Carbonaceous acid catalyst with high acid content was synthesized by metal (Zr) ion chelation and sulfonation of sodium carboxymethylcellulose. It catalyzed the esterification of oleic acid, with ...biodiesel yield > 99% at 40–90 °C (activation energy of 24.7 KJ/mol).
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•Carbon-based catalyst with various acid sites was synthesized.•Catalyst had high total acid content (8.45 mmol/g) for esterification of oleic acid.•High biodiesel yield (> 99%) was achieved at 40–90 °C with Ea of 24.7 KJ/mol.•10 cycles with biodiesel yield > 87% at 90 °C for 2 h reaction.•3 cycles with biodiesel yield > 93% at 50 °C for 6 h reaction.
Carbonaceous catalyst, with a variety of acid sites, was successfully synthesized by a two-step method at low temperature. The synthesized catalyst (Zr-SO3H@CMC) was characterized by elemental analysis, XRD, ICP-OES, FT-IR, BET, SEM-EDX and Boehm titration. It had high total acid content (8.45 mmol/g) for oleic acid esterification with high biodiesel yields (> 99%) at 40–90 °C. Under conditions of 90 °C, 20/1 methanol/oleic acid molar ratio, 5 wt% catalyst and 2 h reaction time, biodiesel yield of > 87% was achieved after 10 cycles of use. At lower temperatures (40, 50 and 60 °C), biodiesel yield still reached 82%, 93% and 90% after 3 cycles, respectively. The high activity of Zr-SO3H@CMC benefited from low activation energy of 24.7 KJ/mol. It shows potential application for esterification of free fatty acids or pretreatment of oils with high acid value for the green production of biodiesel.
Ether based electrolytes have surfaced as alternatives to conventional carbonates allowing for enhanced electrochemical performance of sodium-ion batteries; however, the primary source of the ...improvement remains poorly understood. Here we show that coupling titanium dioxide and other anode materials with diglyme does enable higher efficiency and reversible capacity than those for the combination involving ester electrolytes. Importantly, the electrolyte dependent performance is revealed to be the result of the different structural evolution induced by a varied sodiation depth. A suit of characterizations show that the energy barrier to charge transfer at the interface between electrolyte and electrode is the factor that dominates the interfacial electrochemical characteristics and therefore the energy storage properties. Our study proposes a reliable parameter to assess the intricate sodiation dynamics in sodium-ion batteries and could guide the design of aprotic electrolytes for next generation rechargeable batteries.
Here an efficient copper‐catalyzed cascade cyclization of azide‐ynamides via α‐imino copper carbene intermediates is reported, representing the first generation of α‐imino copper carbenes from ...alkynes. This protocol enables the practical and divergent synthesis of an array of polycyclic N‐heterocycles in generally good to excellent yields with broad substrate scope and excellent diastereoselectivities. Moreover, an asymmetric azide–ynamide cyclization has been achieved with high enantioselectivities (up to 98:2 e.r.) by employing BOX‐Cu complexes as chiral catalysts. Thus, this protocol constitutes the first example of an asymmetric azide–alkyne cyclization. The proposed mechanistic rationale for this cascade cyclization is further supported by theoretical calculations.
An efficient copper‐catalyzed cascade cyclization of azide‐ynamides via α‐imino copper carbene intermediates is disclosed, enabling divergent synthesis of polycyclic N‐heterocycles in generally good to excellent yields with broad substrate scope and excellent diastereoselectivities, representing the first generation of α‐imino copper carbenes directly from alkynes. The asymmetric azide–ynamide cyclization has been achieved with high enantioselectivities.
The electrochemical N2 fixation, which is far from practical application in aqueous solution under ambient conditions, is extremely challenging and requires a rational design of electrocatalytic ...centers. We observed that bismuth (Bi) might be a promising candidate for this task because of its weak binding with H adatoms, which increases the selectivity and production rate. Furthermore, we successfully synthesized defect‐rich Bi nanoplates as an efficient noble‐metal‐free N2 reduction electrocatalyst via a low‐temperature plasma bombardment approach. When exclusively using 1H NMR measurements with N2 gas as a quantitative testing method, the defect‐rich Bi(110) nanoplates achieved a 15NH3 production rate of 5.453 μg mgBi−1 h−1 and a Faradaic efficiency of 11.68 % at −0.6 V vs. RHE in aqueous solution at ambient conditions.
Beneficial defects: Defect‐rich bismuth nanoplates achieve a 15NH3 production rate of 5.453 μg mgBi−1 h−1 and a Faradaic efficiency of 11.68 % at −0.6 V vs. RHE in aqueous solutions at ambient conditions because of their poor binding with H adatoms, which increases the selectivity and production rate. Also, 1H NMR measurements with N2 gas ware used as a quantitative test method in aqueous electrolytes.
Rational utilization of the rich light‐bio‐matter interplay taking place in single‐cell analysis represents a new technological direction in the field. The light‐fueled operation is expected to ...achieve advanced photoelectrochemical (PEC) single‐cell analysis with unknown possibilities. Here, a PEC nanoreactor capable of single‐cell sampling and near zero‐background Faradaic detection of intracellular microRNA (miR) is devised by the construction of a small reaction chamber accommodating the target‐triggered hybridization chain reaction for binding the metallointercalator of Ru(bpy)2(dppz)2+ as the signal reporter. Light stimulation of the dsDNA/metallointercalator adduct will induce the generation of photocurrents, underpinning a zero‐biased and near zero‐background PEC method toward Faradaic detection of non‐electrogenic miR at the single‐cell level. Using this nanotool, lower miR concentration in the near‐nucleus region than that in the main cytosol was revealed.
A photoelectrochemical nanoreactor was devised for single‐cell sampling and near zero‐background faradic detection of intracellular microRNA. This platform provided a new perspective for exploring light‐biomatter interplay toward single‐cell studies.
Aqueous rechargeable microbatteries are promising on-chip micropower sources for a wide variety of miniaturized electronics. However, their development is plagued by state-of-the-art electrode ...materials due to low capacity and poor rate capability. Here we show that layered potassium vanadium oxides, K
V
O
·nH
O, have an amorphous/crystalline dual-phase nanostructure to show genuine potential as high-performance anode materials of aqueous rechargeable potassium-ion microbatteries. The dual-phase nanostructured K
V
O
·nH
O keeps large interlayer spacing while removing secondary-bound interlayer water to create sufficient channels and accommodation sites for hydrated potassium cations. This unique nanostructure facilitates accessibility/transport of guest hydrated potassium cations to significantly improve practical capacity and rate performance of the constituent K
V
O
·nH
O. The potassium-ion microbatteries with K
V
O
·nH
O anode and K
MnO
·nH
O cathode constructed on interdigital-patterned nanoporous metal current microcollectors exhibit ultrahigh energy density of 103 mWh cm
at electrical power comparable to carbon-based microsupercapacitors.
Spheroid-based three-dimensional (3D) liver culture models, offering a desirable biomimetic microenvironment, are useful for recapitulating liver functions in vitro. However, a user-friendly, robust ...and specially optimized method has not been well developed for a convenient, highly efficient, and safe in situ perfusion culture of spheroid-based 3D liver models. Here, we have developed a biomimetic and reversibly assembled liver-on-a-chip (3D-LOC) platform and presented a proof of concept for long-term perfusion culture of 3D human HepG2/C3A spheroids for building a 3D liver spheroid model. On the basis of a fast and reversible seal of concave microwell-based PDMS-membrane-PDMS sandwich multilayer chips, it enables a high-throughput and parallel perfusion culture of 1080 cell spheroids in a high mass transfer and low fluid shear stress biomimetic microenvironment as well as allowing the convenient collection and analysis of the cell spheroids. In terms of reducing spheroid loss and maintaining cell morphology and viability in long-term perfusion culture, the cell spheroids in the 3D-LOC were more safe and efficient. Notably, the polarisation, liver-specific functions, and metabolic activity of the cell spheroids in 3D-LOC were also remarkably improved and exhibited better long-term maintenance over conventional perfusion methods. Additionally, a robust micromilling method that incorporates secondary PDMS coating techniques (SPCs) for fabricating V-shaped concave microwells was also developed. The V-shaped concave microwell arrays exhibited a higher distribution density and aperture ratio, making it easy to form large-scale and uniform-sized cell spheroids with minimum cell loss. In summary, the proposed 3D-LOC could provide a convenient and robust solution for the long-term safe perfusion culture of hepatic spheroids and be beneficial for a variety of potential applications including development of bio-artificial livers, disease modeling, and drug toxicity screening.
Medicines for the treatment of 2019-novel coronavirus (2019-nCoV) infections are urgently needed. However, drug screening using live 2019-nCoV requires high-level biosafety facilities, which imposes ...an obstacle for those institutions without such facilities or 2019-nCoV. This study aims to repurpose the clinically approved drugs for the treatment of coronavirus disease 2019 (COVID-19) in a 2019-nCoV-related coronavirus model.
A 2019-nCoV-related pangolin coronavirus GX_P2V/pangolin/2017/Guangxi was described. Whether GX_P2V uses angiotensin-converting enzyme 2 (ACE2) as the cell receptor was investigated by using small interfering RNA (siRNA)-mediated silencing of ACE2. The pangolin coronavirus model was used to identify drug candidates for treating 2019-nCoV infection. Two libraries of 2406 clinically approved drugs were screened for their ability to inhibit cytopathic effects on Vero E6 cells by GX_P2V infection. The anti-viral activities and anti-viral mechanisms of potential drugs were further investigated. Viral yields of RNAs and infectious particles were quantified by quantitative real-time polymerase chain reaction (qRT-PCR) and plaque assay, respectively.
The spike protein of coronavirus GX_P2V shares 92.2% amino acid identity with that of 2019-nCoV isolate Wuhan-hu-1, and uses ACE2 as the receptor for infection just like 2019-nCoV. Three drugs, including cepharanthine (CEP), selamectin, and mefloquine hydrochloride, exhibited complete inhibition of cytopathic effects in cell culture at 10 μmol/L. CEP demonstrated the most potent inhibition of GX_P2V infection, with a concentration for 50% of maximal effect EC50 of 0.98 μmol/L. The viral RNA yield in cells treated with 10 μmol/L CEP was 15,393-fold lower than in cells without CEP treatment (6.48 ± 0.02 × 10vs. 1.00 ± 0.12, t = 150.38, P < 0.001) at 72 h post-infection (p.i.). Plaque assays found no production of live viruses in media containing 10 μmol/L CEP at 48 h p.i. Furthermore, we found CEP had potent anti-viral activities against both viral entry (0.46 ± 0.12, vs.1.00 ± 0.37, t = 2.42, P < 0.05) and viral replication (6.18 ± 0.95 × 10vs. 1.00 ± 0.43, t = 3.98, P < 0.05).
Our pangolin coronavirus GX_P2V is a workable model for 2019-nCoV research. CEP, selamectin, and mefloquine hydrochloride are potential drugs for treating 2019-nCoV infection. Our results strongly suggest that CEP is a wide-spectrum inhibitor of pan-betacoronavirus, and further study of CEP for treatment of 2019-nCoV infection is warranted.
Carbon materials, including graphite, hard carbon, soft carbon, graphene, and carbon nanotubes, are widely used as high‐performance negative electrodes for sodium‐ion and potassium‐ion batteries ...(SIBs and PIBs). Compared with other materials, carbon materials are abundant, low‐cost, and environmentally friendly, and have excellent electrochemical properties, which make them especially suitable for negative electrode materials of SIBs and PIBs. Compared with traditional carbon materials, modifications of the morphology and size of nanomaterials represent effective strategies to improve the quality of electrode materials. Different nanostructures make different contributions toward improving the electrochemical performance of electrode materials, so the synthesis of nanomaterials is promising for controlling the morphology and size of electrode materials. This paper reviews the progress made and challenges in the use of carbon materials as negative electrode materials for SIBs and PIBs in recent years. The differences in Na+ and K+ storage mechanisms among different types of carbon materials are emphasized.
Carbon materials represent one of the most promising candidates for negative electrode materials of sodium‐ion and potassium‐ion batteries (SIBs and PIBs). This review focuses on the research progress of carbon materials such as graphite, hard carbon, soft carbon, graphene and carbon nanotubes, and other carbon nanomaterials as negative electrode materials for SIBs and PIBs.
People extend the MSSM with the local gauge group U(1)X to obtain the U(1)XSSM. In the framework of the U(1)XSSM, we study the flavor transition process b→sγ with the mass insertion approximation ...(MIA). By the MIA method and some reasonable parameter assumptions, we can intuitively find the parameters that have obvious effect on the analytic results of the flavor transition process b→sγ. By means of the influences of different sensitive parameters, we can obtain reasonable results to better fit the experimental data.