we design a supramolecular imaging ensemble for spermine by the host-guest complexation of amphiphilic sulfonatocalix[5]arene (SC5A12C) assembly with lucigenin (LCG). Strong binding ability and complexation-induced fluorescence quenching properties enable SC5A12C to quench the fluorescence of LCG dramatically and to recover it completely due to the competition of overexpressed spermine in cancer cells. SC5A12C also exhibits excellent biocompatibility and promotes cellular uptake due to its ability to form ultra-stable assembly. Co-assembling folate further promotes the cellular uptake of folate receptor overexpressed cancer cells, contributing to enhanced bioimaging.

An Amphiphilic Sulfonatocalix[5]arene as an Activator for Membrane Transport of Lysine-rich Peptides and Proteins.

Lysine (K) is an important target residue for protein and peptide delivery across membranes. K is the most frequently exposed residue in proteins, leading to high demand for the development of K-compatible transport activators. However, designing activators for K-rich peptides and proteins is more challenging than for arginine-rich species because of the kosmotropic nature of K and its recognition difficulty. In this study, we designed a new amphiphilic sulfonatocalix[5]arene (sCx5-6C) as a K-compatible transport activator. sCx5-6C was tailored with two key elements, recognition of K and the ability to embed into membranes. We measured the membrane transport efficiencies of α-poly-l-lysine, heptalysine, and histones across artificial membranes and of α-poly-l-lysine into live cells, activated by sCx5-6C. The results demonstrate that sCx5-6C acts as an efficient activator for translocating K-rich peptides and proteins, which cannot be achieved by known arginine-compatible activators.

Assessment of heavy metal(loid)s contamination risk and grain nutritional quality in organic waste-amended soil.

Studies that evaluate the human health risk of heavy metal(loid)s pollution have not been widely performed for organic waste-amended soils on the Loess Plateau of China. With this respect, we conducted a 3-year field trial to estimate the heavy metal(loid)s contamination of soil and maize, the resultant nutritional quality of maize grains and the health risk under treatments of conventional fertilizer (CF), traditional Chinese medicine residue (TCMR) and sheep manure (SM). We found that protein, amino acids and lysine in maize grains were increased by 12.3, 11.3 and 5.88 % under TCMR treatments relative to SM application, respectively. Meanwhile, this treatment reduced the levels of Cr, Pb, Cd, As and Hg in soil and maize grains. All fertilization regimens resulted in greater health risks for children, with HI values ranging from 1.06 to 1.52 and CR levels for Cr and As being ï¹¥1.0 × 10-4, especially higher in SM treatments. This presented the beneficial effect of TCMR than SM. The further investigated of toxic metal(loid)s level in SM and its application risks, based on meta-analysis and Monte Carlo simulation, indicated Cd, Hg and Pb were the most cautionary heavy metal(loid)s and contamination risk were greater on the southwest regions of China.

Calixarene-Based Supramolecular AIE Dots with Highly Inhibited Nonradiative Decay and Intersystem Crossing for Ultrasensitive Fluorescence Image-Guided Cancer Surgery.

Host-guest complexation between calix[5]arene and aggregation-induced emission luminogen (AIEgen) can significantly turn off both the energy dissipation pathways of intersystem crossing and thermal deactivation, enabling the absorbed excitation energy to mostly focus on fluorescence emission. The co-assembly of calix[5]arene amphiphiles and AIEgens affords highly emissive supramolecular AIE nanodots thanks to their interaction severely restricting the intramolecular motion of AIEgens, which also show negligible generation of cytotoxic reactive oxygen species. In vivo studies with a peritoneal carcinomatosis-bearing mouse model indicate that such supramolecular AIE dots have rather low in vivo side toxicity and can serve as a superior fluorescent bioprobe for ultrasensitive fluorescence image-guided cancer surgery.

Amphiphilic p-sulfonatocalix[6]arene based self-assembled nanostructures for enhanced clarithromycin activity against resistant Streptococcus Pneumoniae.

Amphiphilic calixarenes are preferred to generate nano-cargos for drugs due to their stability, possibilities for modification and intrinsic host cavities. Here we are reporting the synthesis of amphiphilic calixarene and its evaluation as drug delivery system. Water soluble amphiphilic p-sulfonatocalix[6]arene was synthesized through sulfonation and lipophilic conjugation on its upper and lower rims respectively. The synthesized amphiphile self-assembled into nanostructures in the presence of Clarithromycin and FITC as model hydrophobic drugs followed by a wide range of characterization. Clarithromycin loaded self-assembled nanostructures was screened for its bactericidal potential in resistant S. pneumonia through various in-vitro assays. The amphiphilic calixarene self-assembled into polydispersed nanostructures with 136.45 ±â€¯2.41 nm mean diameter and -49.93 ±â€¯0.35 mV surface charges. The amphiphile was capable to load Clarithromycin (57.54 ±â€¯1.88 %) and fluorescent dye and was highly stable. Clarithromycin loaded nanostructures revealed significant biofilm and bacterial growth inhibition and cell destruction properties. Results authenticate calixarene amphiphile as an efficient nano-carrier for improving Clarithromycin efficacy.

Non-histone nuclear protein HMGN2 differently regulates the urothelium barrier function by altering expression of antimicrobial peptides and tight junction protein genes in UPEC J96-infected bladder epithelial cell monolayer.

The urinary tract is vulnerable to frequent challenges from environmental microflora. Uropathogenic Escherichia coli (UPEC) makes a major contribution to urinary tract infection (UTI). Previous studies have characterized positive roles of non-histone nuclear protein HMGN2 in lung epithelial innate immune response. In the study presented here, we found HMGN2 expression was up-regulated in UPEC J96-infected urothelium. Surprisingly, over-expression of HMGN2 promoted disruption of BECs 5637 cells' intercellular junctions by down-regulating tight junction (TJs) components' expression and physical structure under J96 infection. Further investigation showed that BECs 5637 monolayer, in which HMGN2 was over-expressed, had significantly increased permeability to J96. Our study systemically explored the regulatory roles of HMGN2 in BECs barrier function during UPEC infection and suggested different modulations of intracellular and paracellular routes through which UPEC invades the bladder epithelium.

Subinhibitory Concentrations of Allicin Decrease Uropathogenic Escherichia coli (UPEC) Biofilm Formation, Adhesion Ability, and Swimming Motility.

Uropathogenic Escherichia coli (UPEC) biofilm formation enables the organism to avoid the host immune system, resist antibiotics, and provide a reservoir for persistent infection. Once the biofilm is established, eradication of the infection becomes difficult. Therefore, strategies against UPEC biofilm are urgently required. In this study, we investigated the effect of allicin, isolated from garlic essential oil, on UPEC CFT073 and J96 biofilm formation and dispersal, along with its effect on UPEC adhesion ability and swimming motility. Sub-inhibitory concentrations (sub-MICs) of allicin decreased UPEC biofilm formation and affected its architecture. Allicin was also capable of dispersing biofilm. Furthermore, allicin decreased the bacterial adhesion ability and swimming motility, which are important for biofilm formation. Real-time quantitative polymerase chain reaction (RT-qPCR) revealed that allicin decreased the expression of UPEC type 1 fimbriae adhesin gene fimH. Docking studies suggested that allicin was located within the binding pocket of heptyl α-d-mannopyrannoside in FimH and formed hydrogen bonds with Phe1 and Asn135. In addition, allicin decreased the expression of the two-component regulatory systems (TCSs) cognate response regulator gene uvrY and increased the expression of the RNA binding global regulatory protein gene csrA of UPEC CFT073, which is associated with UPEC biofilm. The findings suggest that sub-MICs of allicin are capable of affecting UPEC biofilm formation and dispersal, and decreasing UPEC adhesion ability and swimming motility.

Luteolin decreases the attachment, invasion and cytotoxicity of UPEC in bladder epithelial cells and inhibits UPEC biofilm formation.

Urinary tract infection (UTI), primarily caused by uropathogenic Escherichia coli (UPEC), is one of the most common infectious diseases worldwide. Emerging antibiotic resistance requires novel treatment strategies. Luteolin, a dietary polyphenolic flavonoid, has been confirmed as a potential antimicrobial agent. Here, we evaluated the sub-MICs of luteolin for potential properties to modulate the UPEC infection. We found that luteolin significantly decreased the attachment and invasion of UPEC J96 or CFT073 in human bladder epithelial cell lines T24. Meanwhile, obvious decreased expression of type 1 fimbriae adhesin fimH gene, lower bacterial surface hydrophobicity and swimming motility, were observed in luteolin-pretreated UPEC. Furthermore, luteolin could attenuate UPEC-induced cytotoxicity in T24 cells, which manifested as decreased activity of lactate dehydrogenase (LDH). Simultaneously, the inhibition of luteolin on UPEC-induced cytotoxicity was confirmed by ethidium bromide/acridine orange staining. Finally, the luteolin-pretreated UPEC showed a lower ability of biofilm formation. Collectively, these results indicated that luteolin decreased the attachment and invasion of UPEC in bladder epithelial cells, attenuated UPEC-induced cytotoxicity and biofilm formation via down-regulating the expression of adhesin fimH gene, reducing the bacterial surface hydrophobicity and motility.