Efficient Chemical Protein Synthesis using Fmoc-Masked N-Terminal Cysteine in Peptide Thioester Segments

We report an operationally simple method to facilitate chemical protein synthesis by fully convergent and one-pot native chemical ligations utilizing the fluorenylmethyloxycarbonyl (Fmoc) moiety as an N-masking group of the N-terminal cysteine of the middle peptide thioester segment(s). The Fmoc group is stable to the harsh oxidative conditions frequently used to generate peptide thioesters from peptide hydrazide or o-aminoanilide. The ready availability of Fmoc-Cys(Trt)-OH, which is routinely used in Fmoc solid-phase peptide synthesis, where the Fmoc group is pre-installed on cysteine residue, minimizes additional steps required for the temporary protection of the N-terminal cysteinyl peptides. The Fmoc group is readily removed after ligation by short exposure (<7 min) to 20 % piperidine at pH 11 in aqueous conditions at room temperature. Subsequent native chemical ligation reactions can be performed in presence of piperidine in the same solution at pH 7.     

Computation-led design of pollutant gas sensors with bare and carbon nanotube supported rhodium alloys

Quantum chemical study has been performed on finite-sized bi-metallic Rh3M alloys, M = Ag, Ir, Pd, Pt, Au, derived from magic cluster, Rh4. Bond length of C–O and N–O are noticed to be elongated in the presence of rhodium alloy clusters. CO2 and NO2 gases are found to be highly adsorbed on Rh3M clusters, which is confirmed by stretching frequency of C–O and N–O. DFT evaluated dipole moment and electronic charge redistribution suggests the sensing capability of CO2 and NO2 gases by Rh3M clusters which is further confirmed by the calculated HOMO–LUMO gap. Mixed rhodium alloy clusters supported on single-wall carbon nanotube (SWCNT) exhibits much higher ability to sense CO2 and NO2. On the other hand, SWCNT@Rh3M shows higher catalytic activity for the activation of CO2 and NO2 in comparison to bare Rh3M because of the higher electronic charge redistribution in the case of SWCNT@Rh3M. In case of SWCNT-supported gas adsorbed clusters, p electrons play a major role in bonding.     

Highly Mesoporous Metal‐Organic Frameworks as Synergistic Multimodal Catalytic Platforms for Divergent Cascade Reactions

Rational engineering and assimilation of diverse chemo‐ and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal‐organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo‐ and biocatalytic components. This was shown by one‐pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]‐catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields.     

Quality Related Safety Evaluation of a South African Traditional Formulation (PHELA®) as Novel Anti-Biofilm Candidate

A South African traditional formulation, PHELA^®, is consumed by the traditional people for severe chest problems with coughing, diarrhea, oral ulcers etc. The present study focused on establishing the anti-infective properties of a safe and standardized poly-herbal formulation through a series of criteria and specifications.     

Formation of Gallium-induced nanostructures on single crystal HOPG surface

The room temperature growth of gallium atoms on the highly oriented pyrolytic graphite (HOPG) surface has been performed. The gallium atoms were deposited by thermal evaporation method in an ultra high vacuum system at a base pressure 5 × 10⁻¹⁰ torr. The X-ray photo electron spectroscopy (XPS) studies had been performed to confirm the presence of gallium atoms on HOPG surface. Scanning tunneling spectroscopy (STM) technique was employed to study the surface morphology of the clean HOPG surface and gallium covered HOPG surfaces which recognize the formation of gallium induced nanostructures. The deconvoluted XPS core level spectra of C (1s) and Ga (3d) demonstrate the possible interaction between substrate and the adsorbate atoms. The STM analysis revealed that the gallium deposition on HOPG led to significant change in the surface morphology. It was observed that the Ga atoms adsorbed as layer structure on HOPG surface for low coverage while quasi one-dimensional chain like nanostructure (1 ± 0.2 nm) has been formed for higher Ga coverage. The nanostructured surfaces induced by Ga deposition are found to be stable and could be used as a template for the growth of metallic nanostructures.     

Exploring a hidden fermionic dark sector

In this paper, we present a generalized unified method for finding multiwave solutions of the time-fractional (2+1)-dimensional Nizhnik–Novikov–Veselov equations. The fractional derivatives are described in the modified Riemann–Liouville sense. The fractional complex transform has been suggested to convert fractional-order differential equations with modified Riemann–Liouville derivatives into integer-order differential equations, and the reduced equations can be solved by symbolic computation. Multiauxiliary equations have been introduced in this method to obtain not only multisoliton solutions but also multiperiodic or multielliptic solutions. It is shown that the considered method is very effective and convenient for solving wide classes of nonlinear partial differential equations of fractional order.     

Vortex dynamics of a trapezoidal bluff body placed inside a circular pipe

The influence of Reynolds number and blockage ratio on the vortex dynamics of a trapezoidal bluff body placed inside a circular pipe is studied experimentally and numerically. Low aspect ratio, high blockage ratio, curved end conditions (junction of pipe and bluff body), axisymmetric upstream flow with shear and turbulence are some of the intrinsic features of this class of bluff body flows which have been scarcely addressed in the literature. A large range (200:200,000) of Reynolds number (Re_D) is covered in this study, encompassing all the three pipe flow regimes (laminar, transition and turbulent). Four different flow regimes are defined based on the distinct features of Strouhal number (St)–Re_D relation: steady, laminar irregular, transition and turbulent. The wake in the steady regime is stationary with no oscillations in the shear layer. The laminar regime is termed as irregular owing to irregular vortex shedding. The vortex shedding in this regime is observed to be symmetric. The emergence of separation bubble downstream of the bluff body on either side is another interesting feature of this regime, which is further observed to be symmetric. Two pairs of mean streamwise vortices are noticed in the near-wake regime, which are termed as reverse dipole-type wake topology. Beyond the irregular laminar regime, the Strouhal number falls gradually and vortex shedding becomes more periodic. This regime is named transition and occurs close to the Reynolds number at which transition to turbulence takes place in a fully developed pipe. The turbulent regime is characterised by a nearly constant Strouhal number. Typical Karman-type vortex shedding is noticed in this regime. The convection velocity, wake width formation length and irrecoverable pressure loss are quantified to highlight the influence of blockage ratio. These results will be useful to develop basic understanding of vortex dynamics of confined bluff body flow for several practical applications.     

Diffusion of water in molecular magnet Cu(0.75)Mn(0.75)[Fe(CN)6]·7H2O

Here we report the dynamical behaviour of water in Prussian blue analogue (PBA) Cu(0.75)Mn(0.75)[Fe(CN)(6)]·7H(2)O molecular magnet in the temperature range 260-360 K as studied using the quasielastic neutron scattering technique. While significant quasielastic broadening is observed in the hydrated sample, no broadening was observed in the dehydrated one. Data analysis showed that the observed quasielastic broadening in Cu(0.75)Mn(0.75)[Fe(CN)(6)]·7H(2)O corresponds to the dynamics of the non-coordinated water molecules at the 32f site and the coordinated water molecules at the 24e site, existing in the cavities created by the absence of Fe(CN)(6) units. The non-coordinated water molecules at 8c interstitial sites do not contribute to the broadening, suggesting that they are immobile at least within the time window of the spectrometer used. Behaviour of the elastic incoherent structure factor is consistent with the model where the water molecules undergo translational diffusion localized within the cavity of 5.1 ?. While all the non-coordinated water molecules at the 32f site are dynamic over the entire range of temperatures, the coordinated ones at the 24e site become progressively dynamic with temperature. The water molecules were found to undergo hindered (~1.16 × 10(-5) cm(2) s(-1) at 300 K) diffusion compared to bulk water and the diffusivity followed Arrhenius behaviour within the measured temperature range with an activation energy of 1.26 kcal mol(-1).     

Performance analysis of an integrated scheme in optical burst switching high-speed networks

A new integrated scheme based on resource-reservation and adaptive network flow routing to alleviate contention in optical burst switching networks is proposed. The objective of the proposed scheme is to reduce the overall burst loss in the network and at the same time to avoid the packet out-of-sequence arrival problem. Simulations are carried out to assess the feasibility of the proposed scheme. Its performance is compared with that of contention resolution schemes based on conventional routing. Through extensive simulations, it is shown that the proposed scheme not only provides significantly better burst loss performance than the basic equal proportion and hop-length based traffic routing algorithms, but also is void of any packet re-orderings.     

Epidemiological impact of waning immunization on a vaccinated population

This is an epidemiological SIRV model based study that is designed to analyze the impact of vaccination in containing infection spread, in a 4-tiered population compartment comprised of susceptible, infected, recovered and vaccinated agents. While many models assume a lifelong protection through vaccination, we focus on the impact of waning immunization due to conversion of vaccinated and recovered agents back to susceptible ones. Two asymptotic states exist, the “disease-free equilibrium” and the “endemic equilibrium” and we express the transitions between these states as function of the vaccination and conversion rates and using the basic reproduction number. We find that the vaccination of newborns and adults have different consequences on controlling an epidemic. Also, a decaying disease protection within the recovered sub-population is not sufficient to trigger an epidemic at the linear level. We perform simulations for a parameter set mimicking a disease with waning immunization like pertussis. For a diffusively coupled population, a transition to the endemic state can proceed via the propagation of a traveling infection wave, described successfully within a Fisher-Kolmogorov framework.