Cover Picture: A Single Polymer Nanowire Photodetector (Adv. Mater. 18/2006)

Redmond and co‐workers report on p. 2379 the successful application of solution‐assisted template wetting to the high‐yield controlled synthesis of poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐(bithiophene)] (F8T2) nanowires (main picture and lower inset). Photoconductivity measurements (schematic in center) yield single‐nanowire device responsivities of ca. 0.4 mA W^–1 and external quantum efficiencies of ca. 0.1 % under monochromatic illumination, comparable with data reported for single inorganic nanowire devices.     

CtpB Facilitates Mycobacterium tuberculosis Growth in Copper-Limited Niches

Copper is required for aerobic respiration by Mycobacterium tuberculosis and its human host, but this essential element is toxic in abundance. Copper nutritional immunity refers to host processes that modulate levels of free copper to alternately starve and intoxicate invading microbes. Bacteria engulfed by macrophages are initially contained within copper-limited phagosomes, which fuse with ATP7A vesicles that pump in toxic levels of copper. In this report, we examine how CtpB, a P-type ATPase in M. tuberculosis, aids in response to nutritional immunity. In vitro, the induced expression of ctpB in copper-replete medium inhibited mycobacterial growth, while deletion of the gene impaired growth only in copper-starved medium and within copper-limited host cells, suggesting a role for CtpB in copper acquisition or export to the copper-dependent respiration supercomplex. Unexpectedly, the absence of ctpB resulted in hypervirulence in the DBA/2 mouse infection model. As ctpB null strains exhibit diminished growth only in copper-starved conditions, reduced copper transport may have enabled the mutant to acquire a “Goldilocks” amount of the metal during transit through copper-intoxicating environments within this model system. This work reveals CtpB as a component of the M. tuberculosis toolkit to counter host nutritional immunity and underscores the importance of elucidating copper-uptake mechanisms in pathogenic mycobacteria.     

Non‐Covalent Functionalization of Graphene Using Self‐Assembly of Alkane‐Amines

A simple, versatile method for non‐covalent functionalization of graphene based on solution‐phase assembly of alkane‐amine layers is presented. Second‐order Møller–Plesset (MP2) perturbation theory on a cluster model (methylamine on pyrene) yields a binding energy of ≈220 meV for the amine–graphene interaction, which is strong enough to enable formation of a stable aminodecane layer at room temperature. Atomistic molecular dynamics simulations on an assembly of 1‐aminodecane molecules indicate that a self‐assembled monolayer can form, with the alkane chains oriented perpendicular to the graphene basal plane. The calculated monolayer height (≈1.7 nm) is in good agreement with atomic force microscopy data acquired for graphene functionalized with 1‐aminodecane, which yield a continuous layer with mean thickness ≈1.7 nm, albeit with some island defects. Raman data also confirm that self‐assembly of alkane‐amines is a non‐covalent process, i.e., it does not perturb the sp² hybridization of the graphene. Passivation and adsorbate n‐doping of graphene field‐effect devices using 1‐aminodecane, as well as high‐density binding of plasmonic metal nanoparticles and seeded atomic layer deposition of inorganic dielectrics using 1,10‐diaminodecane are also reported.     

Predictors of summertime heat index levels in New York City apartments

During heat waves, fatal overexposure to heat most often occurs at home. It is not known how factors such as building size, floor level, and different types of air conditioning (AC) contribute to excess indoor heat. We monitored indoor temperature and humidity in 36 apartments in New York City during summers 2014 and 2015 and used these values to calculate the indoor heat index (HI). We investigated the role of AC type and building‐level factors on indoor HI using multilevel regression models. Thirty‐four of 36 homes had AC. Central and ductless AC types were associated with the coolest indoor conditions; homes with window and portable AC were significantly warmer. Apartments on the top floor of a building were significantly hotter during heat advisory periods than other apartments regardless of the presence of AC. High indoor HI levels persisted in some homes for approximately 1 day following the end of the two heat advisory periods. We provide concrete evidence of higher heat levels in top floor apartments and in homes with certain types of AC. High heat levels that persist indoors after outdoor heat has subsided may present an underappreciated public health risk.     

An Atomistic Understanding of Allosteric Inhibition of Glutamate Racemase: a Dampening of Native Activation Dynamics

Glutamate racemases (GR) are members of the family of bacterial enzymes known as cofactor-independent racemases and epimerases and catalyze the stereoinversion of glutamate. D-amino acids are universally important for the proper construction of viable bacterial cell walls, and thus have been repeatedly validated as attractive targets for novel antimicrobial drug design. Significant aspects of the mechanism of this challenging stereoinversion remain unknown. The current study employs a combination of MD and QM/MM computational approaches to show that the GR from H. pylori must proceed via a pre-activation step, which is dependent on the enzyme's flexibility. This mechanism is starkly different from previously proposed mechanisms. These findings have immediate pharmaceutical relevance, as the H. pylori GR enzyme is a very attractive allosteric drug target. The results presented in this study offer a distinctly novel understanding of how AstraZeneca's lead series of inhibitors cripple the H. pylori GR's native motions, via prevention of this critical chemical pre-activation step. Our experimental studies, using SPR, fluorescence and NMR WaterLOGSY, show that H. pylori GR is not inhibited by the uncompetitive mechanism originally put forward by Lundqvist et al.. The current study supports a deep connection between native enzyme motions and chemical reactivity, which has strong relevance to the field of allosteric drug discovery.     

Polyethylene multiwalled carbon nanotube composites

Polyethylene (PE) multiwalled carbon nanotubes (MWCNTs) with weight fractions ranging from 0.1 to 10 wt% were prepared by melt blending using a mini-twin screw extruder. The morphology and degree of dispersion of the MWCNTs in the PE matrix at different length scales was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). Both individual and agglomerations of MWCNTs were evident. An up-shift of 17 cm⁻¹ for the G band and the evolution of a shoulder to this peak were obtained in the Raman spectra of the nanocomposites, probably due to compressive forces exerted on the MWCNTs by PE chains and indicating intercalation of PE into the MWCNT bundles. The electrical conductivity and linear viscoelastic behaviour of these nanocomposites were investigated. A percolation threshold of about 7.5 wt% was obtained and the electrical conductivity of PE was increased significantly, by 16 orders of magnitude, from 10⁻²⁰ to 10⁻⁴ S/cm. The storage modulus (G′) versus frequency curves approached a plateau above the percolation threshold with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behaviour. The ultimate tensile strength and elongation at break of the nanocomposites decreased with addition of MWCNTs. The diminution of mechanical properties of the nanocomposites, though concomitant with a significant increase in electrical conductivity, implies the mechanism for mechanical reinforcement for PE/MWCNT composites is filler-matrix interfacial interactions and not filler percolation. The temperature of crystallisation (T_c) and fraction of PE that was crystalline (F_c) were modified by incorporating MWCNTs. The thermal decomposition temperature of PE was enhanced by 20 K on addition of 10 wt% MWCNT.     

Development and evaluation of an ultrasonic personal aerosol sampler

Assessing personal exposure to air pollution has long proven challenging due to technological limitations posed by the samplers themselves. Historically, wearable aerosol monitors have proven to be expensive, noisy, and burdensome. The objective of this work was to develop a new type of wearable monitor, an ultrasonic personal aerosol sampler (UPAS), to overcome many of the technological limitations in personal exposure assessment. The UPAS is a time‐integrated monitor that features a novel micropump that is virtually silent during operation. A suite of onboard environmental sensors integrated with this pump measure and record mass airflow (0.5–3.0 L/min, accurate within 5%), temperature, pressure, relative humidity, light intensity, and acceleration. Rapid development of the UPAS was made possible through recent advances in low‐cost electronics, open‐source programming platforms, and additive manufacturing for rapid prototyping. Interchangeable cyclone inlets provided a close match to the EPA PM_2.5 mass criterion (within 5%) for device flows at either 1.0 or 2.0 L/min. Battery life varied from 23 to 45 hours depending on sample flow rate and selected filter media. Laboratory tests of the UPAS prototype demonstrate excellent agreement with equivalent federal reference method samplers for gravimetric analysis of PM_2.5 across a broad range of concentrations.     

Neural network pruning with Tukey-Kramer multiple comparison procedure

Reducing a neural network's complexity improves the ability of the network to generalize future examples. Like an overfitted regression function, neural networks may miss their target because of the excessive degrees of freedom stored up in unnecessary parameters. Over the past decade, the subject of pruning networks produced nonstatistical algorithms like Skeletonization, Optimal Brain Damage, and Optimal Brain Surgeon as methods to remove connections with the least salience. The method proposed here uses the bootstrap algorithm to estimate the distribution of the model parameter saliences. Statistical multiple comparison procedures are then used to make pruning decisions. We show this method compares well with Optimal Brain Surgeon in terms of ability to prune and the resulting network performance.