MANET Routing with Provably Low Complexity Through Constant Density Clustering and Route Request Broadcast

As mobile ad hoc networks (MANETs) are emerging as important components in critical and large-scale applications, it is crucial to develop MANET routing mechanisms with provably low complexity. In this paper, we give a tutorial overview of the efficient use of elementary node clustering and route request broadcast mechanisms for low-complexity MANET routing. We explain these mechanisms with illustrative examples and discuss their theoretical performance characteristics. We demonstrate that node clustering with constant density and route request broadcasting with a doubling radius technique over the network of cluster leaders can be employed for MANET routing with theoretically proven low complexity. Moreover, we contrast these efficient elementary clustering and route request broadcast mechanisms with clustering and route information accumulation mechanisms in the widely studied AODV and DSR routing protocols and discuss the implications of these various mechanisms for scalable MANET routing.     

Magnetic dilution in the geometrically frustrated SrCr(9p)Ga(12-9p)O19 and the role of local dynamics: A muon spin relaxation study

We investigate the spin dynamics of SrCr(9p)Ga(12-9p)O19 for p below and above the percolation threshold p(c) using muon spin relaxation. Our major findings are as follows: (i) At T-->0 the relaxation rate is T independent and approximately p(3), (ii) the slowing down of spin fluctuation is activated with an energy U, which is also a linear function of p(3) and lim U as p-->0 = 8 K; this energy scale could stem only from a single ion anisotropy, and (iii) the p dependence of the dynamical properties is identical below and above p(c), indicating that they are controlled by local excitation.     

Synthesis and biochemical characterisation of fluorinated analogues of pepstatin A and grassystatin A

Pepstatin A and grassystatin A are natural, statine-containing peptides that act as inhibitors of aspartic protease enzymes. In this work, stereoselective fluorination is investigated as a strategy for enhancing the pharmacodynamic and pharmacokinetic properties of these lead compounds. Fluorination is found to modestly affect the protease inhibitory potency, leading to the identification of two highly active new inhibitors of the cancer-associated protease, cathepsin D. However, no dramatic changes are observed in terms of target selectivity, lipophilicity, membrane permeability or metabolic stability.     

Strong,Self‐Healable,and Recyclable Visible‐Light‐Responsive Hydrogel Actuators

The most pressing challenges for light‐driven hydrogel actuators include reliance on UV light, slow response, poor mechanical properties, and limited functionalities. Now, a supramolecular design strategy is used to address these issues. Key is the use of a benzylimine‐functionalized anthracene group, which red‐shifts the absorption into the visible region and also stabilizes the supramolecular network through π–π interactions. Acid–ether hydrogen bonds are incorporated for energy dissipation under mechanical deformation and maintaining hydrophilicity of the network. This double‐crosslinked supramolecular hydrogel developed via a simple synthesis exhibits a unique combination of high strength, rapid self‐healing, and fast visible‐light‐driven shape morphing both in the wet and dry state. As all of the interactions are dynamic, the design enables the structures to be recycled and reprogrammed into different 3D objects.     

Modular Chemoenzymatic Synthesis of Terpenes and their Analogues

Non‐natural terpenoids offer potential as pharmaceuticals and agrochemicals. However, their chemical syntheses are often long, complex, and not easily amenable to large‐scale production. Herein, we report a modular chemoenzymatic approach to synthesize terpene analogues from diphosphorylated precursors produced in quantitative yields. Through the addition of prenyl transferases, farnesyl diphosphates, (2E,6E)‐FDP and (2Z,6Z)‐FDP, were isolated in greater than 80 % yields. The synthesis of 14,15‐dimethyl‐FDP, 12‐methyl‐FDP, 12‐hydroxy‐FDP, homo‐FDP, and 15‐methyl‐FDP was also achieved. These modified diphosphates were used with terpene synthases to produce the unnatural sesquiterpenoid semiochemicals (S)‐14,15‐dimethylgermacrene D and (S)‐12‐methylgermacrene D as well as dihydroartemisinic aldehyde. This approach is applicable to the synthesis of many non‐natural terpenoids, offering a scalable route free from repeated chain extensions and capricious chemical phosphorylation reactions.     

Enantioselective Syntheses of Strychnos and Chelidonium Alkaloids through Regio‐ and Stereocontrolled Cooperative Catalysis

We describe enantioselective syntheses of strychnos and chelidonium alkaloids. In the first case, indole acetic acid esters were established as excellent partner nucleophiles for enantioselective cooperative isothiourea/Pd catalyzed α‐alkylation. This provides products containing indole‐bearing stereocenters in high yield and with excellent levels of enantioinduction in a manner that is notably independent of the N‐substituent. This led to concise syntheses of (?)‐akuammicine and (?)‐strychnine. In the second case, the poor performance of ortho‐substituted cinnamyl electrophiles in the enantioselective cooperative isothiourea/Ir catalyzed α‐alkylation was overcome by appropriate substituent choice, leading to enantioselective syntheses of (+)‐chelidonine, (+)‐norchelidonine, and (+)‐chelamine.     

A nonstationary model of newborn EEG

The detection of seizure in the newborn is a critical aspect of neurological research. Current automatic detection techniques are difficult to assess due to the problems associated with acquiring and labelling newborn electroencephalogram (EEG) data. A realistic model for newborn EEG would allow confident development, assessment and comparison of these detection techniques. This paper presents a model for newborn EEG that accounts for its self-similar and nonstationary nature. The model consists of background and seizure submodels. The newborn EEG background model is based on the short-time power spectrum with a time-varying power law. The relationship between the fractal dimension and the power law of a power spectrum is utilized for accurate estimation of the short-time power law exponent. The newborn EEG seizure model is based on a well-known time-frequency signal model. This model addresses all significant time-frequency characteristics of newborn EEG seizure which include; multiple components or harmonics, piecewise linear instantaneous frequency laws and harmonic amplitude modulation. Estimates of the parameters of both models are shown to be random and are modelled using the data from a total of 500 background epochs and 204 seizure epochs. The newborn EEG background and seizure models are validated against real newborn EEG data using the correlation coefficient. The results show that the output of the proposed models have a higher correlation with real newborn EEG than currently accepted models (a 10% and 38% improvement for background and seizure models, respectively).     

Fingerprint vibrational spectra of protonated methyl esters of amino acids in the gas phase

Infrared spectra of the protonated monomers of glycine, alanine, valine, and leucine methyl esters are presented. These protonated species are generated in the gas phase via matrix assisted laser desorption ionization (MALDI) within the cell of a Fourier transform ion cyclotron resonance spectrometer (FTICR) where they are subsequently mass selected as the only species trapped in the FTICR cell. Alternatively, they have also been generated by electrospray ionization and transferred to a Paul ion-trap mass spectrometer where they are similarly isolated. In both cases IR spectra are then derived from the frequency dependence of the infrared multiple photon dissociation (IRMPD) in the mid-infrared region (1000-2200 cm(-1)), using the free electron laser facility Centre de Laser Infrarouge d'Orsay (CLIO). IR bands are assigned by comparison with the calculated vibrational spectra of the lowest energy isomers using density functional theory (DFT) calculations. There is in general good agreement between experimental IRMPD spectra and calculated IR absorption spectra for the lowest energy conformer which provides evidence for conformational preferences. The two different approaches to ion generation and trapping yield IRMPD spectra that are in excellent agreement.     

Enantioselective chemisorption of propylene oxide on a 2-butanol modified Pd(111) surface: the role of hydrogen-bonding interactions

The enantioselective chemisorption of R- and S-propylene oxide has been measured either on clean Pd(111) that has been exposed to S-2-butanol at various temperatures to vary the proportion of 2-butanol and 2-butoxide species or by adsorbing S-2-butanol on oxygen-covered Pd(111) to form exclusively 2-butoxide. The results reveal that enantioselective chemisorption is only found when 2-butanol is present on the surface. This is ascribed to enantiospecific hydrogen-bonding interactions between 2-butanol and propylene oxide. Measurements of the variation in enantiospecificity with 2-butanol exposure suggest that propylene oxide can interact either with a single adsorbed 2-butanol molecule or, at higher coverages, with two adsorbed 2-butanol species to form enantioselective sites.     

Functional and mechanistic analyses of biomimetic aminoacyl transfer reactions in de novo designed coiled coil peptides via rational active site engineering

Ribosomes and nonribosomal peptide synthetases (NRPSs) carry out instructed peptide synthesis through a series of directed intermodular aminoacyl transfer reactions. We recently reported the design of coiled-coil assemblies that could functionally mimic the elementary aminoacyl loading and intermodular aminoacyl transfer steps of NRPSs. These peptides were designed initially to accelerate aminoacyl transfer mainly through catalysis by approximation by closely juxtaposing four active site moieties, two each from adjacent noncovalently associated helical modules. In our designs peptide self-assembly positions a cysteine residue that is used to covalently capture substrates from solution via transthiolesterification (substrate loading step to generate the aminoacyl donor site) adjacent to an aminoacyl acceptor site provided by a covalently tethered amino acid or modeled by the epsilon-amine of an active site lysine. However, through systematic functional analyses of 48 rationally designed peptide sequences, we have now determined that the substrate loading and intermodular aminoacyl transfer steps can be significantly influenced (up to approximately 103-fold) by engineering changes in the active site microenvironment through amino acid substitutions and variations in the inter-residue distances and geometry. Mechanistic studies based on 15N NMR and kinetic analysis further indicate that certain active site constellations furnish an unexpectedly large pK(a) depression (1.5 pH units) of the aminoacyl-acceptor moiety, helping to explain the observed high rates of aminoacyl transfer in those constructs. Taken together, our studies demonstrate the feasibility of engineering efficient de novo peptide sequences possessing active sites and functions reminiscent of those in natural enzymes.