Hybrid liquid crystals tetrazolyl and isoxazolyl cinnamates

In this work, a series of isoxazolyl and tetrazolylcinnamic ester hybrid liquid crystals (HLCs) were synthesised and their mesomorphic behaviour was analysed. Cinnamic acid derivatives were prepared by Knoevenagel condensation of malonic acid and arylaldehydes. Five-membered tetrazoles and isoxazoles were prepared by [3 + 2] 1,3-dipolar cycloaddition. Tetrazoles were synthesised by sodium azide addition to arylnitrile, while isoxazoles were synthetised by arylnitrile oxide addition to alkenes to form isoxazolines, followed by MnO₂-oxidation. Tetrazolyltolane compounds were also synthesised and their LC behaviour compared with cinnamic esters. HLCs containing isoxazole rings displayed a large mesophase range with high clearing temperature (T_c), with predominance of smectic mesophases SmA and SmC. The HLCs decomposed upon heating due to their high clearing temperature (>250°C). HLCs with tetrazole rings showed a narrow nematic mesophase range with enantiotropic or monotropic behaviour.     

Development of Gold‐catalyzed [4+1] and [2+2+1]/[4+2] Annulations between Propiolate Derivatives and Isoxazoles

Two new gold‐catalyzed annulations of isoxazoles with propiolates have been developed. Most isoxazoles follow an initial O attack on the alkyne to afford a [4+1] annulation product. This process results in a remarkable alkyne cleavage of initial propiolates. Unsubstituted isoxazoles proceed through an N attack step to yield formal [2+2+1]/[4+2] annulation products. These two annulation products arise initially from two seven‐membered heterocyclic intermediates, which then lead to products.     

Synthetic strategies for 1,4,5/4,5-substituted azoles: A perspective review

Azole nucleus represents an important class of biologically active compounds that are gaining more attention in the field of medicinal chemistry due to large number of structure diversity. Among azoles, pyrazoles, and isoxazoles five-membered nitrogen containing heterocyclic compounds are associated wide range of biological activities such as anticancer, antimicrobial, anti-inflammatory, antioxidant, etc. Some of azole derivatives (e.g., 1,4,5-trisubstituted pyrazoles, 4,5-disubstituted isoxazoles, and 4,5-disubstituted-1H-pyrazoles) are still unexplored in literature, these unexplored azoles have fascinated the consideration of many researchers to study their framework synthetically and biologically. This present review is an attempt to update and understand the chemistry of unexplored pyrazoles and isoxazoles along with their medicinal importance. This article would definitely help the researchers to bring further enhancement in the synthesis of biologically active pyrazoles and isoxazoles.     

Folded nanosheet-like Co<Subscript>0.85</Subscript>Se array for overall water splitting

Active, stable, and earth-abundant bifunctional electrocatalyst for overall water splitting is pivotal to actualize large-scale water splitting via electrolysis. In this work, the hierarchical folded nanosheet-like Co_0.85Se array on Ni foam is constructed by liquid-phase chemical conversion with cobalt precursor nanorod array. It can serve as an efficient bifunctional electrocatalyst for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline electrolyte, with a current density of 10 mA cm^?2 at overpotential of 232 mV for OER and 129 mV for HER and Tafel slope of 78.9 mV dec^?1 for OER and 95.0 mV dec^?1 for HER, respectively. The two-electrode alkaline water electrolyzer utilizing this folded nanosheet-like Co_0.85Se array as both anode and cathode toward overall water splitting offered a current of 10 mA cm^?2 at a cell voltage of 1.60 V. This work explores an efficient and low-cost electrocatalyst for overall water splitting application in alkaline electrolytes.     

A Facile One‐Pot Synthesis of 3,5‐Disubstituted Isoxazole Derivatives Using Hydroxy (Tosyloxy) Iodobenzene

Hydroxy (tosyloxy) iodobenzene (HTIB), a hypervalent iodine reagent, has been extensively used for oxidative transformations. We have developed a one‐pot synthesis wherein aldoximes when reacted with alkynes in the presence of HTIB result in the direct formation of isoxazoles. This simple and straightforward reaction allows for ease of purification while leading to the formation of high purity 3,5‐disubstituted isoxazoles in moderate yields.     

A Versatile Iron‐Catalyzed Protocol for the One‐Pot Synthesis of Isoxazoles or Isoxazolines from the Same Propargylic Alcohols

The use N‐sulfonyl‐protected hydroxylamines as bi‐nucleophiles in iron‐catalyzed propargylic substitutions allows the selective one‐pot synthesis of four classes of substituted isoxazoles or isoxazolines from the same propargylic alcohols (21 examples) by simply tuning the nature of the base. By using an iron(III) catalyst and a base such as triethylamine (3 equiv), isoxazoles 3 are obtained in good isolated yields (56–95%), whereas N‐sulfonyl‐protected isoxazolines 6 are selectively obtained (77–93% yield) by using iron and gold catalysts in the presence of a catalytic amount of pyridine (10 mol%).     

Copper(0) Nanoparticles in Click Chemistry: Synthesis of 3,5‐Disubstituted Isoxazoles

An efficient procedure for the synthesis of 3,5‐disubstituted isoxazoles via [3 + 2] cycloaddition reaction of in situ generated nitrile oxides with acetylenes employing readily preparable copper(0) nanoparticles is described. A variety of in situ generated nitrile oxide and acetylenic substrates were engaged in the study and found to undergo cyclization in short duration affording respective isoxazoles in excellent yield. Several amino acid‐derived isoxazoles were also prepared in high yield. Consistent activity of the recovered catalyst was found to be almost same up to three cycles.     

Mesogenic heterocyclic pyrazoles,isoxazoles and 1,3,4-oxadiazoles

Three new series of liquid crystals 1-3 derived from heterocyclic pyrazoles, isoxazoles and 1,3,4-oxadiazoles exhibiting smectic A or C phases were reported. Compound 1a exhibited monotropic smectic A phase, while the other two compounds 2-3a were not mesogenic. In contrast, all other compounds 1-3b bearing longer alkoxy chains exhibited smectic X and C phases, which were confirmed by powder XRD diffractometer. The clearing temperatures decreased in the order of compounds 1b > 2b > 3b, in contrast the temperature range of smectic C phases increased in the order of compounds 1b < 2b < 3b. The smectic phases in 1-3b were formed by a monomeric structure, confirmed and consistent with powder X-ray diffraction data. The formation of mesomorphic behavior might be probably attributed to their exocyclic angles and/or H-bonds. All derivatives showed good stabilities at temperature below T = 346 °C on TGA analysis.     

Capture of 3‐Amino‐4‐oxycyanofurazan and Characterization of Isoxazole Product

1,3‐Dipolar cycloaddition reaction between nitrile oxide and alkyne was used to capture 3‐amino‐4‐oxycyanofurazan (AOCF), which was considered as the key intermediate during the synthesis of 3,4‐bis(4‐aminofurazano‐3‐yl)furoxan (DATF) from 3‐amino‐4‐chloroximinofurazan. The isolated isoxazoles from the reaction afforded evidences for the existence of AOCF. The structures of the isoxazoles were characterized by IR, ¹H NMR, ¹³C NMR, MS, and elemental analysis. In addition, single crystal X‐ray diffraction of one isoxazole was obtained.     

Alkaline Protease Production from <Emphasis Type="Italic">Brevibacterium luteolum</Emphasis> (MTCC 5982) Under Solid-State Fermentation and Its Application for Sulfide-Free Unhairing of Cowhides

Enzyme-based unhairing in replacement of conventional lime sulfide system has been attempted as an alternative for tackling pollution. The exorbitant cost of enzyme and the need for stringent process control need to be addressed yet. This study developed a mechanism for regulated release of protease from cheaper agro-wastes, which overcomes the necessity for stringent process control along with total cost reduction. The maximum protease activity of 1193.77 U/g was obtained after 96 h of incubation with 15% inoculum of the actinomycete strain Brevibacterium luteolum (MTCC 5982) under solid-state fermentation (SSF). The medium after SSF was used for unhairing without the downstream processing to avoid the cost involved in enzyme extraction. This also helped in the regulated release of enzyme from bran to the process liquor for controlled unhairing and avoided the problem of grain-pitting. Unhairing process parameters were standardized as 20% enzyme offer, 40% Hide-Float ratio at 5 ± 1 rpm, and process pH of 9.0. The cost of production of 1000 kU of the protease was calculated as 0.44 USD. The techno-economic feasibility studies for setting up an SSF enzyme production plant showed a high return on investment of 15.58% with a payback period of 6.4 years.     

Enhanced electrochemical performance of LiFePO<Subscript>4</Subscript>/C nanocomposites due to in situ formation of Fe<Subscript>2</Subscript>P impurities

We have studied LiFePO₄/C nanocomposites prepared by sol-gel method using lauric acid as a surfactant and calcined at different temperatures between 600 and 900 °C. In addition to the major LiFePO₄ phase, all the samples show a varying amount of in situ Fe₂P impurity phase characterized by x-ray diffraction, magnetic measurements, and Mössbauer spectroscopy. The amount of Fe₂P impurity phase increases with increasing calcination temperature. Of all the samples studied, the LiFePO₄/C sample calcined at 700 °C which contains ～15 wt% Fe₂P shows the least charge transfer resistance and a better electrochemical performance with a discharge capacity of 136 mA h g^?1 at a rate of 1 C, 121 mA h g^?1 at 10 C (～70 % of the theoretical capacity of LiFePO₄), and excellent cycleability. Although further increase in the amount of Fe₂P reduces the overall capacity, frequency-dependent Warburg impedance analyses show that all samples calcined at temperatures ≥700 °C have an order of magnitude higher Li⁺ diffusion coefficient (～1.3?×?10^?13 cm² s^?1) compared to the one calcined at 600 °C, as well as the values reported in literature. This work suggests that controlling the reduction environment and the temperature during the synthesis process can be used to optimize the amount of conducting Fe₂P for obtaining the best capacity for the high power batteries.     

Synthesis of isomeric series of aryltetrahydrobenz-isoxazoles and arylcyclopentisoxazoles

Four series of potential PAF-antagonists in which the isoxazole nucleus is condensed with a polyhydrogenated five- or six-carbon ring were prepared. The synthesis of the compounds 3-aryl-4,5,6,7-tetrahydrobenz[c]isoxazoles 1 , 3-arylcyclopent[c]isoxazoles 2 , 3-aryl-4,5,6,7-tetrahydrobenz[d]isoxazoles 3 , and 3-arylcyclopent[d]isoxazoles 4 , required an extensive optimization and comparison of the methods available in the literature.     

Transition‐Metal‐Free Multicomponent Approach to Stereoenriched Cyclopentyl‐isoxazoles through C−C Bond Cleavage

An efficient multicomponent reaction for the synthesis of stereoenriched cyclopentyl‐isoxazoles from camphor‐derived α‐oximes, alkynes, and MeOH is reported. Our method involved a series of cascade transformations, including the in situ generation of an I^III catalyst, which catalyzed the addition of MeOH to a sterically hindered ketone. Oxidation of the oxime, and rearrangement of the α‐hydroxyiminium ion generated a nitrile oxide in situ, which, upon [3+2] cycloaddition reaction with an alkyne, delivered the regioselective product. This reaction was very selective for the syn‐oxime. This multicomponent approach was also extended to the synthesis of a new glycoconjugate, camphoric ester‐isoxazole C‐galactoside.     

Préparation d'isoxazoles trisubstitués par réduction chimique et électrochimique d'α-acyl β-nitrostilbènes

Nitration of α-acylstilbenes with dinitrogen tetroxide leads to corresponding Z-α-acyl-β-nitrostilbenes. By chemical or electochemical reduction of these compounds, trisubstituted isoxazoles were prepared in good yields.     

Synthesis and characterization of a new monophosphate (C<Subscript>6</Subscript>H<Subscript>16</Subscript>N<Subscript>2</Subscript>)(H<Subscript>2</Subscript>PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

Chemical preparation, crystal structure, and NMR spectroscopy of a new trans-2,5-dimethylpiperazinium monophosphate are given. This new compound crystallizes in the triclinic system, with the space group P-1 and the following parameters: a = 6.5033(3), b = 7.6942(4), c = 8.1473(5) Å, α = 114.997(3), β = 92.341(3), γ = 113.136(3), V = 329.14(3) ų, Z = 1, and D_x = 1.565 g cm^?3. The crystal structure has been determined and refined to R = 0.030 and R _w(F ²) = 0.032 using 1558 independent reflections. The structure can be described as infinite [H₂PO₄] _n ^n? chains with (C₆H₁₆N₂)²⁺ organic cations anchored between adjacent polyanions to form columns of anions and cations running along the b axis. This compound has also been investigated by IR, thermal, and solid-state, ¹³C and ³¹P MAS NMR spectroscopies and Ab initio calculations.     

A new calix[4]arene Schiff base sensor for Hg<Superscript>2+</Superscript> and Au<Superscript>3+</Superscript>

This article reports the selective sensing ability of a newly synthesized calix[4]arene Schiff base (C4TSB) derivative. C4TSB exhibited strong turn-off fluorescence affinity for Hg²⁺ and Au³⁺. The selective sensing ability of receptor was investigated in the presence of different co-existing competing ions. The limit of detection for Hg²⁺ and Au³⁺ was determined as 1.9 × 10^?5 and 1.0 × 10^?6 M, respectively. Receptor forms 1:1 stoichiometric complex with both metals and their binding constants were calculated as 7.9 × 10³ M^?1 for Hg²⁺ and 5.7 × 10³ M^?1 for Au³⁺. Complexes were also characterized through FT-IR spectroscopy.     

Rapid dissolution of spruce cellulose in H<Subscript>2</Subscript>SO<Subscript>4</Subscript> aqueous solution at low temperature

Dissolution of cellulose is the key challenge in its applications. It has been discovered that spruce cellulose with high molecular weight (4.10 × 10⁵ g mol^?1) can be dissolved in 64 wt% H₂SO₄ aqueous solution at low temperature within 2 min, and the cellulose concentration in solution can reach as high as 5 % (w/v). FT-IR spectra and XRD spectra proved that it is a direct solvent for cellulose rather than a derivative aqueous solution system. The cold H₂SO₄ aqueous solution broke the hydrogen bonds among cellulose molecules and the low temperature dramatically slowed down the hydrolysis, which led to the dissolution of cellulose. The resultant cellulose solution was relatively stable, and the molecular weight of cellulose only slightly decreased after storage at ?20 °C for 1 h. Due to the high molecular weight of cellulose, cellulose solution could form regenerated films with good mechanical properties and transparency at low concentration (2 % w/v). This work has not only provided the new evidence of cellulose dissolution which facilitated the development of cellulose solvent, but also suggested a convenient way to directly transfer cellulose with high molecular weight into materials without structure modifications.     

Facile synthesis of Fe@Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> core-shell nanowires as O<Subscript>2</Subscript> electrode for high-energy Li-O<Subscript>2</Subscript> batteries

Fe@Fe₂O₃ core-shell nanowires were synthesized via the reduction of Fe³⁺ ions by sodium borohydride in an aqueous solution with a subsequent heat treatment to form Fe₂O₃ shell and employed as a cathode catalyst for non aqueous Li-air batteries. The synthesized core-shell nanowires with an average diameter of 50–100 nm manifest superior catalytic activity for oxygen evolution reaction (OER) in Li-O₂ batteries with the charge voltage plateau reduced to ～3.8 V. An outstanding performance of cycling stability was also achieved with a cutoff specific capacity of 1000 milliampere hour per gram over 40 cycles at a current density of 100 mA g^?1. The excellent electrochemical properties of Fe@Fe₂O₃ as an O₂ electrode are ascribed to the high surface area of the nanowires’ structure and high electron conductivity. This study indicates that the resulting iron-containing nanostructures are promising catalyst in Li-O₂ batteries.     

Novel Method for Soluble‐Polymer‐Supported Synthesis of 3,4,5‐Trisubstituted Isoxazoles

A practical and efficient liquid‐phase synthesis of 3,4,5‐trisubstituted isoxazoles using poly(ethylene glycol) as supported is described. Soluble‐polymer‐supported nitrile oxide generated in situ reacted with chalcones to afford polymer‐supported isoxazolines, which were cleaved by sodium methoxide to generate 3,4,5‐trisubstituted isoxazoles instead of 3,4,5‐trisubstituted isoxazolines. This sequential process provided a novel method to synthesize 3,4,5‐trisubstituted isoxazoles.     

Production and Biotechnological Application of Extracellular Alkalophilic Lipase from Marine Macroalga-Associated <Emphasis Type="Italic">Shewanella algae</Emphasis> to Produce Enriched C<Subscript>20-22</Subscript><Emphasis Type="Italic">n</Emphasis>-3 Polyunsaturated Fatty Acid Concentrate

An extracellular alkalophilic lipase was partially purified from heterotrophic Shewanella algae (KX 272637) associated with marine macroalgae Padina gymnospora. The enzyme possessed a molecular mass of 20 kD, and was purified 60-fold with a specific activity of 36.33 U/mg. The enzyme exhibited V_max and K_m of 1000 mM/mg/min and 157 mM, respectively, with an optimum activity at 55 °C and pH 10.0. The catalytic activity of the enzyme was improved by Ca²⁺ and Mg²⁺ ions, and the enzyme showed a good tolerance towards organic solvents, such as methanol, isopropanol, and ethanol. The purified lipase hydrolyzed the refined liver oil from leafscale gulper shark Centrophorus squamosus, yielding a total C_20-22 n-3 PUFA concentration of 34.99% with EPA + DHA accounting the major share (34% TFA), after 3 h of hydrolysis. This study recognized the industrial applicability of the thermostable and alkalophilic lipase from marine macroalga-associated bacterium Shewanella algae to produce enriched C_20-22 n-3 polyunsaturated fatty acid concentrate.