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The origin of the interface formation appearing due to the realization of contacts to ultrathin gold nanowire devices is revealed. Such interfaces play an important role in transport mechanisms in nanowire structures and can determine the electrical and operating parameters of a nanodevice. Based on experimental results, the specific electrical properties of bundles of ultrathin gold nanowires fabricated by wet chemical synthesis and subsequently assembled and contacted with gold electrodes are reported. It is demonstrated that these properties are strongly affected by the monolayers of organic molecules inevitably present on the surface of the nanowires due to synthetic conditions. In particular, such layers form a potential barrier to tunneling of the electrons from contacts to the nanowires. The electric transport behavior of the investigated nanowire structures in the temperature range from 500 mK to 300 K obeys the model of thermal fluctuation-induced tunneling conduction through the nanowire-metal electrode molecular junction. Application of this model allows calculation of the parameters of the molecular potential barrier. The formation of such a molecular barrier is verified by scanning tunneling microscope (STM) and transmission electron microscope (TEM) measurements performed using a supporting graphene layer. These findings are important for designing novel nanodevices for molecular electronics on the basis of ultrathin nanowires.

The fabrication of ultrathin single-crystal Au nanowires with high aspect ratio and that are stable in air is challenging. Recently, a simple wet-chemical approach using oleylamine has been reported for the synthesis of Au nanowires with micrometer length and 2 nm in diameter. Despite efforts to understand the mechanism of the reaction, an ultimate question about the role of oxygen (O(2)) during the synthesis remained unclear. Here we report that the synthesis of ultrathin Au nanowires employing oleylamine is strongly affected by the amount of O(2) absorbed in the reaction solution. Saturating the solution with O(2) leads to both a high-yield production of nanowires and an increase in their length. Nanowires with diameters of about 2 nm and lengths of 8 μm, which corresponds to an aspect ratio of approximately 4000, were produced. The role of oxygen is attributed to the enhanced oxidation of twin defects on Au nanoparticles formed in the first stage of the reaction. Understanding the role of oxidative etching is crucial to significantly increasing the yield and the length of ultrathin Au nanowires.

Ultrathin metal nanowires are ultimately analytical tools that can be used to survey the interfacial properties of the functional groups of organic molecules immobilized on nanoelectrodes. The high ratio of surface to bulk atoms makes such ultrathin nanowires extremely electrically sensitive to adsorbates and their charge and/or polarity, although little is known about the nature of surface chemistry interactions on metallic ultrathin nanowires. Here we report the first studies about the effect of functional groups of short-chain alkanethiol molecules on the electrical resistance of ultrathin gold nanowires. We fabricated ultrathin nanowire electrical sensors based on chemiresistors using conventional microfabrication techniques, so that the contact areas were passivated to leave only the surface of the nanowires exposed to the environment. By immobilizing alkanethiol molecules with head groups such as -CH3, -NH2 and -COOH on gold nanowires, we examined how the charge proximity due to protonation/deprotonation of the functional groups affects the resistance of the sensors. Electrical measurements in air and in water only indicate that beyond the gold-sulfur moiety interactions, the interfacial charge due to the acid-base chemistry of the functional groups of the molecules has a significant impact on the electrical resistance of the wires. Our data demonstrate that the degree of dissociation of the corresponding functional groups plays a major role in enhancing the surface-sensitive resistivity of the nanowires. These results stress the importance of recognizing the effect of protonation/deprotonation of the surface chemistry on the resulting electrical sensitivity of ultrathin metal nanowires and the applicability of such sensors for studying interfacial properties using electrodes of comparable size to the electrochemical double layer.

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Cracking the cytoarchitectural organization, activity patterns, and neurotransmitter nature of genetically-distinct cell types in the lateral hypothalamus (LH) is fundamental to develop a mechanistic understanding of how activity dynamics within this brain region are generated and operate together through synaptic connections to regulate circuit function. However, the precise mechanisms through which LH circuits orchestrate such dynamics have remained elusive due to the heterogeneity of the intermingled and functionally distinct cell types in this brain region. Here we reveal that a cell type in the mouse LH identified by the expression of the calcium-binding protein parvalbumin (PVALB; LHPV) is fast-spiking, releases the excitatory neurotransmitter glutamate, and sends long range projections throughout the brain. Thus, our findings challenge long-standing concepts that define neurons with a fast-spiking phenotype as exclusively GABAergic. Furthermore, we provide for the first time a detailed characterization of the electrophysiological properties of these neurons. Our work identifies LHPV neurons as a novel functional component within the LH glutamatergic circuitry.

Methods to prepare ultrathin gold nanowires and monodisperse nanoparticles based on the intrinsic property of gold(I) ions to form aurophilic interactions stabilized by oleylamine and long-chain alkylamine have been widely explored. Due to the low thermodynamic stability of the high aspect ratio nanostructures, their conjugation and assembly into functional nanosystems have not been explored so far. One of the reasons for this is that the surface of the nanostructures is insulated by stabilization compounds, which preserve the integrity of the nanostructures but at the same time form an insulating barrier in electronic and electrochemical systems in contact areas and for the charge transfer reactions. Conjugation of a metalloprotein cytochrome c (Cyt c) with oleylamine-stabilized gold ultrathin nanowires and nanoparticles into a bioelectrochemically active nanoarchitecture is presented here for the first time. Methods of preparing and assembling the ultrathin nanowires and nanoparticles on the thin-film gold electrodes are shown. Thermodynamic and kinetic parameters were obtained for the direct electron transfer reaction of cyt c on these surfaces. Nanowires are responsible for an approximately −20 mV shift in the redox potential of the ferri/ferro-cyt c couple relative to a thin-film gold electrode.