Solution combustion synthesis,energy and environment: Best parameters for better materials

Solution combustion synthesis (SCS) is a worldwide used methodology for the preparation of inorganic ceramic and composite materials with controlled properties for a wide number of applications, from catalysis to photocatalysis and electrocatalysis, from heavy metal removal to sensoristics and electronics. The high versatility and efficiency of this technique have led to the introduction of many variants, which allowed important optimization to the prepared materials. Moreover, its ecofriendly nature encouraged further studies about the use of sustainable precursors for the preparation of nanomaterials for energy and environment, according to the concept of circular economy. On the other hand, the large variety of expressions to define SCS and the often-contradictory definitions of the SCS parameters witnessed a scarce consciousness of the potentiality of this methodology. In this review article, the most important findings about SCS and the selection criteria for its main parameters are critically reviewed, in order to give useful guidelines to those scientists who want to use this methodology for preparing materials with improved or new functional properties. This review aims as well (i) to bring more clarity in the SCS terminology (ii) to increase the awareness of the SCS as a convenient tool for the synthesis of materials and (iii) to propose a new perspective in the SCS, with special attention to the use of ecofriendly procedures. Part of the review is also dedicated to precautions and limitations of this powerful methodology.     

γ-Valerolactone (GVL) as a green and efficient dipolar aprotic reaction medium

The great challenge for modern research is to define the most efficient tools to make more sustainable the industrial production and manufacturing. Among the different aspects that require attention the replacement of toxic and/or non-renewable solvents it is certainly playing a crucial role. Dealing with widely used dipolar aprotic solvents, among the different alternatives proposed in the literature γ-valerolactone (GVL) plays a pivotal role covering different application area. In this contribution, the benefits derived from the use of GVL as a circular, safe, biomass-derived reaction medium are highlighted covering most recent publications (2021). The presentation has been divided into three major sections: (i) biomass valorization, (ii) materials synthesis, manufacturing and recycle and (iii) new synthetic methodologies.     

A facile synthesis of non-aqueous LiPO2F2 solution as the electrolyte additive for high performance lithium ion batteries

Constructing a reliable and favorable electrode-electrolyte interface is crucial to utilize the exceptional energy storage capability in commercial lithium-ion batteries. Here, we report a facile synthesis approach for the lithium difluorophosphate (LiPO₂F₂) solution as an effective film-forming additive via direct adding the Li₂CO₃ into LiPF₆ solution at 45 °C. Benefiting from the significantly reduced interface resistance (R_SEI) and charge transfer impedance (R_ct) of both the cathode and anode by adding the prepared LiPO₂F₂ solution into a baseline electrolyte, the cycling performance of the graphite||LiNi_0.5Mn_0.3Co_0.2O₂ pouch cell is remarkably improved under all-climate condition.     

A novel synthetic route to rac-(Z)-recifeiolide from cyclooctanone and acetaldehyde

A novel synthetic approach to (±)-Z-recifeiolide 6, a 12-membered-ring lactone which can be selectively isomerized into (E)-recifeiolide, a natural antibiotic product isolated from fungus (Cephalosporium recifei) is reported. The synthesis is accomplished in five steps starting from readily available cyclooctanone and acetaldehyde based on the Lewis acid-catalyzed TMS-directed oxy-2-oxonia-Cope rearrangement. The work represents a novel strategy to assemble related macrolides.     

Synthesis and electrochemical properties of copper(II), manganese(III) phthalocyanines bearing chalcone groups at peripheral or nonperipheral positions

In this study, new chalcone compound 1 , new phthalonitrile derivatives 2 and 3, new copper(II), manganese(III) phthalocyanines bearing chalcone groups at peripheral or nonperipheral positions were synthesized. Electrochemistry of tetra-(4-{(2 E )-3-[2-fluoro-4-(trifluoromethyl)phenyl]prop-2-enoyl}phenoxy) substituted Co(II)Pc and Mn(III)Pcs were studied with cyclic voltammetry (CV) to determine the redox properties of the phthalocyanines. According to the results, while the CuPcs 2a and 3a showed two Pc based reduction reactions and one Pc based oxidation reaction, MnPcs 2b and 3b gave two metal-based reduction reactions. All the redox processes are shifted toward positive potentials as a result of the increased electron-withdrawing ability of the trifluoromethyl substituents.     

Novel synthesis of sensor for selective detection of Fe+3 ions under various solvents

Naked-eye colored chemo dosimeter based on vanilline based conjugated sensor was synthesized and characterized. The main point of this paper is that the solvent also affects on selectivity of metals. Vanilline based conjugate sensor exhibited high selectivity and sensitivity for detection of Ferric ions (Fe⁺³) in all (both polar and nonpolar) solvents according to absorbance which can be observed by naked eye. The selectivity was more prominent in nonpolar or less polar solvent due to solubility factor of ions and sensor but not for polar. The detection of limit of the synthesized probes was shown up to 0.84 ppm. The dielectric constant of solvents affected on the complex formation of ligand with transition metal ions. A filter paper strip system was used for rapid monitoring of detection by color variation.     

K6In2Q6 (Q = S,Se, Te): Missing Links in the Series of Alkali Chalcogenido Ditrielates(III)

The chalcogenido indates K₆In₂Q₆ (Q = S, Se, Te) were synthesized from melts of the pure elements at a maximum temperature of 700 °C. All three potassium salts contain dinuclear units [In₂Q₆]^6– of two edge-sharing [InQ₄] tetrahedra. The sulfido and the selenido indate are isotypic and crystallize in the K₆Mn₂O₆-type structure [monoclinic, space group P2₁/c, a = 784.32(9)/809.32(3), b = 1274.58(14)/1322.37(4), c = 836.48(9)/870.53(3) pm, β = 97.900(2)/97.5877(8)°, Z = 2, R₁ = 0.0123/0.0109; for Q = S/Se]. The tellurido indate K₆In₂Te₆ crystallizes in a new orthorhombic structure type [space group Pnma, a = 1793.70(12), b = 1491.55(11), c = 837.40(6) pm, Z = 4, R₁ = 0.0157]. In this structure, the telluride anions form a hexagonal close packing, in which K⁺ cations occupy all octahedral voids; the In³⁺ ions take 1/6 (but always adjacent) tetrahedral voids. This structure-chemical relation to the h.c.p. packing, which is similarly found for most of the sodium dimetallates (e.g. Na₆Fe₂S₆), is substantiated by a full crystallographic group-subgroup tree. The crystal chemistry of the new indates is discussed and compared with that of alkali chalcogenido metallates(III) of Fe, Al and Ga containing [M₂Q₆]^6– dimers, which overall form as many as ten different structure types. DFT band structure calculations of the three title compounds exhibit bandgaps, which continuously decrease from the S to the Te compound and which are also in accordance with the pale yellow (S), bright yellow (Se) and red-brown (Te) color of the compounds. The chemical bonding in the salts and within the metallate anion is discussed on the basis of the partial DOS and a Bader analysis of the calculated electron density.     

Bioinspired Total Synthesis of Complex Nucleoside Antibiotics A201A,A201D and A201E

Herein, bioinspired total syntheses of A201A, A201D, and A201E based on a previously reported biosynthetic pathway are presented. The challenging 1,2-cis-furanoside, a core structure of the A201 family, was obtained by remote 2-quinolinecarbonyl-assisted glycosylation. We accomplished the total synthesis of A201A and A201E based on the critical 1,2-cis-furanoside moiety through late-stage glycosylation without any interference from basic dimethyl adenosine. We also confirmed the absolute configuration of A201E by total synthesis. This modular synthesis strategy enables efficient preparation of A201 family antibiotics, allowing the study of their structure–activity relationships and mode of action. This study satisfies the increasing demand for developing novel antibiotics inspired by the A201 family.     

Organocatalytic Enantioselective Pictet–Spengler Reaction of α-Ketoesters: Development and Application to the Total Synthesis of (+)-Alstratine A

We report herein an asymmetric Pictet–Spengler reaction of α-ketoesters. In the presence of a catalytic amount of simple alanine-derived squaramide and p-nitrobenzoic acid, reaction of tryptamines with methyl 2-oxoalkanoates afforded the corresponding 1-alkyl-1-methoxycarbonyl tetrahydro-β-carbolines (THBCs) in high yields and ee values. A primary kinetic isotope effect (KIE=4.5) using C2-deteurium-labelled tryptamine indicates that rearomatization through deprotonation of the pentahydro-β-carbolinium ion could be the rate- and enantioselectivity-determining step. A concise enantioselective total synthesis of (+)-alstratine A, a hexacyclic cagelike monoterpene indole alkaloid, featuring this reaction as a key step, was subsequently accomplished. Remeasurement of the [a]_D value of the natural product indicates that natural alstratine A is dextrorotatory rather than levorotatory as it was initially reported in the isolation paper.     

中空MOFs材料制备及电催化应用的研究进展

水分裂、金属-空气电池和燃料电池等能源转换技术对解决未来的能源危机和环境问题至关重要.氧还原反应(ORR)、氧析出反应(OER)和氢析出反应(HER)作为其核心反应,存在反应动力学速率较慢的问题,因此,开发研制高效的非贵金属电催化剂具有重要意义.金属有机骨架(MOFs)材料因具有高度可调的组成和多孔晶体结构,在不同的应用领域引起了越来越多的关注.中空MOFs纳米材料具有MOFs材料高度可调的组成和结构优势,又具有中空结构纳米材料的优点(如更快的物质传输、更丰富的孔隙率、灵活多变的活性组分、更多的暴露活性位点及对苛刻条件的更好相容性等),在电催化领域显现出巨大的应用潜力.本文对近几年来基于中空结构MOFs材料的制备及在电催化方面应用的研究进展进行了综合评述,并对该领域面临的挑战和发展前景进行了总结和展望.