Addition Of LiCl Research Articles

Environment-tolerant gelatin based ionic conductive organohydrogel for flexible sensor

Flexible wearable devices based on hydrogels have attracted more and more attention, however, the preparation of hydrogels with high toughness, conductivity and anti-freezing and anti-drying is still a challenge. In this study, a chemical-physical cross-linked double network conductive organohydrogel was designed by incorporating gelatin and Lithium chloride (LiCl) into polyacrylamide (AM) network with water-glycerol binary solvent. The results displayed that the organohydrogel exhibited high toughness, high stretchability, anti-freezing and anti-drying capability. With the addition of glycerol and LiCl, the organohydrogel has shown good conductivity in wide ranges of temperature. Moreover, the organohydrogel could be used as a strain sensor for the detection of various human body motions. Meanwhile, it was found that the introduction of LiCl enhanced the strain sensing performance, the stability and working temperature range. The sensors exhibited a high thermal sensitivity (5.72 % /℃), broad temperature detection range (0–65℃). These outstanding advantages indicated that the organohydrogels have potential application as strain and temperature sensors.

Controlling the polymorphs of PVDF membranes: Effects of a salt additive on PVDF polarization during phase separation processes

Polyvinylidene fluoride (PVDF) membranes, acclaimed for their outstanding chemical resistance, thermal stability, and mechanical properties, play a crucial role in diverse industrial purification applications. While various methods have been employed for fabricating PVDF membranes such as thermally induced, evaporation-induced, vapor-induced, and nonsolvent-induced phase separation processes, controlling the polarity of PVDF chains using these techniques remains challenging. Recent studies have shown that the nonpolar α-phase PVDF is susceptible to organic acid fouling owing to hydrophobic interactions, whereas the β-phase PVDF has demonstrated polarity and offers antifouling properties. Herein, porous PVDF membranes predominantly composed of the β-phase were successfully fabricated by incorporating a small amount of LiCl salt into the PVDF dope solution. The addition of LiCl influences ion–dipole moments between ions and PVDF during phase separation, simultaneously affecting the PVDF chain arrangement and membrane morphology. Since the LiCl additive alters both the pore size and structure of PVDF membranes, both freestanding and non-woven supported membranes were prepared and characterized to assess the effects of polarity and pore size on fouling tendency. Characterizations of prepared PVDF membranes revealed considerable changes in the PVDF polymorph, membrane morphology, pore size, and antifouling properties upon introducing the salt additive. Our findings imply that β-phase–dominant PVDF membranes can be effectively utilized in water purification applications.

A Study of Hygroscopicity Improvements to Adsorbents in Solar-Powered Air Water Extraction

As a global freshwater shortage is imminent, solar-powered adsorption-based atmospheric water harvesting technology is gradually attracting people’s attention due to its environmental friendliness and many other advantages. Among the many adsorbents used in this technology, MOF-801 has a large adsorption capacity in a wide range of humidity. In the current field, carbon materials are usually added to improve the photothermal properties of MOF-801, but hybrid adsorbents made in this way usually weaken the adsorption performance of MOF-801. If the MOF-801/carbon material adsorbent is used as a base and mixed with hygroscopic salt, which also has good adsorption properties, the hygroscopic properties of MOF-801 can be improved and the drawback of hygroscopic salt, which is prone to be lost after absorbing water, can be ameliorated. In this study, a hybrid adsorbent combining MOF-801 with carbon black (CB) and LiCl was prepared, and the effects of carbon black and LiCl on the performance of the MOF-801 adsorbent were compared. The experiments showed that the adsorption capacity of the hybrid adsorbent obtained a significant enhancement after the addition of LiCl, which increased by 38.2% versus 112.3% compared with MOF-801 and MOF-801/CB.

Preparation and thermal properties of zeolite 13X/MgSO4-LiCl binary-salt composite material for sorption heat storage

Thermal energy storage can play a pivotal role in waste heat recovery and solar energy thermal utilization by balancing the time and space-mismatch between supply and demand of energy. Thermochemical sorption heat storage technology has gained the enormous interest for its ability to make use of the low-grade thermal energy. However, the slow sorption reaction kinetics of sorbents remains an obstacle for the large-scale industrial applications of thermochemical sorption heat storage technology. In this study, a new type of zeolite 13X/MgSO4-LiCl composite sorbent material has been fabricated by impregnating zeolite 13X with the mixed solution of MgSO4 and LiCl. The structural characteristics and sorption heat storage performance of composite adsorbents with different mass ratios of MgSO4 and LiCl were studied experimentally by scanning electron microscopy (SEM), full-automatic specific surface area and pore analyzer (ASAP), and thermogravimetry analysis-differential scanning calorimetry (TGA-DSC). The results indicate that binary-salt sorbents show the faster sorption kinetics and higher water sorption capacity compared to single salt sorbents. When the mass ratio of MgSO4 and LiCl is 2:1, the zeolite 13X/MgSO4-LiCl composite sorbent (XML-2/1) has the best sorption heat storage performance. Under the sorption temperature of 25 °C and relative humidity (RH) of 60 %, the maximum sorption capacity is 0.24 g/g, and the corresponding heat storage density of 458.3 kJ/kg can be achieved. The results indicate that the zeolite 13X/MgSO4-LiCl composite adsorbent can improve the sorption rate and heat storage density. Compared with pure zeolite 13X and zeolite 13X/MgSO4 composite sorbents, the addition of LiCl can effectively improve the sorption rate and sorption heat storage capacity. The findings of this investigation could promote the growing body of research on the mixed salt (binary-salt or multiple-salt) composite materials and new insights can be offered by broadening the application of zeolite-based composite materials in low-grade thermal energy storage for space heating, which can guide further research and development in this field and ultimately help facilitate the transition toward the clean energy.

Identification of exosomal miR-484 role in reprogramming mitochondrial metabolism in pancreatic cancer through Wnt/MAPK axis control

The microRNAs (miRNAs) are potent regulators of tumorigenesis in various cancers, especially pancreatic cancer. The abnormal expression of miRNAs can be observed in tumor cells. Noteworthy, miRNAs could be transferred by exosomes as small extracellular vesicles in regulation of carcinogenesis. This research focused on exploring the roles and mechanisms of exosomal miR-484, derived from human bone marrow mesenchymal stem cells (hBMSCs), in the context of molecular interactions and regulation of mitochondrial metabolism. Exosomes were isolated for the examination of miR-484 expression. The impacts of hBMSCs-derived exosomal miR-484 on pancreatic cancer cells were studied using various assays. Evaluation of mitochondrial function and metabolism was performed. Wnt/MAPK pathway-related protein expression was assessed, and an in vivo tumor xenograft model was utilized to examine the functions. Our findings demonstrated a decreased miR-484 expression in pancreatic cancer cells. However, hBMSCs-derived exosomal miR-484 inhibited the proliferation and migration of these cells, while inducing apoptosis. Moreover, miR-484 led to an upsurge in reactive oxygen species production, a decrease in ATP levels, and a disruption in mitochondrial metabolism. In vivo analyses showed that hBMSCs-derived exosomal miR-484 lessened tumor size and weight, while also suppressing the expression of mitochondrial biomarkers. Further, there was a decline in β-catenin and p-p38 protein levels both in vitro and in vivo. The addition of LiCl restored the disrupted mitochondrial metabolism. Conclusively, our results suggest that hBMSCs-derived exosomal miR-484 mitigates the malignant transformation and mitochondrial metabolism of pancreatic cancer by deactivating the Wnt/MAPK pathway.

Apoptotic bodies of bone marrow mesenchymal stem cells inhibit endometrial stromal cell fibrosis by mediating the Wnt/β-catenin signaling pathway

BackgroundIntrauterine adhesions (IUAs) are a common illness of the uterine cavity. Endometrial fibrosis is the main pathological feature. In addition to a high recurrence rate, patients with severe IUAs have a low pregnancy rate. However, there are few effective treatments for IUAs. This study aims to confirm the influence of apoptotic bodies of bone marrow mesenchymal stem cells (BMSCs) on endometrial stromal cell fibrosis by mediating the Wnt/β-catenin signaling pathway and to provide new insight for the clinical treatment of IUAs. MethodsHuman endometrial stromal cells (HESCs) were used to establish an IUA cell model by treatment with TGF-β1, and a rat IUA model was established by the double injury method. Apoptosis of BMSCs was detected by TUNEL assays, and cell morphology was observed by the CM-DiI tracer. The morphology of apoptotic vacuoles and apoptotic bodies (ABs) was detected by TEM. We used Western blotting to detect the expression of histone H3.3, histone H2B, C3b, cyclin D1, C1QC, α-SMA, COL1A1, COL5A2, FN, CTGF, Wnt2b, c-MYC, CK-18 and VIM. The expression levels of α-SMA, COL1A1, COL5A2, FN and CTGF were detected by RT‒qPCR. The expression levels of α-SMA, COL1A1, FN and CTGF were detected by immunofluorescence. Immunohistochemistry was used to detect the expression of TGF-β, CK-18 and VIM. Flow cytometry, cell scratch assays, CCK-8 assays, and H & E and Masson staining were used to detect the cell cycle, cell migration, cell proliferation, and endometrial pathology, respectively. ResultsWe found that ultraviolet light (UV) irradiation induced apoptosis of BMSCs and increased the production of ABs. TGF-β1 treatment can induce HESCs to form extracellular matrix (ECM), and aggravate cell fibrosis, and adding ABs or FH535, an inhibitor of the Wnt/β-catenin signaling pathway, can inhibit TGF-β1-induced HESC fibrosis. However, the inhibitory effect of ABs on TGF-β1-induced fibrosis of HESCs was attenuated by the addition of LiCl. In the Wnt/β-catenin signaling pathway, LiCl is an activator after coculture with TGF-β1. In vivo, IUA-induced narrowing of the uterine cavity was accompanied by intrauterine adhesions, increased deposition of collagen fibers, upregulation of TGF-β1, VIM, α-SMA, COL1A1 and COL5A2, and downregulation of CK-18. These changes in expression were reversed after treatment with ABs or FH535. When ABs and LiCl were added at the same time, the inhibitory effect of ABs on IUA fibrosis was weakened. ConclusionBMSC-derived ABs inhibit the fibrosis of HESCs by inhibiting the Wnt/β-catenin signaling pathway. These results provide a new direction for the clinical treatment of IUAs.

Thermal and structural properties of polyzwitterions: Effects of monomer chemistry and salt addition

Thermal and structural properties of polyzwitterions (PZI)s comprising the sulfobetaine moiety were studied as a function of LiCl addition and variations in monomer chemistry. The polyzwitterions chosen for this study are: poly(sulfobetaine methacrylate), PSBMA; poly(sulfobetaine acrylate), PSBA; and, poly(ethyl sulfobetaine methacrylate), PESBMA. When LiCl salt is added, the Li+and Cl− ions disrupt the dipole-dipole electrostatic interaction of the PZI side groups. Fourier transform infrared spectroscopy shows that the vibrational frequencies of the symmetric and asymmetric S=O bonds increase as LiCl content increases. Structural studies by wide angle X-ray scattering show that all the PZIs are amorphous, and the average interatomic spacing, d, increases in the order: dPSBA(= 0.456±0.006nm) < dPSBMA (= 0.474±0.015nm) < dPESBMA (= 0.493±0.011nm). Upon the addition of LiCl, d-spacing for a given PZI decreases as LiCl content increases. Thermogravimetry showed that PZIs had degradation onset temperatures Td ∼ 300°C. As LiCl content increases, the onset temperature of degradation decreases suggesting that the disruption of dipole-dipole crosslinks destabilizes the polymer. All the PZIs are hydrophilic and hygroscopic, and a drying procedure was developed so that well-defined glass-to-liquid transitions could be observed in the dry solid state. PZIs without LiCl have glass transition temperatures, Tg, increasing in the order: Tg,PSBA(= 200±1°C) < Tg,PESBMA (= 204±1°C) < Tg,PSBMA (= 237±1°C). As the LiCl content increases, Tg decreases, and the liquid state heat capacity increases, in all PZIs. The specific heat capacity increment at Tg was studied for PSBA as a function of LiCl content. In PSBA, the heat capacity increment reached a maximum for molar ZI:LiCl content at and above 1:1, and its value agreed well with predictions based on an empirical bead model of polymers. Thermal data on the dry state of PZI-LiCl complexes suggest an analogy between electrostatically crosslinked, fully amorphous PZIs and semicrystalline polymers. The dipolar crosslinks confine the molecular motion of PZIs just as crystal domains confine the molecular motion of the amorphous phase in semicrystalline polymers.

Effective Recognition of Lithium Salt in (Choline Chloride: Glycerol) Deep Eutectic Solvent by Reichardt’s Betaine Dye 33

Deep eutectic solvents (DESs) have emerged as novel alternatives to common solvents and VOCs. Their employment as electrolytes in batteries has been an area of intense research. In this context, understanding changes in the physicochemical properties of DESs in the presence of Li salts becomes of utmost importance. Solvatochromic probes have the potential to gauge such changes. It is reported herein that one such UV–vis molecular absorbance probe, Reichardt’s betaine dye 33, effectively manifests changes taking place in a DES Glyceline composed of H-bond accepting salt choline chloride and H-bond donor glycerol in a 1:2 molar ratio, as salt LiCl is added. The lowest energy intramolecular charge–transfer absorbance band of this dye exhibits a 17 nm hypsochromic shift as up to 3.0 molal LiCl is added to Glyceline. The estimated ETN parameter shows a linear increase with the LiCl mole fraction. Spectroscopic responses of betaine dye 33, N,N-diethyl-4-nitroaniline and 4-nitroaniline are used to assess empirical Kamlet–Taft parameters of dipolarity/polarizability (π*), H-bond-donating acidity (α) and H-bond-accepting basicity (β) as a function of LiCl concentration in Glyceline. LiCl addition to Glyceline results in an increase in α and no change in π* and β. It is proposed that the added lithium interacts with the oxygen of the –OH functionalities on the glycerol rendering of the solvent with increased H-bond-donating acidity. It is observed that pyrene, a popular fluorescence probe of solvent polarity, does respond to the addition of LiCl to Glyceline, however, the change in pyrene response starts to become noticeable only at higher LiCl concentrations (mLiCl ≥ 1.5 m). Reichardt’s betaine dye is found to be highly sensitive and versatile in gauging the physicochemical properties of DESs in the presence of LiCl.

LiCl-assisted polysiloxane electrolyte complexes for highly sensitive humidity sensing

Polyelectrolytes with hydrophilic and hydrophobic structures are widely employed in humidity sensors, but their response properties necessitate improvement. This paper introduces the development of crosslinked polysiloxane electrolytes via Zr4+ coordination and LiCl assistance for humidity sensing applications. The composition, microstructure, thermal stability, and humidity response of polymer complexes based on ZrOCl2 were thoroughly investigated. The resulting complexes exhibited porous structures and demonstrated excellent thermal stability. The ionic conductivity displayed an exponential change of 106 - 107 within the relative humidity (RH) range of 43–95 %. The polymer complexes with 5 mol% ZrOCl2 exhibited the most favorable humidity sensing properties, including a response time of 90 s and a recovery time of 7 s. The addition of LiCl as an assistant further enhanced the humidity sensing properties of the polymer complexes. The optimal sensor exhibited high sensitivity, reaching 1175 throughout the entire RH range from 11 % to 95 %. It demonstrated good linearity, minimal humidity hysteresis (2.3 % RH), and rapid response/recovery time of 16/9 s. The development of LiCl-assisted polysiloxane polyelectrolyte-Zr complexes has provided a strategy for the creation of high-performance humidity sensors.

A non-nucleophilic electrolyte based on all-inorganic salts with conditioning-free characteristic for rechargeable magnesium batteries

Conditioning-free electrolytes with high reversibility of Mg plating/stripping are of vital importance for the commercialization of the superior rechargeable magnesium batteries (RMBs). In the present work, a non-nucleophilic electrolyte (denoted as MLCH) based on all-inorganic salts of MgCl2, LiCl and CrCl3 for RMBs is prepared by a straightforward one-step reaction. As a result, the MLCH electrolyte shows the noticeable performance of high ionic conductivity (3.40 mS cm−1), low overpotential (∼46 mV vs Mg/Mg2+), high Coulombic efficiency (∼93%), high anodic stability (SS, ∼2.56 V vs Mg/Mg2+) and long-term (more than 500 h) cycling stability, especially the conditioning-free characteristic. The main equilibrium species in the MLCH electrolyte are confirmed to be the tetracoordinated anions of [LiCl2(THF)2]− and solvated dimers of [Mg2(µ-Cl)3(THF)6]+. The addition of LiCl can assist the dissolution of MgCl2 and activation of the electrode/electrolyte interface, resulting in a superior Mg plating/stripping efficiency. The synergistic effect of LiCl, CrCl3, a small amount of HpMS and the absence of polymerization THF enable the conditioning-free characteristic of the MLCH electrolyte. Moreover, the MLCH electrolyte exhibits decent compatibility with the cathodic materials of CuS. The Mg/CuS full cell using the MLCH electrolyte presents a discharge specific capacity of 215 mAh g−1 at 0.1 C and the capacity can retain ∼72% after 40 cycles. Notably, the MLCH electrolyte has other superiorities such as the broad sources of materials, low-cost and easy-preparation, leading to the potential prospect of commercial application.

Modification of PVDF membrane for harvesting of Nannochloropsis sp. and its cleaning results

One of the biggest challenges in implementing microalgae-based biofuels is the effective harvesting process. Filtration membrane has become one of the flexible methods in microalgae harvesting. This study investigated the harvesting of Nannochloropsis sp. using a modified PVDF membrane at various LiCl as an additive with N-methyl-2-pyrrolidone (NMP) solvent. Harvesting of Nannochloropsis sp. with PVDF membrane has never been reported before. The addition of LiCl can improve the performance of PVDF membrane due to LiCl has a great affinity for water, resulted in inducing the formation of the pore structure of membrane. The optimum membrane composition was determined at various LiCl additive from 1% to 3% (w/w). The hydrophilicity of the membrane increased as indicated by the increasing of water permeance, which were 516, 546, 660, and 614 l m−2h−1 bar−1 for neat PVDF, PVDF/LiCl-1, PVDF/LiCl-2, and PVDF/LiCl-3 membrane, respectively. PVDF/LiCl-2 membrane showed the highest water permeance and the highest total average permeance (150 l m−2h−1 bar−1) with 100% rejection of Nannochloropsis sp. harvesting. The membranes was cleaned using sodium hypochlorite, citric acid, and nitric acid. The SEM results showed that the membrane after cleaning appears the algae particles in the membrane pore. Furthermore, algae particles were almost not visible on cleaned membrane. The FTIR results showed an absorption at 3401 cm−1, which was a characteristic of the hydrogen N–H bond, also including a typical amide uptake (C=O) at 1648 cm−1 indicating protein appearance. Moreover, the cleaned membrane did not appear any absorption that indicates the foulant.

#5930 ENDOTHELIAL CELL PROTEOME AND SECRETOME ALTERATION UNDER CHRONIC UREMIC EXPOSURE

Abstract Background and Aims Dialysis therapies including peritoneal dialysis (PD) are described to lead to premature vascular aging, atherosclerosis and associated cardiomyopathies, which are associated with high cardiovascular morbidity and mortality. Chronic inflammation, incomplete clearance of uremic toxins, and dyslipidaemia, are factors affecting the vasculature system. However, how these factors affect the endothelium, the fist cell layer in contact with these molecules, and the molecular mechanisms triggered by uremic toxins remain poorly understood. In vitro and in vivo studies have shown that cytoprotective additives (e.g. dipeptide alanyl-glutamine (AlaGln) or kinase inhibitor lithium chloride (LiCl)) to PD fluids reduce peritoneal damage in mesothelial and endothelial (EC) cells. Their potential systemic effects were not studied so far. Here, we demonstrate, in a newly developed model system, the changes induced by chronic exposure to serum of PD patients in the proteome and secretome of endothelial cells, and the effects of cytoprotective additives. Method For modelling systemic conditions of PD patients, primary EC were cultured for 5 passages in medium containing 10% serum collected from PD patients (n = 26) during regular PET tests, or from healthy donors (n = 12). Cytoprotective additives were added in parallel experiments. Cells were stably labelled (SILAC) to differentiate cell and donor serum proteins and the cellular proteome and secretome profiles were analysed by quantitative mass spectrometry. Prior to analysis of the secretome, equalizer beads, to enrich low abundant and deplete high abundant proteins, were used. ECIS (Electric Cell-substrate Impedance Sensing), was used to measure barrier function, growth rate, and permeability. Results Proteome analysis revealed perturbation of major cellular processes by serum of PD patients including inflammatory related processes such TLR regulation and complement activation, as well membrane related processes such as extracellular matrix interactions and junctions, and plasma lipoprotein remodelling. Addition of LiCl counteracted cell-adhesion related proteins. ECIS analysis showed that in uremic conditions the EC monolayer has a decreased barrier function compared to healthy conditions, and LiCl partially restores the tightness of the membrane. Secretome analysis showed differentially regulated proteins related to oxidative stress, senescence-associated secretory phenotype (SASP), and apoptosis. Interestingly, in the secretome, LiCl addition counter regulated INHBA and tissue factor pathway inhibitor 2, both proteins related to vascular calcification. Conclusion Surprisingly few studies have analysed uremic effects on EC using proteomics approaches, and no reports of chronic settings, modelling the patient situation, are available. Our data demonstrates that EC react to serum factors of PD patients with increased inflammation, permeability and a secretory profile. Interestingly, our model reflects many of the known effects on the vasculature, but unravels the molecular mechanism that may induce those processes. We have also identified potential mechanisms by which the addition of cytoprotective additives may counteract some of the uremic effects systemically. Secretomics data identified several proteins secreted by EC that are regulated in uremia with potential for cellular crosstalk with other cells of the vasculature, showing the potential to identify therapeutic targets to reduce the cardiovascular risk of PD patients and current limitations of the therapy.

An Effective Additive for Introducing the Triazole Unit of Ensitrelvir: Combination of LiCl and Et3N to Easily Generate Lithium Triazinolate

AbstractAn efficient and robust method was developed to introduce the triazole unit of Ensitrelvir, a COVID-19 therapeutic agent. One of the key steps is introducing the triazole unit in the triazinone with Cs2CO3 and KI in a heterogeneous system. Detailed reaction screening revealed that addition of LiCl allowed the reaction to proceed quantitatively in the presence of inexpensive Et3N, and the selectivity of the N-alkylation was greatly improved. The key to promoting the reaction is the mild formation of the lithium triazinolate accompanied by precipitation of Et3N·HCl (the only insoluble matter in this reaction). Dissolving all the substrates and reagents should contribute to further improvement of the process robustness.

Performance evaluation of PVA/PEO/LiCl composite as coated heat exchangers desiccants

Composite desiccants have led to a growing interest because of their eco-friendliness, sustainability, and excellent dehumidification properties. In this paper, we present a method for constructing a dehumidification composite of PVA/PEO/LiCl that is eco-friendly and recyclable. The results show that PVA/PEO/LiCl has better dehumidification performance than SG, SG/LiCl, PVA/PEO, and PVA/PEO/CaCl2 as coated heat exchangers desiccants. The addition of LiCl caused the internal hydrophilic polymeric hygroscopic carriers to work in concert with the membrane porosity. This resulted in a considerable increase in the membrane's hygroscopic rate and capacity, as well as improved mechanical qualities. As the concentration of LiCl was increased, the surface sealing of the PVA/PEO polymer improved dramatically, and the shape of the polymer-formed film changed from loose to firmly packed. The structural shift toward densification boosted the strength of the co-blended dehumidified films. With a PVA/PEO/LiCl ratio of 1:1:2.5 and the coating thickness of 10–15 µm, the greatest dehumidification effectiveness is achieved. During five subsequent sorption and desorption procedures, the sorption of PVA/PEO/LiCl remained between 70 and 75%, demonstrating its outstanding reusability and cycling stability.

Effect of salt addition on cellulose conversion into 5-hydroxymethylfurfural in metal chloride aqueous solution

Metal chloride aqueous solution is an effective method to promote the conversion of cellulose into 5-hydroxymethylfurfural (HMF). In this work, the influences of sodium chloride (NaCl) and lithium chloride (LiCl) on the conversion of cellulose into HMF in ferric chloride (FeCl3) aqueous solution were investigated. The conversion of glucose and fructose in FeCl3–NaCl and FeCl3–LiCl aqueous solutions were studied, and the interaction between active species and cellobiose was characterized by UV spectrum and electrospray ion mass spectrometry to explore salt addition on the reaction of cellulose conversion and the active specie. Results showed that the yield of HMF converted from cellulose in FeCl3 aqueous solution was low, while the yield of HMF was significantly increased when NaCl or LiCl added to the system. In FeCl3–NaCl aqueous solutions, the yield of HMF reach a maximum of 40.0% at a concentration of 0.02 M FeCl3, and hydrolysis of cellulose was the key step in the conversion of cellulose; In FeCl3–LiCl aqueous solutions, the yield of HMF reach a maximum of 36.7% at a concentration of 0.06 M FeCl3, and isomerization of glucose was the controlling step. The characterization results illustrated that the addition of NaCl or LiCl changed the active species in FeCl3 aqueous solutions, and [Fe(OH)2]+ and [FeCl2(OH) + Li]+ were the active species in FeCl3–NaCl and FeCl3–LiCl aqueous solution for cellulose conversion, respectively.

Activation of Wnt/β‑Catenin‑p130/E2F4 promotes the differentiation of bone marrow‑derived mesenchymal stem cells into typeII alveolar epithelial cells through cell cycle arrest.

The results of our previous study demonstrated that activation of the Wnt/β-catenin pathway increased the differentiation of mesenchymal stem cells (MSCs) into type II alveolar epithelial (AT II) cells; however, the specific mechanisms remain unclear. The present study aimed to evaluate the role of Wnt/β-catenin-p130/E2F transcription factor 4 (E2F4) in regulating the differentiation of mouse MSCs (mMSCs) into AT II cells, and to determine the specific mechanisms. mMSCs with p130 or E2F4 overexpression were constructed using lentiviral vectors. Differentiation of mMSCs into AT II cells was promoted using a modified coculture system with murine lung epithelial-12 cells incubated in small airway growth medium for 7-14 days. The differentiation efficiency was detected using immunofluorescence, western blot analysis and transmission electron microscopy. To detect the association between the canonical Wnt pathway and p130/E2F4, 4 mmol/l lithium chloride (LiCl) or 200 ng/ml Dickkopf-related protein 1 (DKK-1) was also added to the coculture system. Following differentiation, the cell cycle of mMSCs was evaluated using flow cytometry. The results of the present study demonstrated that surfactant protein C (SP-C) protein expression was higher in the p130 overexpression (MSC-p130) and E2F4 overexpression (MSC-E2F4) groups compared with the normal control mMSCs group following differentiation into AT II cells. Similar results for SP-C protein expression and lamellar body-like structures were also observed using immunofluorescence analysis and electron microscopy. Following the addition of LiCl into the coculture system for activation of the Wnt/β-catenin signaling pathway, phosphorylated (p)-p130/p130 was slightly decreased at 7 days and E2F4 was increased both at 7 and 14 days in mMSCs. Furthermore, the p-p130/p130 ratio was significantly increased at 14 days and E2F4 was decreased both at 7 and 14 days following DKK-1-mediated inhibition of the Wnt pathway. The results of the present study demonstrated that the numbers of cells in G1 and S phases were increased following activation of the Wnt pathway and decreased following Wnt pathway inhibition. However, the number of cells in G1 phase was increased following the differentiation of mMSCs overexpressing p130 or E2F4. Therefore, the results of the present study revealed that the canonical Wnt signaling pathway may affect the differentiation of MSCs into AT II cells via regulation of downstream p130/E2F4. The specific mechanisms may be associated with G1 phase extension in the cell cycle of MSCs.

Umfassende Studie der Gesteigerten Reaktivität von Turbo‐Grignard‐Reagenzien**

AbstractSeit ihrer Einführung im Jahr 2004 revolutionierten Knochel's sogenannte Turbo‐Grignard‐Reagenzien die Anwendung der Grignard‐Reagenzien. Durch die einfache Zugabe von LiCl zu einem Magnesium‐Alkyl kann eine außerorderliche Steigerung der Reaktivität beobachtet werden. Die genaue Zusammensetzung der reaktiven Spezies blieb jedoch lange Zeit ein Rätsel, obwohl das reaktive Gemisch nicht nur in der Synthese breite Anwendung fand, sondern auch in anderen Bereichen wie der Materialwissenschaft Einzug hielt. Um dieses Rätsel zu lösen, kombinierten wir Einkristall‐Röntgendiffraktometrie mit NMR‐Spektroskopie in Lösung und vollendeten unsere Untersuchungen mit quantenchemischen Berechnungen. Durch die breite Vielfalt unserer Methoden, gelang uns ein Einblick in und eine erstmalige Erklärung für die außergewöhnliche Reaktivität dieses äußerst praktikablen Reagenzes, indem wir die Struktur der ersten bimetallischen Spezies [t‐Bu2Mg ⋅ LiCl ⋅ 4 THF] mit zwei tert‐Butylanionen am Magnesium‐zentrum und eingebautem Lithiumchlorid aufklärten.

Comprehensive Study of the Enhanced Reactivity of Turbo-Grignard Reagents.

Since its introduction in 2004, Knochel's so called Turbo-Grignard reagents revolutionized the usage of Grignard reagents. Through the simple addition of LiCl to a magnesium alkyl an outstanding increase in reactivity can be achieved. Though the exact composition of the reactive species remained mysterious, the reactive mixture itself is readily used not only in synthesis but also found its way into more distant fields like material science. To unravel this mystery, we combined single-crystal X-ray diffraction with in-solution NMR-spectroscopy and closed our investigations with quantum chemical calculations. Using such a variety of methods, we have gained insight into and an explanation for the extraordinary reactivity of this extremely convenient reagent by determining the structure of the first bimetallic reactive species [t-Bu2 Mg ⋅ LiCl ⋅ 4 thf] with two tert-butyl anions at the magnesium center and incorporated lithium chloride.

Lithium Chloride Promotes Endogenous Synthesis of CLA in Bovine Mammary Epithelial Cells.

Although conjugated linoleic acid (CLA) can promote human health, its content in milk is insufficient to have a significant impact. The majority of the CLA in milk is produced endogenously by the mammary gland. However, research on improving its content through nutrient-induced endogenous synthesis is relatively scarce. Previous research found that the key enzyme, stearoyl-CoA desaturase (SCD) for the synthesis of CLA, can be expressed more actively in bovine mammary epithelial cells (MAC-T) when lithium chloride (LiCl) is present. This study investigated whether LiCl can encourage CLA synthesis in MAC-T cells. The results showed that LiCl effectively increased SCD and proteasome α5 subunit (PSMA5) protein expression in MAC-T cells as well as the content of CLA and its endogenous synthesis index. LiCl enhanced the expression of proliferator-activated receptor-γ (PPARγ), sterol regulatory element-binding protein 1 (SREBP1), and its downstream enzymes acetyl CoA carboxylase (ACC), fatty acid synthase (FASN), lipoprotein lipase (LPL), and Perilipin 2 (PLIN2). The addition of LiCl significantly enhanced p-GSK-3β, β-catenin, p-β-catenin protein expression, hypoxia-inducible factor-1α (HIF-1α), and downregulation factor genes for mRNA expression (P < 0.05). These findings highlight that LiCl can increase the expression of SCD and PSMA5 by activating the transcription of HIF-1α, Wnt/β-catenin, and the SREBP1 signaling pathways to promote the conversion of trans-vaccenic acid (TVA) to the endogenous synthesis of CLA. This data suggests that the exogenous addition of nutrients can increase CLA content in milk through pertinent signaling pathways.

Redox Behavior of Cobalt-Phosphine Complexes vs Their Catalytic Activity in Organozinc Compound Formation: Background for Mechanistic Investigations.

Catalytic activity in arylzinc compound formation was studied for eight Co complexes with phosphines along with their redox properties for implementing the idea of rational design. It was found that Co(XantPhos)Cl2 and Co(N-XantPhos)Cl2 demonstrated distinct reversible CoII/CoI redox processes and acted as efficient catalysts of arylzinc compound formation. Meanwhile, for Co(DPEphos)Cl2, Co(dppf)Cl2, Co(dppb)Cl2, Co(PPh3)2Cl2, and Co(XantPhos)(Piv)2 (the latter one without the addition of LiCl), reversible redox processes were not observed. These catalysts did not act efficiently for the model process of organozinc compound formation. Co4(dppe)5Cl8 was the only exception, explained by a completely different structure (CoP4Cl and CoPCl3) of donor sets instead of CoP2X2 (X = Cl or O). The stability of complexes in tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) solutions was studied by UV-vis spectroscopy. Previously unknown X-ray structures for Co(XantPhos)(Piv)2, Co(N-XantPhos)Cl2, and {Co(DMF)6}{(CoCl3)2(dppb)} were determined. The use of pivalate counterions instead of chloride for Co(XantPhos)2+ led to a significant (ca. 20 times) increase of the kinetic solubility in THF compared to Co(XantPhos)Cl2, preserving high catalytic productivity upon the addition of LiCl. This allowed the latter to be efficiently used in combination with LiCl as the catalyst for arylzinc compound formation on a 2 g scale. The data obtained in this work can be regarded as experimental confirmation of the first and last stages of the plausible reaction pathway of arylzinc compound formation, involving CoII → CoI and CoI → CoII transformations, which could be a significant framework for further mechanistic investigations.