Thiolate-gold nanoclusters exhibit unique optical, magnetic and chiral properties, which are attractive for novel applications in nanotechnology. A fundamental challenge facing these nanomaterials is being able to study and understand their physical properties in various experimental conditions. To overcome this, extended X-ray absorption fine structure (EXAFS) spectroscopy can be employed to probe the Au local structure of thiolate-gold nanoclusters in a variety of conditions, providing valuable structural information from multiple bonding environments (i.e. metal-metal and metal-ligand interactions). This study discusses a methodology for conducting a multishell EXAFS fitting analysis that can be implemented for thiolate-gold nanocluster systems. Specifically, experimental and simulated EXAFS data for Au36(SR)24 nanoclusters are examined with a total of 5 scattering paths fitted to the experimental data.

A microcantliever based crack healing experiment is described and utilized in order to study the capillary nucleation rate for typical MEMS surfaces. An advanced test chamber that allows exquisite environmental control is also described and used in this study. Crack healing experiments prove to be a viable experimental technique to investigate the dynamics of capillary nucleation. The effective capillary nucleation time for the multi-asperity surface of microcantilever samples appears to increase logarithmically with adhesion energy.

Hydrogen atom H (≡ proton + electron) transfer (HAT), is the most common reaction that involves the transfer of two elementary particles, a proton and an electron. Antioxidant, proton-coupled electron transfer (PCET) reactions involve also the transfer of two elementary particles, a proton and an electron. These constitute the fundamental step in a wide range of processes, chemical energy technologies, which rely on e–/H+ transfer from combustion and aerobic oxidations, to enzymatic catalysis and the destructive effects of reactive oxygen species in vivo. Here we describe a novel phenomenon, plasmonically-enhanced PCET, using nanothin silica-coated plasmonic Ag nanoparticles, functionalized with gallic acid, a natural antioxidant molecule, that is able to perform PCET. These nanoparticles can transfer rapidly electrons and protons to stable radicals. The kinetics and yield of these PCET reactions can be enhanced by plasmonic resonance modes excited by low-power, near-Infrared (785nm) laser irradiation. The demonstration that these plasmonic nanoparticles can enhance the HAT rates for both electrons and protons expands the traditional view of interfacial PCET. The occurrence of interfacial plasmon-enhancement of PCET brings together so far unrelated domains of nanoplasmonics, electron/proton translocation with significant impact on a variety of applications and most notably in theranostics.

The increasing use of polymeric reinforcements in concrete structures requires either the development of a new design theory or the adaptation of current designs considering the engineering properties of this type of materials. In this work a method for calculating the deflections of reinforced concrete elements is proposed, which can be used in predicting the flexural behavior of longitudinally reinforced concrete with PET strips in amounts up to 1%. The model theory assumes that concrete has a tensile load capacity different to zero, characterized by a uniaxial tensile stress-strain diagram. A series of tests were conducted to corroborate the validity of the suggested method, showing that the theory also correctly predicts the creep deformation post-cracking. The deflection results of reinforced concrete with recycled PET strips are presented. The tests are carried out by a simple beam with center-point loading, using three different amounts of reinforcement and comparing the experimental results with the theoretical results of the proposed model.

Our research is focused on the engineering of novel, highly sensitive and miniaturized hybrid materials from carbon nanotubes (CNTs) and DNA molecules for applications in biosensors and medical devices. These hybrid sensors allow for a high degree of miniaturization, a key factor in the design of lightweight components while maintaining the advantages of in-situ and real-time analysis capabilities. In the first phase of the sensor design process, we investigated the structural and electrical properties of the supramolecular complexes made of amide-functionalized CNTs and double-stranded DNA. The solubilization properties of the hybrid nanotubes in aqueous solutions with different concentrations of DNA were studied, and an optimal ratio of nanotubes and biomolecules to achieve a good level of dispersion was found. Complexes formed in aqueous solution from CNTs and DNA are highly stable and maintain their properties up to one month from preparation. The morphology of the CNT-DNA composites was investigated at the nanoscale level using atomic force microscopy (AFM) and electron microscopy (SEM). Results from these experiments show the strong affinity between the surface of the amide-functionalized CNTs and the DNA strands. Further, the CNT-DNA films were investigated by atomic force microscopy in the PeakForce TUNA mode to assess the suitability of this technique in determining the local conductive properties of the hybrid films.

Liposomal drug delivery products have been already commercialized in tumor therapeutics, which can realize passive tumor targeting via enhanced permeability and retention (EPR) effect resulting from the leaky tumor vasculature. To control drug release out of the liposomes, thermo-sensitive liposomes (TSLs) have been developed so that an abrupt exposure of highly concentrated drugs to tumor tissues was enabled by locally treated thermal stimuli. As interests upon TSL have increased along with ongoing clinical trials, some types of TSLs with different physical properties in pharmacokinetics and the mechanism of drug release have been formulated. However, there are few protocols established with a desirable heat source to maximize the efficacy of different TSLs as treating tumors. In this study, we examined different protocols for the most effective application of different TSLs to tumor therapy. First, we examined if enhancing the accumulation of TSLs within tumor tissues prior to bursting drugs out of TSLs could lead to increasing anti-tumor efficacy. Second, we compared the efficiency of two different heat sources on the use of TSL, a warm water bath (42°C) and high intensity focused ultrasound (HIFU). Our study suggests that the specified protocol be setup for TSLs with different physical properties to optimally function in tumor therapies.

Ho2O3-TiO2 based metal-insulator-metal capacitors were grown by ALD, using Ho(thd)3, Ti(OCH(CH3)2)4 and ozone as precursors. The thicknesses of the films were in the range of 7.7 to 25 nm. Some of the films were post-deposited annealed in order to study the treatment effects. The capacitors were electrically characterized. Leakage current decreases as the amount of holmium increased in the films. Resistive switching behavior was obtained in the samples where the leakage current was low. This effect was also observed in Ho2O3 films, where no titanium was present in the films.

The High Throughput Experimentation (HTE) project of the Joint Center for Artificial Photosynthesis (JCAP, http://solarfuelshub.org/) performs accelerated discovery of new earth-abundant photoabsorbers and electrocatalysts. Through collaboration within the DOE solar fuels hub and with the broader research community, the new materials will be utilized in devices that efficiently convert solar energy, water and carbon dioxide into transportation fuels. JCAP-HTE builds high-throughput pipelines for the synthesis, screening and characterization of photoelectrochemical materials. In addition to a summary of these pipelines, we will describe several new screening instruments for high throughput (photo-)electrochemical measurements. These instruments are not only optimized for screening against solar fuels requirements, but also provide new tools for the broader combinatorial materials science community. We will also describe the high throughput discovery, follow-on verification, and device implementation of a new quaternary metal oxide catalyst. This rapid technology development from discovery to device implementation is a hallmark of the multi-faceted JCAP research effort.

It is well known that exposure to ultraviolet (UV) light can result in various physical and psychological diseases. Therefore, there is a strong demand for a reliable sensor to monitor UV exposure levels in the physiologically relevant intensity ranges of mW/cm2. Here, we demonstrate a UV sensor based on a silica whispering gallery mode microresonator. This UV sensor works over physiologically relevant intensity ranges with linear performance both in the forward and backward operating directions, with very high signal-to-noise ratio that can be utilized in monitoring the UV exposure for various applications.

In this report we present results comparing lateral MOSFET properties of devices fabricated on Si-face (0001) and A-face (11-20) 4H-SiC, with nitric oxide passivation anneals. We observe a field-effect mobility of 33 cm2/V.s on p-type 5×1015 doped Si-face. These devices have a peak field-effect mobility which increases with temperature, indicative of a channel mobility limited by coulomb scattering. On 1×1016 p-type A-face SiC, the peak channel mobility is observed to be 80 cm2/V.s, with a negative temperature dependence, indicating that phonon-scattering effects dominate, with a much lower density of shallow acceptor traps. This > 2x higher channel mobility would result in a substantial decrease in on-resistance, hence lower power losses, for 4H-SiC power MOSFETs with voltage ratings below 2 kV. However, MOS C-V and gate leakage measurements indicate very different oxide and interface quality on each SiC face. For example, the Fowler-Nordheim (FN) conduction-band (CB) barrier height for electron tunneling at the SiO2/SiC interface is 2.8 eV on Si-face SiC, while it is 2.5 eV or less on A-face SiC. For the valence-band side, the effective FN barrier height at the valence-band (VB) side of only 1.6 eV on A-face SiC, while the VB barrier height is about 3.1 eV on Si-face SiC. Moreover, C-V of the MOS gate on A-face indicates the presence of a high-density of deep hole traps. It is apparent that oxides on alternative crystal faces, very promising in terms of channel mobility, require further study for complete understanding and control of the interface properties.

Poly(N-isopropylacrylamide) (PNIPAM) is a thermosensitive polymer that is well-known for its behavior at a lower critical solution temperature (LCST) around 305 K. Below the LCST, PNIPAM is soluble in water, and above this temperature, polymer chains collapse and transform into a globule state. The conformational dynamics of single chains of polymer in a solution is known to be different from those of grafted structures that comprise of an ensemble of such single chains. In this study, we have carried out MD simulations of a mesoscopic nanostructure of PNIPAM polymer chains consisting of 60 monomer units grafted onto gold nanoparticles of different diameters, to study the effect of temperature and core particle size on the polymer conformations. Additionally, we have also studied the effect of grafting density on the coil-to-globule transition exhibited by PNIPAM through the LCST. The systems investigated consisted of ∼3 and ∼6 million atoms. Simulations were carried out below and above the LCST of PNIPAM, at 275K and 325K. Simulation trajectories were analyzed for radius of gyration of PNIPAM chains.

An actual trend to enhance solar cells efficiency is to build multijunction cells, creating a bandshape wavelength collection. However, the best multijuction cells are actually made of III-V compounds when silicon and its alloys don’t lead to high efficiency devices. In this article, we study a 3C-SiC/Si heterojunction as a first step for 3C-SiC/Si tandem cells. Four samples were fabricated by depositing 3C-SiC on Si wafers with different SiC doping levels. Simulations of the structures are performed, as well as optical and electrical characterizations of the heterojunction cells.

A solution-processed method is developed to fabricate fully transparent resistive random access memory (RRAM) devices with a configuration of FTO/ZrO2/ITO, where the zirconium dioxide (ZrO2) layer was firstly deposited on fluorine tin oxide (FTO) substrate by sol-gel and then indium tin oxide (ITO) films were deposited on ZrO2 layer by sol-gel as the top electrodes.The solution processed FTO/ZrO2/ITO based RRAM devices show the fully transparency and excellent bipolar resistance switching behaviors. The resistance ratio between high and low resistance states was more than 10, and more than 100 switching cycles and good data retention and multilevel resistive switching have been demonstrated.

One of promising photorechargeable electrode, which has two functions of photovoltaic and electrical energy storage, is a composite film of mesoporous TiO2 and conducting polymer polyaniline. Galvanostatic charge/discharge characteristics of the TiO2-polyaniline composite were examined to reveal how fast the film was charged. The film with a specific capacity 60-120 mAh g–1 was found to be fully charged at high charging rate 20 mA cm–2 which is comparable to high performance solar cells. Such high charging rate was achieved by the compact polyaniline layer covering the large specific surface area of mesoporous TiO2 film.

Flexible electronics and microsystems are an emerging technology with a tremedous impact to the future electronics and information technology and widespread applications. Various devices and microsystems have been developed. Surface acoustic wave (SAW) devices are a type of essential device for electronics, microsensors and microsystems; however there is no activity on the development of flexible SAW devices yet. This paper reports the development of flexible SAW devices on cheap, bendable and disposable plastic films. Flexible SAW devices with resonant frequency of 198.1 MHz and 447 MHz for the Rayleigh and Lamb waves respectively have been obtained with a large transmission signal up to 18dB. The flexible SAW devices have also demonstrated their ability for acoustic streaming with a velocity up to 3.4 cm/s and for particle concentration. The results have clearly demonstrated that the flexible SAW devices have great potential for applications in electronics and microsystems.

Herein, we detail the fabrication of atomic force microscope (AFM) probes that have two and three coaxial electrodes at their tips. This fabrication strategy leverages the availability of conductive AFM probes and encompasses a general method for processing their complex and delicate structure through the deposition of insulating and conductive layers by shadow masked chemical and physical vapor deposition, respectively. Focused ion beam milling is used to expose the two electrode (coaxial) or three electrode (triaxial) structures at the tip of the AFM probe. Finally, we discuss new imaging modalities enabled by these probes including electrically-driven contact resonance imaging for nanoscale mechanical characterization, imaging the local dielectric constant by quantifying the dielectrophoretic force, and trapping functional particles at the tip of a probe using dielectrophoresis. These imaging techniques illustrate the generality and utility of this fabrication approach and suggest that such probes could be widely applied to image many nanoscale materials.

Hexagonal boron nitride (hBN) crystals enriched in 10B and 11B isotopes were synthesized using a high temperature (1500° C) Ni-Cr-B reactive-precipitation growth under a N2 atmosphere. Two growth mechanisms were observed: conventional defect-facilitated bulk growth which produced crystals with a platelet-like habit with width and thickness of 20-30 μm and 5 μm, respectively, and vapor-liquid-solid interface growth of hBN whiskers with lengths and diameters as large as 70 μm and 5 μm, respectively. Similar growth mechanisms were seen for samples enriched in either isotope. Isotopic analysis via secondary-ion mass spectrometry showed boron concentrations of 84.4 at% and 93.0 at% for the majority isotopes in the 10B-rich and 11B-rich samples, respectively. Raman spectroscopy showed an increase in peak Raman shift for the 10B-rich sample, having two barely resolved peaks at 1393.5 and 1388.8 cm-1, and a decrease for the 11B-rich sample, having peak at 1359.5 cm-1 (FWHM of 9.4 cm-1), compared to that of natural hBN, with its peak at 1365.8 cm-1 (FWHM of 10.3 cm-1). Raman shift showed a linear trend with increasing 10B concentration allowing for a calibration curve to be developed to estimate 10B enrichment in hBN using non-destructive methods.

Nanomaterials engineered in novel multi-modular systems in which every component works in a synergistic way with others could potentially lead to a completely new type of tools for nanomedicine. The development of nanostructures able to release drugs directly within the target after a stimulus can drastically improve the therapeutics efficiency by reducing side effects. Gold nanoparticles offer one of the most suitable platforms for the development of modular nano-devices. On the one hand, their surface properties enable effective coating by peptides containing at least one cysteine, thus yielding stable and non-cytotoxic systems. On the other, their intriguing photophysics, characterized by the surface plasmon resonance, can be exploited for novel excitation schemes. Doxorubicin is a widely used, but toxic, cancer chemotherapeutic agent. In order to localize its therapeutic action while minimizing its side effects, doxorubicin was covalently conjugated to 30 nm peptide-encapsulated gold nanospheres by click-chemistry and then it was photo-released in a controlled fashion through the cleavage of the 1,2,3-triazolic ring by a multiphoton process using 561 nm irradiation at µW power. Selective apoptosis of human osteosarcoma (U2OS) cells was observed only in the irradiated 100x100 micron area in less than six minutes after the stimulus. Notably, the apoptotic effect of doxorubicin was completely inhibited for at least eight hours until its release “on demand” was externally light-triggered.