Exploration of an arabinogalactan isolated from Odina wodier Roxb.: Physicochemical,compositional characterisations and functional attributes

Exudate gum polysaccharides have a diverse range of functionalities in food, cosmetics, textiles, biomedical, pharmaceutical and other industries for centuries. The potentiality of gum odina as tablet binder, coacervates (chitosan‐gum odina complex) for colon‐targeted drug delivery system and also as prebiotic with immunomodulating properties was reported earlier. Since no detail study of the physicochemical, functional properties of the gum has been reported, the present investigation deals with physicochemical, compositional and functional characterisations of purified gum odina (PGO) for adopting in food and pharmaceutical industry. PGO, an arabinogalactan, was obtained by ethanol precipitation from exudates (gum odina) of tropical deciduous plant Odina wodier Roxb. Colour profiling of PGO including L* (87.74 ± 0.42), a* (1.73 ± 0.65) and b* (7.79 ± 0.58) was determined. Physicochemical parameters revealed good flow ability and compressibility desired for an excipient. Concentration‐dependent surface tension was measured by du Noüy ring method. Rheological study showed pseudoplastic behaviour of PGO dispersion. Sugar analysis by gas liquid chromatography indicated presence of arabinogalactan in PGO. Size exclusion chromatography of PGO revealed two high‐molecular‐weight components PGO‐I (95%, Arabinose:Galactose :: 1:1.6) and PGO‐II (5%, Arabinose:Galactose :: 1:4). Further characterisations of PGO by means of CHNS, FTIR, differential scanning calorimetry, X‐ray diffraction, transmission electron microscopy, scanning electron microscopy and energy‐dispersive X‐ray diffraction, conductivity, pH, zeta potential analysis and antioxidant activity indicated typical polysaccharide characteristics. Collectively, this work established the fundamental properties of PGO and the results presented here will facilitate the applications of PGO as sustainable food additive, pharmaceutical excipient for commercial adoption.     

Drying of alkoxide gels—Observation of an alternate phenomenology

The process of drying of a porous material as per the current phenomenological theory can be divided into two stages. At first the body shrinks by an amount equal to the volume of liquid that evaporates, and the liquid-vapor interface remains at the exterior surface of the body. The second stage begins when the body becomes too stiff to shrink and the liquid recedes into the interior, leaving air filled pores near the surface. We shall refer to this phenomenology as the drying front model. In our investigation of drying of alkoxide silica gels of less than 50 Angstroms pore radius, we have observed a different drying pattern, in which even after the gel body stops shrinking, drying continues to occur by evaporation on the exterior surface of the gel body, causing spontaneous nucleation of partially or fully dried opaque clusters, randomly distributed in the interior parts of the gel. These clusters than increase in number and size till they coalesce to form an opaque body. Upon further drying, the gel returns to its transparent form. We postulate that this is possible only if the rate of fluid flow in the pores by diffusion is faster than that by Darcy's flow, as well as the evaporation rate at the surface of the gel body. We shall refer to this as the cluster drying model. We shall present results of pin-hole drying experiments on cylindrical alkoxide gels showing that for identical gels the evaporation rate can be increased to change the phenomenology from cluster drying to one that exhibits both phenomenology simultaneously and finally to that of the drying front phenomenology. We shall also show the effect of gel pore size distribution on the phenomenology of drying under identical drying conditions. Finally, we will present evidence that for successful drying of large cylindrical alkoxide gels, drying conditions favoring cluster drying phenomenology is desirable.     

A stereocontrolled total synthesis of methyl (±)-O-methylpodocarpate

A stereocontrolled total synthesis of methyl (±)-O-methyl podocarpate (4) has been successfully accomplished using the trans-fused diester 21 as a key intermediate. Intramolecular Michael reaction of the enone-diester 18 afforded the cis-fused keto-diester 19 in high yield which was stereoselectively converted into 21 via the enone 20.     

Biomolecular hybrid of a conducting polymer with DNA: morphology, structure, and doping behavior

A poly(o-methoxyaniline) (POMA)/DNA [weight fraction of DNA (W(DNA)) = 0.45] hybrid was prepared by mixing their solutions in sterilized double distilled water. The solution turned green upon aging for a longer time, and the doping of POMA by DNA was complete after about 15 d of aging. The doping was confirmed from the UV-vis spectra where the 599 nm peak of POMA(EB) disappeared and a new peak for a pi to localized polaron band-transition appeared. With increasing aging time the new peak gradually shifted from 674 nm at 3 h to 820 nm at 15 d of mixing and thereafter it remained constant. The absence of a free carrier tail in the UV-vis spectra indicated a coiled structure of POMA in the complex. Circular dichroism spectra of the hybrid solution indicated that the DNA conformation (double helical structure) remained unchanged in the hybrid. The SEM micrograph of the freeze-dried hybrid showed a needle-like morphology of the DNA dispersed in a polymer matrix and it was completely different from the fibrillar network morphology of pure DNA in the solid state. The TEM micrograph indicated a homogeneous dispersion of DNA fibrils in the POMA matrix. The melting temperature of the POMA-DNA hybrid showed an increase compared to that of pure DNA by 5 degrees C, probably caused by an electrostatic interaction between the DNA anion and the POMA radical cation generated in the doping process. WAXS investigations revealed that the DNA crystal structure remained unchanged in the hybrid whereas the POMA crystal structure might be lost. An FT-IR study suggested that interaction occurred between the phosphoric acid group of DNA and a nitrogen atom of POMA through proton transfer from the OH group of the former. A schematic model of the POMA-DNA complex randomly anchoring POMA chains with the DNA molecule was proposed. The dc conductivity of the POMA-DNA complex was found to be ca. 10(-7) S . cm(-1). Hence, this work describes a procedure for making a DNA-conducting polymer hybrid without changing the conformation and structure of DNA. [Diagram: see text]     

Effect of varying bases on preferential crystallization of C-methylresorcin[4]arene and calix[6]arene

Preferential crystallization from a mixture of C-methylresorcin[4]arene (RsC1) and calix[6]arene (Calix6) in the presence of different bases has been investigated. In the presence of pyridine, a boat conformer of RsC1 crystallizes, whereas in the presence of triethylamine, Calix6 crystallizes in a symmetrically distorted conformation. The packing arrangements of the macrocycles show discrete solvent pockets for calixarenes and channels for resorcinarenes.     

Reduction of Sulfur Dioxide to Sulfur Monoxide by Ferrous Porphyrin**

The reduction of SO₂ to fixed forms of sulfur can address the growing concerns regarding its detrimental effect on health and the environment as well as enable its valorization into valuable chemicals. The naturally occurring heme enzyme sulfite reductase (SiR) is known to reduce SO₂ to H₂S and is an integral part of the global sulfur cycle. However, its action has not yet been mimicked in artificial systems outside of the protein matrix even after several decades of structural elucidation of the enzyme. While the coordination of SO₂ to transition metals is documented, its reduction using molecular catalysts has remained elusive. Herein reduction of SO₂ by iron(II) tetraphenylporphyrin is demonstrated. A combination of spectroscopic data backed up by theoretical calculations indicate that Fe^IITPP reduces SO₂ by 2e⁻/2H⁺ to form an intermediate [Fe^III−SO]⁺ species, also proposed for SiR, which releases SO. The SO obtained from the chemical reduction of SO₂ could be evidenced in the form of a cheletropic adduct of butadiene resulting in an organic sulfoxide.     

Study of a periodically forced magnetohydrodynamic system using Floquet analysis and nonlinear Galerkin modelling

Nonlinear Dynamics - We present a detailed study of Rayleigh–Bénard magnetoconvection with periodic gravity modulation and uniform vertical magnetic field. Linear stability analysis is...     

Activation of Protic,Hydridic and Apolar E−H Bonds by a Boryl-Substituted GeII Cation

The synthesis of a boryl-substituted germanium(II) cation, [Ge{B(NDippCH)₂}(IPrMe)]⁺, (Dipp=2,6-diisopropylphenyl) featuring a supporting N-heterocyclic carbene (NHC) donor, has been explored through chloride abstraction from the corresponding (boryl)(NHC)GeCl precursor. Crystallographic studies in the solid state and UV/Vis spectra in fluorobenzene solution show that this species dimerizes under such conditions to give [(IPrMe){(HCNDipp)₂B}Ge=Ge{B(NDippCH)₂}(IPrMe)]²⁺ (IPrMe = 1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene), which can be viewed as an imidazolium-functionalized digermene. The dimer is cleaved in the presence of donor solvents such as [D₈]thf or [D₅]pyridine, to give monomeric adducts of the type [Ge{B(NDippCH)₂}(IPrMe)(L)]⁺. In the case of the thf adduct, the additional donor is shown to be sufficiently labile that it can act as a convenient in situ source of the monomeric complex [Ge{B(NDippCH)₂}(IPrMe)]⁺ for oxidative bond-activation chemistry. Thus, [Ge{B(NDippCH)₂}(IPrMe)(thf)]⁺ reacts with silanes and dihydrogen, leading to the formation of Ge^IV products, whereas the cleavage of the N−H bond in ammonia ultimately yields products containing C−H and B−N bonds. The facile reactivity observed in E−H bond activation is in line with the very small calculated HOMO–LUMO gap (132 kJ mol⁻¹).