The first stereoselective total synthesis of the Z-isomer of cytospolide E

A convergent and highly stereoselective total synthesis of the Z-isomer of cytospolide E has been achieved via Evan’s aldol reaction, Sharpless kinetic resolution and RCM cyclisation.     

Extraction and Characterization of Cellulose Nanowhiskers from Balsa Wood

Summary: In this study cellulose nanowhiskers were obtained from balsa wood. For this purpose, fibers of balsa wood were exposed to hydrolysis reactions for lignin and hemicellulose digestion and acquisition of nano-scale cellulose. Transmission electron microscopy (TEM) results demonstrated that the obtained cellulose nanocrystals had average length and thickness of 176 (±68 nm) and 7.5 (±2.9 nm), respectively. Infrared spectroscopy (FTIR) and wide angle x-ray diffraction (WAXD) showed that the process for extracting the nanowhiskers digested nearly all the lignin and hemicellulose from the balsa fiber and still preserved the aspect ratio and crystallinity satisfactory enough for future application as nanofillers in polymer nanocomposites. The thermogravimetric analysis (TGA) showed that the onset temperature of thermal degradation of the cellulose nanocrystals (226 °C) was higher than the onset temperature of the balsa fiber (215 °C), allowing its use in molding processes with polymers melts.     

Mechanical loads on a generalized thermoelastic medium with diffusion

The disturbance caused by the application of continuous mechanical source on the free surface of a homogeneous, isotropic elastic half space in the context of the theory of generalized thermoelastic diffusion with one relaxation time parameter is investigated in the Laplace-Fourier transform domain for a two dimensional problem using eigenvalue approach. The integral transforms are inverted by using a numerical technique. The expressions for displacement components, stresses, temperature field, concentration and chemical potential so obtained in the physical domain are computed numerically and illustrated graphically at different times, for copper like material. As a special case the effect of diffusion on various expressions has also been obtained analytically and depicted graphically.     

Micellar liquid chromatographic green enantioseparation of racemic amino alcohols and determination of elution order

A micellar liquid chromatographic method was developed for the green enantioseparation of racemic amino alcohols using an aqueous solution of the mixed surfactants as an alternative for organic solvents. In this study, the derivatives of the amino alcohols were synthesized using highly reactive chiral esters of (S)-levofloxacin (Lfx) under microwave conditions, and an aqueous solution of the surfactants (Brij-35 and SDS) was used for the enantioseparation of the synthesized diastereomeric derivatives (DDs) of amino alcohols using reversed-phase HPLC. The activated ester of Lfx was synthesized by reacting with N-hydroxybenzotriazole and characterized using UV, IR, ¹H NMR, high-resolution mass spectrometry, and elemental analysis. The DDs of racemic amino alcohols were separated on a C₁₈ column using micellar LC. Chromatographic conditions were optimized by varying the concentration of the surfactants in aqueous solution and by varying the concentration and pH of the buffer. The green assessment score was calculated for the developed method (score: 82, an excellent green method). In addition, the density functional theory calculations were performed to develop the lowest energy-optimized structures of DDs. The method was validated according to the International Conference of Harmonization guidelines, and the retention factor (k), selectivity factor (α), resolution factor (R_S), limit of detection (0.198 ng mL⁻¹ or 0.291 pM mL⁻¹), and limit of quantification (0.594 ng mL⁻¹ or 0.873 pM mL⁻¹) were calculated.     

The effect of the finite size of ions and Debye layer overspill on the screened Coulomb interactions between charged flat plates

Screened repulsion between uniformly charged plates with an intervening electrolyte is analyzed for strongly overlapped electrical double layers (EDL), accounting for the steric effect of ions and their expulsion from EDL edges into the surrounding solution. As a generalization of a study by Philipse et al. which does not account for these effects, an analytical expression is derived for the repulsion pressure in the limit of infinitely long plates with a zero-field assumption, which agrees closely with the corresponding numerical solution at low inter-plate separations. Our results show an augmented repulsive pressure for finite-sized ions at strong EDL overlaps. For plates with a finite lateral size, we demonstrate a further extended domain of low inter-plate gaps where the repulsion pressure increases with ion size due to a strong interplay between the steric interaction of ions and the EDL overspill phenomenon, considered earlier in a study by Ghosal & Sherwood limited to the linear Debye-Hückel regime (which cannot account for the steric effect of ions). This investigation on a simple model should enhance our understanding of the interaction between charged particles in electrophoresis, nanoscale self-assembly, active particles, and various other electrokinetic systems.     

Cancer-Cell-Specific Drug Delivery by a Tumor-Homing CPP-Gossypol Conjugate Employing a Tracelessly Cleavable Linker

Tumor-targeted drug delivery is highly important for improving chemotherapy, as it reduces the dose of cytotoxic agents and minimizes the death of healthy tissues. Towards this goal, a conjugate was synthesized of gossypol and a MCF-7 cancer cell specific CPP (cell penetrating peptide), thus providing a selective drug delivery system. Utilizing the aldehyde moiety of gossypol, the tumor homing CPP RLYMRYYSPTTRRYG was attached through a semi-labile imine linker, which was cleaved in a traceless fashion under aqueous conditions and had a half-life of approximately 10 hours. The conjugate killed MCF-7 cells to a significantly greater extent than HeLa cells or healthy fibroblasts.     

Interaction due to mechanical sources in micropolar elastic medium with voids

The present paper is concerned with the dynamic problem of a homogeneous isotropic half-space with voids subjected to a set of normal point sources. The integral transforms have been inverted by using a numerical technique to obtain the normal force stress, normal displacement, tangential couple stress and volume fraction field in the physical domain for the two different sources. The expressions of these quantities have been given and illustrated graphically to depict the effect of micropolarity and voids.     

Dose Dependencies and Biocompatibility of Renal Clearable Gold Nanoparticles: From Mice to Non‐human Primates

While dose dependencies in pharmacokinetics and clearance are often observed in clinically used small molecules, very few studies have been dedicated to the understandings of potential dose‐dependent in vivo transport of nanomedicines. Here we report that the pharmacokinetics and clearance of renal clearable gold nanoparticles (GS‐AuNPs) are strongly dose‐dependent once injection doses are above 15 mg kg^?1: high dose expedited the renal excretion and shortened the blood retention. As a result, the no‐observed‐adverse‐effect‐level (NOAEL) of GS‐AuNPs was >1000 mg kg^?1 in CD‐1 mice. The efficient renal clearance and high compatibility can be translated to the non‐human primates: no adverse effects were observed within 90 days after intravenous injection of 250 mg kg^?1 GS‐AuNPs. These fundamental understandings of dose effect on the in vivo transport of ultrasmall AuNPs open up a pathway to maximize their biomedical potentials and minimize their toxicity in the future clinical translation.     

Polymerization of styrene with the VOCL3–AlEt2Br catalyst system

The rate of polymerization with the VOCl₃–AlEt₂Br catalyst system at 30°C. in n-hexane reached a maximum at an Al/V molar ratio of 1.5. At this ratio, the rate of polymerization was first-order with respect to catalyst and second-order with respect to monomer concentrations. The apparent activation energy calculated was 6.4 kcal./mole. Diethylzine was found to act as a chain transfer agent. However, the molecular weights of polymers obtained were low. The possibility of bromide-containing catalyst sites acting in the termination reaction has been investigated. The average valence of vanadium is discussed in relation to molecular weights.