User-Friendly Multifunctional Red-Emissive Carbon Dots for Rapid Cell Nucleus Staining via Targeting Nuclear Proteins.

Cytoarchitectural staining is of great importance in disease diagnosis and cell biology research. This study developed user-friendly multifunctional red-emissive carbon dots (R-CDs) for rapid cell nucleus staining via targeting nuclear proteins. R-CDs, simply prepared by electrochemical treatment of 1,2,4-benzenetriamine, exhibit strong emission at 635 nm when excited at 507 nm. The R-CDs can rapidly stain the nucleus of human SH-SY5Y, HepG2, and HUH-7 cells with a high signal-to-noise ratio owing to fluorescence enhancement after entering the nucleus. Compared to conventional cytosolic dyes such as Hoechst and DAPI, R-CDs are cheaper, more highly dispersed in water, and more stable (requiring no stringent storage conditions). The R-CDs show stable optical properties with insignificant photobleaching over 7 days and salt resistance up to 2 M of NaCl. More importantly, R-CDs, possessing a positive charge, allow rapid staining of live cells (3 min) and dead cells (10 s) in saline. According to kinetic variation, R-CDs can distinguish live cells from dead cells. Staining exhibits high efficiency in onion epidermal cells, Aspergillus niger, Caenorhabditis elegans, and human spermatozoa. The mechanism for efficient staining is based on their fast accumulation in the nucleus due to their small size and positive charge and strong interaction with nuclear proteins at amino acid residues of histidine and arginine, resulting in fluorescence enhancement by dozens of times. The developed R-CDs do not bind to DNA and would not cause genetic damage and will find various safe applications in biological and medical fields.

d-mannose targets PD-1 to lysosomal degradation and enhances T cell-mediated anti-tumor immunity.

High expression of programmed cell death protein 1 (PD-1), a typical immune checkpoint, results in dysfunction of T cells in tumor microenvironment. Antibodies and inhibitors against PD-1 or its ligand (PD-L1) have been widely used in various malignant tumors. However, the mechanisms by which PD-1 is regulated are not fully understood. Here, we report a mechanism of PD-1 degradation triggered by d-mannose and the universality of this mechanism in anti-tumor immunity. We show that d-mannose inactivates GSK3ß via promoting phosphorylation of GSK3ß at Ser9, thereby leading to TFE3 translocation to nucleus and subsequent PD-1 proteolysis induced by enhanced lysosome biogenesis. Notably, combination of d-mannose and PD-1 blockade exhibits remarkable tumor growth suppression attributed to elevated cytotoxicity activity of T cells in vivo. Furthermore, d-mannose treatment dramatically improves the therapeutic efficacy of MEK inhibitor (MEKi) trametinib in vivo. Our findings unveil a universally unrecognized anti-tumor mechanism of d-mannose by destabilizing PD-1 and provide strategies to enhance the efficacy of both immune checkpoint blockade (ICB) and MEKi -based therapies.

Transcriptome disclosure of hormones inducing stigma exsertion in Nicotiana tabacum by corolla shortening.

BACKGROUND: Stigma exsertion is an essential agricultural trait that can promote cross-pollination to improve hybrid seed production efficiency. However, the molecular mechanism controlling stigma exsertion remains unknown. RESULTS: In this study, the Nicotiana tabacum cv. K326 and its two homonuclear-heteroplasmic lines, MSK326 (male-sterile) and MSK326SE (male-sterile and stigma exserted), were used to investigate the mechanism of tobacco stigma exsertion. A comparison of the flowers between the three lines showed that the stigma exsertion of MSK326SE was mainly due to corolla shortening. Therefore, the corollas of the three lines were sampled and presented for RNA-seq analysis, which found 338 candidate genes that may cause corolla shortening. These genes were equally expressed in K326 and MSK326, but differentially expressed in MSK326SE. Among these 338 genes, 15 were involved in hormone synthesis or signal transduction pathways. Consistently, the content of auxin, dihydrozeatin, gibberellin, and jasmonic acid was significantly decreased in the MSK326SE corolla, whereas abscisic acid levels were significantly increased. Additionally, seven genes involved in cell division, cell cycle, or cell expansion were identified. Protein-protein interaction network analysis identified 45 nodes and 79 protein interactions, and the largest module contained 20 nodes and 52 protein interactions, mainly involved in the hormone signal transduction and pathogen defensive pathways. Furthermore, a putative hub gene coding a serine/threonine-protein kinase was identified for the network. CONCLUSIONS: Our results suggest that hormones may play a key role in regulating tobacco stigma exsertion induced by corolla shortening.

Fe-doping green fluorescent carbon dots via co-electrolysis of chrysoidine G and potassium ferrocyanide for sensitive Cr(VI) detection.

In this study, we aimed to synthesis of Fe-doping green fluorescent carbon dots (G-CDs) through the co-electrolysis of chrysoidine G and potassium ferrocyanide for Cr(VI) detection. The use of potassium ferrocyanide improves the quantum yield and sensing performance of G-CDs toward Cr(VI). The G-CDs have a maximum excitation wavelength of 308 nm and an emission wavelength of 510 nm. Comprehensive analyses including Raman, FT-IR, and XPS provided insights into the chemical structure and composition of the G-CDs. Under optimal conditions, G-CDs demonstrated concentration-dependent quenching upon interaction with Cr(VI). A linear relationship within the range of 0.25-100 µM was established with a calibration equation of ΔF/F0 = 0.005 + 0.015CCr(VI), yielding an R2 value of 0.996 and a limit of detection of 0.15 µM. The applicability of the G-CDs method was demonstrated by successful Cr(VI) detection in water samples with recovery rates ranging from 98.8 % to 100.1 % and relative standard deviation within 3.0 %. The fluorescence lifetime and Zeta potential measurements confirmed that the mechanism was via a static quenching process, while redox reaction, nanoparticle aggregation, and surface charge variation also played significant roles.

Overexpression of NtDOGL4 improves cadmium tolerance through abscisic acid signaling pathway in tobacco.

The DELAY OF GERMINATION1-LIKE (DOGL) genes play an essential role in diverse biological processes in plants. However, their exact involvement in the response to cadmium (Cd) stress via the ABA pathway remains unclear. Here, we focused on NtDOGL4, a tobacco DOGL gene whose expression is highly induced upon exposure to Cd. Overexpression of NtDOGL4 in tobacco resulted in elevated endogenous ABA levels, reduced Cd accumulation, and increased tolerance to Cd. Moreover, NtDOGL4 overexpression led to decreased accumulation of reactive oxygen species (ROS) and improved ROS scavenging capacity under Cd stress. Further analyses revealed the direct binding of the transcription factor ABSCISIC ACID-INSENSITIVE 5 (ABI5) to the NtDOGL4 promoter, positively regulating its expression in tobacco. Notably, NtDOGL4 overexpression promoted suberin formation and deposition, while suppressing the expression of Cd transporter genes in tobacco roots, as evidenced by histochemical staining, suberin fraction determination, and qRT-PCR assays. Collectively, our results demonstrate that NtDOGL4 overexpression reduces Cd accumulation, thereby improving Cd stress tolerance through the modulation of antioxidant system, transcription of Cd transporters, and suberin deposition. Notably, the NtABI5-NtDOGL4 module functions as a positive regulator in tobacco's Cd tolerance, underscoring its potential as a molecular target for developing low-Cd crops to ensure environmental safety.

D-mannose induces TFE3-dependent lysosomal degradation of EGFR and inhibits the progression of NSCLC.

In non-small cell lung cancer (NSCLC), the overexpression or abnormal activation of epidermal growth factor receptor (EGFR) is associated with tumor progression and drug resistance. EGFR tyrosine kinase inhibitors (TKIs) are currently the first-line treatment of NSCLC. However, patients inevitably acquired EGFR TKIs resistance mutations, which led to disease progression, so it is urgent to find new treatment. Here, we report that D-mannose up-regulates lysosomal activity by enhancing TFE3-mediated lysosomal biogenesis, thereby increasing the degradation of EGFR and significantly down-regulating its protein level. Therefore, D-mannose significantly inhibited the proliferation, migration and invasion of wild-type EGFR (WT-EGFR) and EGFR mutant cells (E746-A750 deletion, L858R and T790M mutations) in vitro. Oral administration of D-mannose strongly inhibited tumor growth in mice, showing similar effects with osimertinib. Taken together, these data suggest that D-mannose may represent a new strategy for clinical treatment of NSCLC.

Laparoscopy and laparotomy for patients with transverse colon cancer: comparative analysis of short-term surgical outcomes.

OBJECTIVE: To compare the efficacy of laparoscopy versus laparotomy in the treatment of transverse colon cancer. METHODS: Data from 100 patients with transverse colon cancer treated in our hospital from January 2018 to December 2020 were retrospectively analyzed in this study. According to the treatment methods, these patients were assigned into two groups: a laparotomy group (n=50) and a laparoscopy group (n=50). The intraoperative parameters, postoperative recovery, incidences of complications, postoperative pain, quality of life (QoL) score, postoperative serum inflammatory cytokine (hs-CRP, TNF-α, and IL-6) levels, and prognostic nutritional index (PNI) were analyzed and compared between the two groups. RESULTS: There was no significant difference in number of resected lymph nodes between the two groups. The operation time and intraoperative bleeding in the laparoscopy group were significantly less than those in the laparotomy group (P<0.05). The hospital stay, duration of gastrointestinal function recovery, and time of first postoperative flatus in the laparoscopy group were significantly shorter than those in the laparotomy group (all P<0.001). Moreover, the incidence of overall complications in the laparoscopy group was significantly lower than that in the laparotomy group (P<0.05). Compared with those in the laparotomy group, the VAS score was obviously lower and the QoL score was significantly higher in the laparoscopy group (all P<0.001). Patients in the laparoscopy group exhibited lower levels of postoperative hs-CRP, TNF-α and IL-6 in contrast to those in the laparotomy group (P<0.05). In additional, there was no significant difference in the PNI level before surgery between two groups. After surgery, the PNI level in the laparoscopy group was obviously higher than that in the laparotomy group (P<0.001). CONCLUSION: Laparoscopy is superior to laparotomy in treatment of transverse colon cancer through achieving better intraoperative outcomes, promoting postoperative recovery, reducing the incidence of complications and inflammatory reactions, alleviating postoperative pain, and improving therapeutic effects.

Ammonia Synthesis on Ternary LaSi-based Electrides: Tuning the Catalytic Mechanism by the Third Metal.

Intermetallic electrides have recently drawn considerable attention due to their unique electronic structure and high catalytic performance for the activation of inert chemical bonds under mild conditions. However, the relationship between electride (anionic) electron abundance and catalytic performance is undefined; the key deciding factor for the performance of intermetallic electride catalysts remains to be addressed. Here, the secret behind electride catalysts La-TM-Si (TM=Co, Fe and Mn) with the same crystal structure but different anionic electrons was studied. Unexpectedly, LaCoSi with the least anionic electrons showed the best catalytic activity. The experiments and first-principles calculations showed that the electride anions promote the N2 dissociation which alters the rate-determining step (RDS) for ammonia synthesis on the studied electrides. Different reaction mechanisms were found for La-TM-Si (TM=Fe, Co) and LaMnSi. A dual-site module was revealed for LaCoSi and LaFeSi, in which transition metals were available for the N2 dissociation and La accelerates the NHx formation, respectively, breaking the Sabatier scaling relation. For LaMnSi, which is the most efficient for the N2 activation, the activity for ammonia synthesis is limited and confined by the scaling relations. The findings provide new insight into the working mechanism of intermetallic electrides.

Carbon dots electrochemically prepared from dopamine and epigallocatechin gallate for hypochlorite detection with high selectivity via a dynamic quenching mechanism.

Monitoring hypochlorite levels in water is of great importance because of its high toxicity and wide applications as water disinfectants. In this manuscript, carbon dot (CD) was electrochemically prepared by using dopamine and epigallocatechin gallate (molar ratio 1:1) as the carbon source for efficient hypochlorite determination. By electrolyzing the solution at 10 V for 12 min with PBS as an electrolyte, dopamine would react with epigallocatechin at the anode, and through polymerization, dehydration, and carbonization, strong blue-fluorescent CDs were obtained. CDs were characterized by UV-Vis spectroscopy, fluorescence spectroscopy, high-resolution transmission electron microscopy, FT-IR, etc. These CDs have an excitation wavelength at 372 nm and an emission wavelength at 462 nm, owing an average particle size of 5.5 nm. The presence of hypochlorites can quench the fluorescence of CDs, and its reduction in intensity is linear with hypochlorite concentration over the range of 0.5-50 µM, ΔF/F0 = 0.0056 + 0.0194CClO-, R2=0.997. The detection limit achieved 0.23 µM (S/N = 3). The mechanism for fluorescence quenching is via a dynamic process. Different from many other fluorescence methods based on the strong oxidizing ability of hypochlorites, our method shows strong selectivity toward hypochlorites over other oxidizing agents such as H2O2. The assay was validated by the detection of hypochlorites in water samples, with recoveries between 98.2% and 104.3%.

Chemospecific C3- and C2-Olefinations of Isatins by TfOH-Promoted Tandem Aldol-Grob and Semiacetalization-Grob Fragmentations.

A novel method for TfOH-promoted chemospecific C3- and C2-olefinations of isatins is developed, which offers the first examples of Grob fragmentation using isatins and amides as substrates.

Ultrasonic Characterization of Ibidi µ-Slide I Luer Channel Slides for Studies With Ultrasound Contrast Agents.

Understanding and controlling the ultrasound contrast agent (UCA)'s response to an applied ultrasound pressure field are crucial when investigating ultrasound imaging sequences and therapeutic applications. The magnitude and frequency of the applied ultrasonic pressure waves affect the oscillatory response of the UCA. Therefore, it is important to have an ultrasound compatible and optically transparent chamber in which the acoustic response of the UCA can be studied. The aim of our study was to determine the in situ ultrasound pressure amplitude in the ibidi µ -slide I Luer channel, an optically transparent chamber suitable for cell culture, including culture under flow, for all microchannel heights (200, 400, 600, and [Formula: see text]). First, the in situ pressure field in the 800- [Formula: see text] high channel was experimentally characterized using Brandaris 128 ultrahigh-speed camera recordings of microbubbles (MBs) and a subsequent iterative processing method, upon insonification at 2 MHz, 45° incident angle, and 50-kPa peak negative pressure (PNP). Control studies in another cell culture chamber, the CLINIcell, were compared with the obtained results. The pressure amplitude was -3.7 dB with respect to the pressure field without the ibidi µ -slide. Second, using finite-element analysis, we determined the in situ pressure amplitude in the ibidi with the 800- [Formula: see text] channel (33.1 kPa), which was comparable to the experimental value (34 kPa). The simulations were extended to the other ibidi channel heights (200, 400, and [Formula: see text]) with either 35° or 45° incident angle, and at 1 and 2 MHz. The predicted in situ ultrasound pressure fields were between -8.7 and -1.1 dB of the incident pressure field depending on the listed configurations of ibidi slides with different channel heights, applied ultrasound frequencies, and incident angles. In conclusion, the determined ultrasound in situ pressures demonstrate the acoustic compatibility of the ibidi µ -slide I Luer for different channel heights, thereby showing its potential for studying the acoustic behavior of UCAs for imaging and therapy.

Tandem Synthesis of 2-Azaspiro[4.5]deca-1,6,9-trien-8-ones Based on Tf2O-Promoted Activation of N-(2-Propyn-1-yl) Amides.

Structurally novel 2-azaspiro[4.5]deca-1,6,9-trien-8-ones were synthesized from N-(2-propyn-1-yl) amides and 1,3,5-trimethoxybenzenes by a tandem method consisting of a Tf2O-promoted amide activation and a TfOH-promoted Friedel-Crafts ipso-cyclization. The method offered the first example of using N-(2-propyn-1-yl) amides as substrates in both Tf2O-promoted secondary amide activation and the synthesis of azaspiro[4.5]deca-6,9-diene-8-ones.

Coupling Two Ultra-high-Speed Cameras to Elucidate Ultrasound Contrast-Mediated Imaging and Therapy.

Ultrasound contrast-mediated medical imaging and therapy both rely on the dynamics of micron- and nanometer-sized ultrasound cavitation nuclei, such as phospholipid-coated microbubbles and phase-change droplets. Ultrasound cavitation nuclei respond non-linearly to ultrasound on a nanosecond time scale that necessitates the use of ultra-high-speed imaging to fully visualize these dynamics in detail. In this study, we developed an ultra-high-speed optical imaging system that can record up to 20 million frames per second (Mfps) by coupling two small-sized, commercially available, 10-Mfps cameras. The timing and reliability of the interleaved cameras needed to achieve 20 Mfps was validated using two synchronized light-emitting diode strobe lights. Once verified, ultrasound-activated microbubble responses were recorded and analyzed. A unique characteristic of this coupled system is its ability to be reconfigured to provide orthogonal observations at 10 Mfps. Acoustic droplet vaporization was imaged from two orthogonal views, by which the 3-D dynamics of the phase transition could be visualized. This optical imaging system provides the temporal resolution and experimental flexibility needed to further elucidate the dynamics of ultrasound cavitation nuclei to potentiate the clinical translation of ultrasound-mediated imaging and therapy developments.

Mechanistic Insights into Tf2O-Promoted Electrophilic Activation of 2-Propynamides and a New Synthesis of 2,4-Disubstituted Quinolines.

Direct evidence explaining why 2-propynamides have never been used as substrates in Tf2O-promoted electrophilic activations was obtained. Furthermore, a new method for the synthesis of structurally special 2,4-disubstituted quinolines was developed, by which the substituent at position 2 of quinolines can be diversified easily.

Effects of Living Mulch and Branches Mulching on Soil Moisture, Temperature and Growth of Rain-Fed Jujube Trees.

The influence of different mulching measures on soil moisture, soil temperature, and crop growth was investigated during the jujube growing season in rain-fed jujube orchards using micro-plot experiments. The mulching treatments included clean tillage (CT, control treatment), jujube branches mulching (JBM), and white clover planting (WCP). The results revealed that: (1) The average soil moisture content of JBM was greater than that of CT by 3.76% and 2.34%, respectively, during the 2013 and 2014 jujube growth periods, and its soil water deficit was minimal in each soil layer from 0 to 70 cm. WCP had the greatest soil water deficit. The average soil moisture content of the 0−70 cm soil layer in WCP was 3.88% and 5.55% lower than that in CT during the 2013 and 2014 jujube growth seasons, respectively (p < 0.05). (2) JBM had the highest annual average soil moisture content in each soil layer from 0 to 70 cm, followed by CT, while WCP had the lowest. White clover and jujube competed for water in the 20−40 cm soil layer, and JBM had the lowest variation in soil moisture. (3) Mulching with jujube branches and planting white clover could both control the temperature of the 0−25 cm soil layer and narrow the daily temperature range, with JBM being the least affected by air temperature. (4) Jujube's leaf area index and stem diameter increase in JBM were both significantly greater than in CT and WCP. In conclusion, using pruned jujube branches as surface mulch is appropriate for rain-fed jujube orchards because it can preserve soil moisture, regulate soil temperature, and promote jujube growth.

The Wheat Head Blight Pathogen Fusarium graminearum Can Recruit Collaborating Bacteria from Soil.

In nature, fungal endophytes often have facultative endohyphal bacteria (FEB). Can a model plant pathogenic fungus have them, and does it affect their phenotype? We constructed a growth system/microcosm to allow an F. graminearum isolate to grow through natural soil and then re-isolated it on a gentamicin-containing medium, allowing endohyphal growth of bacteria while killing other bacteria. F. graminearum PH-1 labelled with a His1mCherry gene staining the fungal nuclei fluorescent red was used to confirm the re-isolation of the fungus. Most new re-isolates contained about 10 16SrRNA genes per fungal mCherry gene determined by qPCR. The F. graminearum + FEB holobiont isolates containing the bacteria were sub-cultured several times, and their bacterial contents were stable. Sequencing the bacterial 16SrRNA gene from several Fg-FEB holobiont isolates revealed endophytic bacteria known to be capable of nitrogen fixation. We tested the pathogenicity of one common Fg-FEB holobiont association, F. graminearum + Stenatrophomonas maltophilia, and found increased pathogenicity. The 16SrRNA gene load per fungal His1mCherry gene inside the wheat stayed the same as previously found in vitro. Finally, strong evidence was found for Fg-S. maltophilia symbiotic nitrogen fixation benefitting the fungus.

Repressor element 1-silencing transcription factor deficiency yields profound hearing loss through Kv7.4 channel upsurge in auditory neurons and hair cells.

Repressor element 1-silencing transcription factor (REST) is a transcriptional repressor that recognizes neuron-restrictive silencer elements in the mammalian genomes in a tissue- and cell-specific manner. The identity of REST target genes and molecular details of how REST regulates them are emerging. We performed conditional null deletion of Rest (cKO), mainly restricted to murine hair cells (HCs) and auditory neurons (aka spiral ganglion neurons [SGNs]). Null inactivation of full-length REST did not affect the development of normal HCs and SGNs but manifested as progressive hearing loss in adult mice. We found that the inactivation of REST resulted in an increased abundance of Kv7.4 channels at the transcript, protein, and functional levels. Specifically, we found that SGNs and HCs from Rest cKO mice displayed increased Kv7.4 expression and augmented Kv7 currents; SGN's excitability was also significantly reduced. Administration of a compound with Kv7.4 channel activator activity, fasudil, recapitulated progressive hearing loss in mice. In contrast, inhibition of the Kv7 channels by XE991 rescued the auditory phenotype of Rest cKO mice. Previous studies identified some loss-of-function mutations within the Kv7.4-coding gene, Kcnq4, as a causative factor for progressive hearing loss in mice and humans. Thus, the findings reveal that a critical homeostatic Kv7.4 channel level is required for proper auditory functions.

Land use affects the response of soil moisture and soil temperature to environmental factors in the loess hilly region of China.

Changes in soil moisture and soil temperature result from the combined effects of several environmental factors. Scientific determination of the response characteristics of soil moisture and soil temperature to environmental factors is critical for adjusting the sloping land use structure and improving the ecological environment in China's loess hilly region. Soybean sloping fields, maize terraced fields, jujube orchards, and grasslands in the loess hilly region were selected as the research areas. The change in characteristics of soil moisture and soil temperature, as well as their interactions and statistical relationships with meteorological factors, were analyzed using continuously measured soil moisture, soil temperature, and meteorological factors. The results revealed that air temperature and humidity were the main controlling factors affecting soil moisture changes in the 0-60 cm soil layer of soybean sloping fields and grasslands in the normal precipitation year (2014) and the dry year (2015). Humidity and wind speed were the main meteorological factors affecting soil moisture changes in the maize terraced field. Air temperature had a significant negative effect on soil moisture in the jujube orchard. Soil moisture and soil temperature were all negatively correlated under the four sloping land use types. In normal precipitation years, atmospheric humidity had the greatest direct and comprehensive effect on soil moisture in soybean sloping fields, maize terraced fields, and grasslands; soil temperature had a relatively large impact on soil moisture in jujube orchards. The direct and comprehensive effects of soil temperature on soil moisture under all sloping land use types were the largest and most negative in the dry year. Air temperature had a high correlation with soil temperature in the 0-60 cm soil layer under the four sloping land use types, and the grey relational grade decreased as the soil layer deepened. The coefficient of determination between the 0-20 cm soil temperature and air temperature in the maize terraced field was low, indicating a weak response to air temperature. The above findings can serve as a scientific foundation for optimizing sloping land use structures and maximizing the efficient and sustainable utilization of sloping land resources in China's loess hilly region.

Effect of High-Temperature Hydrothermal Treatment on the Cellulose Derived from the Buxus Plant.

Cellulose has attracted considerable attention as the most promising potential candidate raw material for the production of bio-based polymeric materials. In the last decade, significant progress has been made in the production of biopolymers based on different cellulose forms. In this study, cellulose was obtained in an innovative and environmentally friendly way, using boxwood powder. Crude cellulose was obtained by treating Buxus powder with an ethanol-acetic acid-water mixture. Refined cellulose was then obtained by treatment with an acidic sodium hypochlorite solution and alkaline hydrogen peroxide solution. The novel chemistry of cellulose prepared by this method promises to be not only green, but also highly desirable, because of its lower emissions and low cost. It is crucial for the future of the global polymer industry. The refined cellulose was subjected to a high-temperature hydrothermal treatment under two temperatures and time conditions, with temperature gradients of 120, 140, and 160 °C, and time gradients of 1, 2, and 3 h. The samples were subjected to infrared and thermogravimetric analyses. The cellulose undergoes dehydration and thermal degradation reactions during the heat treatment process, and the thermal stability of the residual is enhanced, compared with that of virgin cellulose. Between 120 and 140 °C, the hydroxyl and hypomethyl groups on the surface of cellulose are shed. Groups in the amorphous region of the polymer are the first to be shed. The dehydration reaction reduces the number of free hydroxyl groups on the surface of the cellulose molecules. The dehydration reaction was accelerated by an increase in temperature. Between 140 and 160 °C, the ß-(1,4)-glycosidic bond begins to slowly break and some furans are generated. The structure of cellulose undergoes reorganization during thermal treatment. The thermal stability of the modified material is greater than that of untreated cellulose.

Unique Catalytic Mechanism for Ru-Loaded Ternary Intermetallic Electrides for Ammonia Synthesis.

Intermetallic electrides have recently shown their priority as catalyst components in ammonia synthesis and CO2 activation. However, their function mechanism has been elusive since its inception, which hinders the further development of such catalysts. In this work, ternary intermetallic electrides La-TM-Si (TM = Co, Fe, and Mn) were synthesized as hosts of ruthenium (Ru) particles for ammonia synthesis catalysis. Although they have the same crystal structure and possess low work functions commonly, the promotion effects on Ru particles rather differ from each other. The catalytic activity follows the sequence of Ru/LaCoSi > Ru/LaFeSi > Ru/LaMnSi. Furthermore, Ru/LaCoSi exhibits much better catalytic durability than the other two. A combination of experiments and first-principles calculations shows that apparent N2 activation energy on each catalyst is much lower than that over conventional Ru-based catalysts, which suggests that N2 dissociation can be conspicuously promoted by the concerted actions of the specific electronic structure and atomic configuration of intermetallic electride-supported catalysts. The NHx formations proceeded on La are energetically favored, which makes it possible to bypass the scaling relations based on only Ru as the active site. The rate-determining step of Ru/La-TM-Si was identified to be NH2 formation. The transition metal (TM) in La-TM-Si electrides has a significant influence on the metal-support interaction of Ru and La-TM-Si. These findings provide a guide for the development of new and effective catalyst hosts for ammonia synthesis and other hydrogenation reactions.