gem-Dibromomethylarenes: a convenient substitute for noncommercial aldehydes in the knoevenagel-doebner reaction for the synthesis of alpha,beta-unsaturated carboxylic acids

A facile synthesis of alpha,beta-unsaturated carboxylic acids from gem-dibromomethylarenes is described. gem-Dibromomethylarenes are employed for the first time in the Knoevenagel-Doebner reaction as aldehyde equivalents for the efficient synthesis of alpha,beta-unsaturated carboxylic acids.     

UHPLC–Q-ToF-MS-guided enrichment and purification of triterpenoids from Centella asiatica (L.) extract with macroporous resin

The aim of the study is to standardize a simple and an effective extraction method for industrial preparation of Centella asiatica (L.) extract rich in triterpenoids. Macroporous resin purification process was adapted to enrich the triterpenes extracted from the herb. A sensitive analytical method with good resolution, linearity, and a shorter run time of 10?min was developed in ultra high-performance liquid chromatography–quadrupole-time-of-flight mass spectrometer for monitoring the triterpene (madecassoside, asiaticoside, madecassic acid, and asiatic acid) content at each stage of the extraction process. The standardized process could enrich the triterpene, madecassoside in the product up to a purity of 72.51% with overall recovery of the compound to 90.79%. A purified form of asiaticoside with a purity of 85% was obtained by dealcoholization and precipitation process exploiting the differential water solubility of the two major triterpenes. The binding and recovery of the aglycones (madecassic acid and asiatic acid) were observed to be poor, and hence the overall recovery of aglycones by this process was found to be very low. The purified triterpenoids were also confirmed by the ¹H NMR. Thus, the results suggest that the standardized process can be converted to industrial-scale preparation of high-value C. asiatica (L.) products rich in madecassoside or asiaticoside.     

The Halogen Bond: An Emerging Supramolecular Tool in the Design of Functional Mesomorphic Materials

Owing to their dynamic attributes, non-covalent supramolecular interactions have enabled a new paradigm in the design and fabrication of multifunctional material systems with programmable properties, performances, and reconfigurable traits. Recently, the “halogen bond” has become an enticing supramolecular synthetic tool that displays a plethora of promising and advantageous characteristics. Consequently, this versatile and dynamic non-covalent interaction has been extensively harnessed in various fields such as crystal engineering, self-assembly, materials science, polymer chemistry, biochemistry, medicinal chemistry and nanotechnology. In recent years, halogen bonding has emerged as a tunable supramolecular synthetic tool in the design of functional liquid-crystalline materials with adjustable phases and properties. In this Concept article, the use of halogen bond in the field of stimuli-responsive smart soft materials, that is, liquid crystals is discussed. The design, synthesis and characterization of molecular and macromolecular liquid crystalline materials are described and the modulation of their properties has been emphasized. The power of halogen bonding in offering a large variety of functional liquid crystalline materials from readily accessible mesomorphic and non-mesomorphic complementary building blocks is highlighted. The article concludes with a perspective on the challenges and opportunities in this emerging endeavor towards the realization of enabling and elegant dynamic functional materials.     

Fuzzy sets and the modelling of physician decision processes,part II: fuzzy diagnosis decision models

Our concern is with the development of a more accurate mathematical model of physician diagnosis decision processes. Using the complete information net of matrices outputed from Part I, the various diagnoses processes—medical hypothesis, initial preliminary diagnoses, other preliminary diagnosis and final diagnoses, are modelled as fuzzy matrices. A general fuzzy decision model which could be particularized to each of the foregoing cases is then developed. Our general technique is based on fuzzy clustering theory with the criterion function being a modified form of the minimum Minkowski metric.     

Acute toxicity and hepatotoxicokinetic studies of Tamarindus indica extract

Tamarindus indica is widely used as a food and beverage and in traditional medicine. The apparent lack of dose standardization in herbal medicine necessitates the evaluation of the lethality T. indica on Artemia salina nauplii and chicken embryos via in vitro and in vivo techniques. Furthermore, hepatotoxicokinetics of the crude extract and fractions on Wister rats was also assessed. At concentrations of 200, 20 and 2 μg/mL, crude extract and fractions showed brine shrimp death percentages ranging from 86.70% to 3.30% and the sub-fractions showed death percentage ranges of 46.70% to 3.30%. Calculated LD?? values ranged from 832 μg/mL to 5,019 μg/mL. Dosing Wister rats with 25% and 50% concentration of LD?? determined for crude extract and fractions on chicken embryos showed an elevation in the ALT and AST levels in the serum. Brine shrimps and chicken embryos showed a positive correlation, with R2 values of 0.541 and 0.588 (P ≤ 0.05) for fractions and subfractions, respectively, as media for the lethality assay. Dose standardization in folk herbal medicine is imperative as T. indica used as food and medicine has been shown to be toxic at high doses. Brine shrimp and chicken embryos may be comparably used as medium for toxicity assay.     

Highly efficient and chemoselective acetalization and thioacetalization of aldehydes catalyzed by propylphosphonic anhydride (®T3P) at room temperature

Propylphosphonic anhydride (®T3P), a low toxic peptide coupling agent, has been demonstrated to be an efficient catalyst for the chemoselective acetalization and thioacetalization of aldehydes in the presence of ketones. Cyclic and acyclic acetals of diverse aldehydes were obtained in good to excellent yields at room temperature in the presence of a catalytic amount of T3P.     

Depth of Initial Ideals of Normal Edge Rings

Let G be a finite graph on the vertex set [d] = {1,…, d} with the edges e ₁,…, e _n and K[t] = K[t ₁,…, t _d ] the polynomial ring in d variables over a field K. The edge ring of G is the semigroup ring K[G] which is generated by those monomials t ^e  = t _i t _j such that e = {i, j} is an edge of G. Let K[x] = K[x ₁,…, x _n ] be the polynomial ring in n variables over K, and define the surjective homomorphism π: K[x] → K[G] by setting π(x _i ) = t ^{e _i} for i = 1,…, n. The toric ideal I _G of G is the kernel of π. It will be proved that, given integers f and d with 6 ≤ f ≤ d, there exists a finite connected nonbipartite graph G on [d] together with a reverse lexicographic order <_rev on K[x] and a lexicographic order <_lex on K[x] such that (i) K[G] is normal with Krull-dim K[G] = d, (ii) depth K[x]/in_<rev (I _G ) = f and K[x]/in_<lex (I _G ) is Cohen–Macaulay, where in_<rev (I _G ) (resp., in_<lex (I _G )) is the initial ideal of I _G with respect to <_rev (resp., <_lex) and where depth K[x]/in_<rev (I _G ) is the depth of K[x]/in_<rev (I _G ).     

Magnetocurrent of charge-polarizable C60-diphenylaminofluorene monoadduct-derived magnetic nanocomposites

We demonstrated the strategy of a nanocomposite design by the incorporation of both a delocalized π-electrons system in a closely bound acceptor-donor analogue chromophore, based on charge-polarizable C(60)(>DPAF-C(9)) nanostructure 1, and spin-polarized d-electrons in the form of γ-FeO(x) nanoparticles. Facile intramolecular electron transfer from the DPAF-C(9) donor moiety to the C(60) acceptor cage of 1 upon activation to the excited state with a long lifetime of the charge-separated state forms a possible mechanism to integrate semiconducting and magnetic properties in a single system. We observed an appreciable magnetocurrent (MC) of C(60)(>DPAF-C(9))-encapsulated magnetic γ-FeO(x) nanoparticles in PMMA matrix upon applying a magnetic field from 0 to 300 mT at either 77 K (12% MC) or 300 K (4.5% MC). Interestingly, the detailed analysis of magnetocurrent curve profiles taken at 77 K allowed us to conclude that the measured magnetocurrent may be attributed to the contributions from magnetic field-dependent excited-state populations in semiconducting structure (density-based MC), magnetism from magnetic structure (mobility-based MC), and product of density and mobility-based MC components (π-d electronic coupling). At the higher temperature region up to 300 K, the semiconducting mechanism dominated the determining factor of measured magnetocurrent. This experimental observation indicated the feasibility of combining delocalized π electrons and spin-polarized d electrons through charge transfer to induce internally coupled dual mobility- and density-based MC through the modulation of spin polarization and excited states in semiconducting/magnetic hybrid materials.     

Reversible visible-light tuning of self-organized helical superstructures enabled by unprecedented light-driven axially chiral molecular switches

Two enantiomeric light-driven azo molecular switches with axial chirality and extended conjugation were found to exhibit unprecedented reversible photoisomerization in both organic-solvent and liquid-crystal media only upon visible-light irradiation. When doped in an achiral liquid crystal with a different concentration, the chiral switch was able either to immediately induce an optically tunable helical superstructure or to retain an achiral liquid-crystal phase whose helical superstructure was induced and tuned reversibly upon visible-light irradiation. Furthermore, reversible dynamic red, green, and blue reflection achieved only by using visible light was demonstrated.