Nanoscale surface reactions by laser irradiation of Al nanoparticles on MoO3 flakes.

Surface reactions between heated aluminum nanoparticles (Al NPs) and thin α-MoO3 sheets are investigated. Localized photothermal heating on Al NP clusters is provided by a Raman spectrometer laser, while enhanced heating rates and imaging resolution are enabled by the use of a plasmonic grating substrate. Prominent linear reaction zones extending from Al NPs in the 〈001〉 crystal direction are observed on the surface of the host MoO3 sheets after heating. Raman spectroscopy and x-ray diffraction indicate that α-Al2O3 is generated within these extended reacted regions, while AFM and SEM indicate that the topology of the reaction regions are indistinguishable from the MoO3 host. We hypothesize that these Al2O3 zones are formed by surface diffusion and subsequent sub-surface adsorption of heated Al adatoms along the low-energy 〈001〉 MoO3 direction. Understanding and controlling these reaction mechanisms could lead to enhanced combustion of Al/MoO3 nanothermite systems.

Ultra-broadband infrared absorption by tapered hyperbolic multilayer waveguides.

Ultra-broadband strong absorption over 92% covering the infrared wavelength range of 1~6µm is demonstrated by using the tapered hyperbolic Au-SiO2 multilayer waveguides on glass substrates. Such broadband absorption is formed by the stop-light modes at various wavelengths located at different waveguide widths. A planar hyperbolic waveguide model is built to determine the stop-light modes by considering both forward and backward guided modes. The stop-light modes located inside the Au-SiO2 multilayer waveguide are simulated at the absorption peaks by reducing the Au loss. Tapered multilayer waveguides with varying top widths are further simulated, fabricated and measured, indicating the almost linear relation between the waveguide width and the stop-light wavelength. Moreover, the broadband absorption of tapered waveguide is proved to be angle-insensitive and polarization-independent, and the heat generation and temperature increase are also discussed.

Plasmonic nano-protrusions: hierarchical nanostructures for single-molecule Raman spectroscopy.

Classical methods for enhancing the electromagnetic field from substrates for spectroscopic applications, such as surface-enhanced Raman spectroscopy (SERS), have involved the generation of hotspots through directed self-assembly of nanoparticles or by patterning nanoscale features using expensive nanolithography techniques. A novel large-area, cost-effective soft lithographic technique involving glancing angle deposition (GLAD) of silver on polymer gratings is reported here. This method produces hierarchical nanostructures with high enhancement factors capable of analyzing single-molecule SERS. The uniform ordered and patterned nanostructures provide extraordinary field enhancements that serve as excitatory hotspots and are herein interrogated by SERS. The high spatial homogeneity of the Raman signal and signal enhancement over a large area from a self-assembled monolayer (SAM) of 2-naphthalenethiol demonstrated the uniformity of the hotspots. The enhancement was shown to have a critical dependence on the underlying nanostructure via the surface energy landscape and GLAD angles for a fixed deposition thickness, as evidenced by atomic force microscopy and scanning electron microscopy surface analysis of the substrate. The nanostructured surface leads to an extremely concentrated electromagnetic field at sharp nanoscale peaks, here referred to as 'nano-protrusions', due to the coupling of surface plasmon resonance (SPR) with localized SPR. These nano-protrusions act as hotspots which provide Raman enhancement factors as high as 108 over a comparable SAM on silver. Comparison of our substrate with the commercial substrate Klarite™ shows higher signal enhancement and minimal signal variation with hotspot spatial distribution. By using the proper plasmon resonance angle corresponding to the laser source wavelength, further enhancement in signal intensity can be achieved. Single-molecule Raman spectra for rhodamine 6G are obtained from the best SERS substrate (a GLAD angle of 60°). The single-molecule spectrum is invariant over the substrate, due to the patterned ordered nanostructures (nano-protrusions).

High Pressure Vibrational Properties of WS2 Nanotubes.

We bring together synchrotron-based infrared and Raman spectroscopies, diamond anvil cell techniques, and an analysis of frequency shifts and lattice dynamics to unveil the vibrational properties of multiwall WS2 nanotubes under compression. While most of the vibrational modes display similar hardening trends, the Raman-active A1g breathing mode is almost twice as responsive, suggesting that the nanotube breakdown pathway under strain proceeds through this displacement. At the same time, the previously unexplored high pressure infrared response provides unexpected insight into the electronic properties of the multiwall WS2 tubes. The development of the localized absorption is fit to a percolation model, indicating that the nanotubes display a modest macroscopic conductivity due to hopping from tube to tube.

Preliminary results of a phase II randomized study to determine the efficacy and safety of genetically engineered allogeneic human chondrocytes expressing TGF-ß1 in patients with grade 3 chronic degenerative joint disease of the knee.

OBJECTIVE: The aim of this study was to preliminarily evaluate the efficacy and outcomes of injectable genetically engineered chondrocytes virally transduced with TGF-ß1 (GEC-TGF-ß1) compared to placebo. DESIGN: A multi-center, double-blinded, placebo-controlled, randomized study of adults with knee osteoarthritis. A total of 102 patients were 2:1 randomized to GEC-TGF-ß1 or placebo. Primary outcomes assessed were (1) function of the knee joint, scored using the International Knee Documentation Committee (IKDC); and (2) pain, measured by Visual Analog Scale (VAS). Secondary endpoints assessed were pain and analgesic use, quality of life (QOL), and adverse events (AEs) including need for total knee arthroplasty after treatment. RESULTS: IKDC showed significant improvement in the GEC-TGF-ß1 group over the placebo at week 12 (least mean square difference (LSMD): 10.3; P = 0.0342), week 52 (LSMD: 13.6; P = 0.0082), and overall (LSMD: 8.6; P = 0.0453). VAS Analysis showed a significant improvement in GEC-TGF-ß1 group compared to placebo at weeks 12 (LSMD: -13.8; P = 0.0162), 52 (LSMD: -13.1; P = 0.0332), and overall (LSMD: -10.1; P = 0.0350). Reduction in pain severity at week 12 and 52, frequency at 24 h and week 52, and the percentage of patients in the GEC-TGF-ß1 group receiving analgesics at week 4 (27 vs 40%) and 12 (27 vs 37%) was observed. CONCLUSIONS: GEC-TGF-ß1 patients had more positive responses on the IKDC, VAS, and were less likely to require analgesics. TRIAL NUMBER: ClinicalTrials.gov (NCT01221441) - "Study of TG-C in Patients with Grade 3 Degenerative Joint Disease of the Knee".

Room temperature Coulomb blockade effects in Au nanocluster/pentacene single electron transistors.

Single-electron transistors incorporating single ∼1 nm gold nanocluster (AuNCs) and pentacene as a complex charge transport system have been used to study the quantum Coulomb blockade and its single electron tunnelling behaviour at room temperature (RT) (300 K). Monodisperse ultra-small (0.86 ± 0.30 nm) AuNCs were deposited by the tilted-target sputtering technique into 12 nm nanogaps fabricated by high-resolution e-beam lithography. Tunnelling resistance was modulated to ∼10(9) Ω by addition of a pentacene layer, allowing clear observation of quantum staircases and Coulomb oscillations with on/off current modulation ratio of ∼100 in RT current-voltage measurements. The electron addition energy and average quantized energy level spacing were found to be 282 and 80.4 meV, respectively, which are significantly larger than the thermal energy at 300 K (25.9 meV).

Experimental characterization of optical nonlocality in metal-dielectric multilayer metamaterials.

The optical nonlocality in metal-dielectric multilayer metamaterials is characterized experimentally as a function of the angle of incidence with respect to the TE-polarized incident light. The physical mechanism of the difference between the nonlocal effective permittivity and the effective-medium-theory-based effective permittivity depending on the incident angle is theoretically revealed through the analysis of the band structure, the dispersion relation, and the iso-frequency contours according to the transfer-matrix method. Such effective permittivity difference is also retrieved in the metal-dielectric multilayers based on the measured transmission and reflection spectra.

Effect of protective coating agents on microleakage and flexural strength of glass ionomer cement and zirconomer. an in vitro study.

PURPOSE: The objective of this study was to assess the microleakage and flexural strength of glass ionomer cement (GIC) and modified GIC (Zirconomer) when coated with protective coating agents such as COAT-IT and G-COAT plus. METHODS: Sixty tooth specimens were grouped into two groups based on the type of restorations (GIC (n = 30) and Zirconomer (n = 30)). The samples were further divided into three subgroups (n = 10) based on the protective coating agent (Petroleum jelly, G-COAT Plus, or COAT IT) applied. This study evaluated the microleakage at the occlusal and cervical margins of class V restoration after being subjected to dye penetration and sectioning. Each specimen was viewed under a 40 × microscope and was given scores based on the depth of dye penetration. They were statistically analyzed using the Kruskal-Wallis test and compared within the groups using the Mann- Whitney Test. In addition, flexural strength was assessed using standardized cuboid (25 × 2 × 2 mm) specimens of restorative materials with and without protective coating agents. The mean flexural strength data of all the subgroups were statistically evaluated using a one-way analysis of variance (ANOVA) and compared within the subgroups using the student t test. RESULTS: A statistically significant difference was found when occlusal margin microleakage scores were evaluated with G-COAT Plus demonstrating the lowest occlusal margin microleakage when applied over GIC restoration. The increasing order of occlusal margin microleakage scores is as follows: GIC with G-COAT Plus, Zirconomer with COAT-IT, GIC with COAT-IT, GIC, Zirconomer with G-COAT Plus, and Zirconomer. However, the cervical margin microleakage scores revealed no significant difference. While flexural strength was found to be highest for the GIC group coated with G-COAT Plus, it was observed that there was a significant improvement in the flexural strength of both GIC and Zirconomer when coated with either of the protective coating agents. CONCLUSION: Within the limitations of this in vitro study, it was observed that the application of protective coating agents can significantly reduce the potential microleakage and improve the flexural strength of the restorative material especially when zirconia-reinforced GIC is the restorative material.

Sub-2 nm size and density tunable platinum nanoparticles using room temperature tilted-target sputtering.

This paper describes a tilted-target RF magnetron sputter deposition system to grow nanoparticles in a controlled way. With detailed characterization of ultra-high density (up to 1.1 × 10¹³ cm⁻²) and ultra-small size Pt nanoparticles (0.5-2 nm), it explains their growth and crystalline properties on amorphous Al2O3 thin films. It is shown that Pt nanoparticle size and number density can be precisely engineered by varying selected experimental parameters such as target angle, sputtering power and time of deposition to control the energy of the metal atoms in the deposition flux. Based on rate equation modelling of nanoparticle growth, three distinct growth regimes, namely nucleation dependent, coalescence dependent and agglomeration dependent regimes, were observed. The correlation between different nanoparticle growth regimes and the consequent crystal structure transformation, non-crystalline clusters → single crystalline nanoparticles → polycrystalline islands, is also discussed.

Magnetoelectric coupling in 4,4'-stilbenedinitrene.

We investigated the optical properties of 4,4'-stilbenedinitrene at low temperature and in high magnetic fields and compared the results with complementary first principles calculations. Both physical tuning parameters allow us to manipulate the singlet-triplet equilibrium, and by doing so, control the optical contrast (which is on the order of -2.5 × 10(2) cm(-1) at 555 nm and 35 T). Moreover, analysis of the magneto-optical response using a combined population and Beer's law framework reveals the singlet-triplet spin gap and identifies particular features in the absorption difference spectrum as deriving from singlet or triplet state excitations. These findings deepen our understanding of coupling in open shell molecules and show how chemical structure modification can modulate charge-spin interactions in organic biradicals.

Technetium-99-Guided Axillary Lymph Node Identification: A Case Report of a Novel Technique for Targeted Lymph Node Excision Biopsy for Node Positive Breast Cancer After Neoadjuvant Chemotherapy.

Targeted axillary lymph node identification for breast cancer involves localization and removal of previously marked metastatic lymph nodes after the completion of neoadjuvant chemotherapy (NACT), when clinical and radiological complete responses of the axillary nodes are achieved. Traditionally, axillary lymph node dissection is performed for patients with node positive disease, but the high rates of pathological complete responses now seen after NACT have ushered in lower morbidity techniques such as sentinel lymph node excision biopsies, targeted axillary lymph node dissection and targeted axillary lymph node identification (clip node identification) in node positive disease which has converted to clinical/radiologically node negative. The latter two techniques often require the use of expensive seeds and advanced localization techniques. Here we describe the case of a 59-year-old woman who was diagnosed with node positive invasive breast cancer who was sequenced with NACT. We developed a novel technique, where technetium-99m was injected directly into a previously clipped metastatic axillary lymph node which was then localized with the Neoprobe gamma detection system intra-operatively and removed. This is a relatively low-cost technique that can be easily introduced in limited resourced health systems where radio-guided sentinel lymph node biopsies are already being performed.

Laser-scribed conductive, photoactive transition metal oxide on soft elastomers for Janus on-skin electronics and soft actuators.

Laser-assisted fabrication of conductive materials on flexible substrates has attracted intense interests because of its simplicity, easy customization, and broad applications. However, it remains challenging to achieve laser scribing of conductive materials on tissue-like soft elastomers, which can serve as the basis to construct bioelectronics and soft actuators. Here, we report laser scribing of metallic conductive, photoactive transition metal oxide (molybdenum dioxide) on soft elastomers, coated with molybdenum chloride precursors, under ambient conditions. Laser-scribed molybdenum dioxide (LSM) exhibits high electrical conductivity, biocompatibility, chemical stability, and compatibility with magnetic resonance imaging. In addition, LSM can be made on various substrates (polyimide, glass, and hair), showing high generality. Furthermore, LSM-based Janus on-skin electronics are developed to record information from human skin, human breath, and environments. Taking advantage of its outstanding photothermal effect, LSM-based soft actuators are developed to build light-driven reconfigurable three-dimensional architectures, reshapable airflow sensors, and smart robotic worms with bioelectronic sensors.

Assessment of prescribing pattern of drugs and completeness of prescriptions as per the World Health Organization prescribing indicators in various Indian tertiary care centers: A multicentric study by Rational Use of Medicines Centers-Indian Council of Medical Research network under National Virtual Centre Clinical Pharmacology activity.

OBJECTIVE: The rational use of medicines as per the World Health Organization (WHO) should be practiced globally. However, data regarding the completeness of the prescriptions and their rational use is lacking from developing countries like India. Thus, the aim of this study was to assess the prescribing patterns of drugs and completeness of prescriptions as per WHO core drug use and complementary indicators to provide real-life examples for the Indian Council of Medical Research (ICMR) online prescribing skill course for medical graduates. METHODS: Prescriptions of the patients, fulfilling inclusion criteria, attending Outpatient Departments of various specialties of tertiary care hospitals, were collected by thirteen ICMR Rational use of medicines centers located in tertiary care hospitals, throughout India. Prescriptions were evaluated for rational use of medicines according to the WHO guidelines and for appropriateness as per standard treatment guidelines using a common protocol approved by local Ethics committees. RESULTS: Among 4838 prescriptions, an average of about three drugs (3.34) was prescribed to the patients per prescription. Polypharmacy was noted in 83.05% of prescriptions. Generic drugs were prescribed in 47.58% of the prescriptions. Further, antimicrobials were prescribed in 17.63% of the prescriptions and only 4.98% of prescriptions were with injectables. During the prescription evaluation, 38.65% of the prescriptions were incomplete due to multiple omissions such as dose, duration, and formulation. CONCLUSION: Most of the parameters in the present study were out of the range of WHO-recommended prescribing indicators. Therefore, effective intervention program, like training, for the promotion of rational drug use practice was recommended to improve the prescribing pattern of drugs and the quality of prescriptions all over the country.

Microwell device for targeting single cells to electrochemical microelectrodes for high-throughput amperometric detection of quantal exocytosis.

Electrochemical microelectrodes are commonly used to detect spikes of amperometric current that correspond to exocytosis of oxidizable transmitter from individual vesicles, i.e., quantal exocytosis. We are developing transparent multielectrochemical electrode arrays on microchips in order to automate measurement of quantal exocytosis. Here, we report development of an improved device to target individual cells to each microelectrode in an array. Efficient targeting (~75%) is achieved using cell-sized microwell traps fabricated in SU-8 photoresist together with patterning of poly(l-lysine) in register with electrodes to promote cell adhesion. The surface between electrodes is made resistant to cell adhesion using poly(ethylene glycol) in order to facilitate movement of cells to electrode "docking sites". We demonstrate the activity of the electrodes using the test analyte ferricyanide and perform recordings of quantal exocytosis from bovine adrenal chromaffin cells on the device. Multiple cell recordings on a single device demonstrate the consistency of spike measurements, and multiple recordings from the same electrodes demonstrate that the device can be cleaned and reused without degradation of performance. The new device will enable high-throughput studies of quantal exocytosis and may also find application in rapidly screening drugs or toxins for effects on exocytosis.

Communication: Manipulating the singlet-triplet equilibrium in organic biradical materials.

We investigated the tunability of the singlet-triplet equilibrium population in the organic biradical 1,4-phenylenedinitrene via magneto-optical spectroscopy. A rich magnetochromic response occurs because applied field increases the concentration of the triplet state species, which has a unique optical signature by comparison with the singlet biradical and the precursor molecule. A Curie-like analysis of the magneto-optical properties allows us to extract the spin gap, which is smaller than previously supposed. These measurements establish the value of local-probe photophysical techniques for magnetic property determination in open-shell systems such as biradicals where a traditional electron paramagnetic resonance Curie law analysis has intrinsic limitations.

Enhanced Third Harmonic Generation in Lead Bromide Perovskites with Ruddlesden-Popper Planar Faults.

Lead halide perovskites provide a test bed for exploring nonlinear optical properties. Although the underlying centrosymmetric crystal structure of 3D lead halide perovskites precludes the phenomenon of second harmonic generation, the third and higher-order harmonic generation are allowed. In this work, we probe the third harmonic generation (THG) from CsPbBr3 nanocrystals (NCs) and compare it to the THG from CsPbBr3 NCs with Ruddlesden-Popper planar faults (RP-CsPbBr3), formed via postsynthetic fusion-growth. The THG from CsPbBr3 NCs is negligible compared with that of RP-CsPbBr3 NCs within a wide range of femtosecond excitation wavelengths. We further compare the THG from a thin film of RP-CsPbBr3 with that of a single crystal of methylammonium lead bromide (MAPbBr3). The THG efficiency of RP-CsPbBr3 is found to be three times greater than that of MAPbBr3. An effective third-order susceptibility of the order of 10-18 m2 V-2 is obtained for a RP-CsPbBr3 film, opening up the prospect of inorganic halide perovskite NCs with planar defects for a range of nonlinear optical applications.

Breast Cancer in Jamaica: Stage, Grade and Molecular Subtype Distributions Across Age Blocks, the Implications for Screening and Treatment.

BACKGROUND: Breast cancer is the most commonly diagnosed and leading cause of cancer-related morbidity and mortality in females worldwide. Significant disparities exist in breast cancer incidence and mortalities between low- to middle- and high-income countries. The purpose of this study was to analyze the distribution of prognostic and predictive clinicopathological features of invasive breast cancer at a single institution in Jamaica across three age groups. METHODS: Data from patients diagnosed with invasive breast cancer who underwent definitive surgery between August 2017 and September 2018 were identified. The patients were divided into three age groups (< 50, 50 - 59 and > 59 years) and the distribution of tumor size, grade, molecular subtype, nodal status and anatomic stage were determined and compared with the US population registry. Comparisons of the various characteristics were performed using the Fisher's exact test. RESULTS: Ninety-nine definitive operations were performed and met the criteria for analysis. Average age at the time of diagnosis was 54 years compared to 62 years reported in the US databases. Thirty-six percent of the patients presented below age 50 years, which was twice the corresponding rate reported for Caucasian females (18%) in the USA. Fifty percent of patients in our registry had axillary lymph node metastases at presentation and they were younger than patients with negative axillary nodes (95% confidence interval (CI) -12.06 to -1.93, P = 0.007). Patients in the age group less than age 50 years were more likely to have advanced stage, high histological grade cancers compared to the older age blocks (95% CI 0.039 - 0.902, P = 0.033). CONCLUSION: Invasive breast cancer presents at an earlier age in Jamaican women and is associated with poor prognostic features such as high rates of axillary lymph node metastases, high histological grade, advanced stage, triple-negative subtypes and low luminal A subtypes.

Traumatic dislocations of the proximal tibiofibular joint: a report of two cases.

Traumatic dislocations of the proximal tibiofibular joint are rare and difficult to diagnose. They can present as an isolated case or in association with multiple injuries. They are typically classified into subluxation, anterolateral, posteromedial, and superior dislocations. We report 2 unusual dislocations (posterolateral and inferior) of the proximal tibiofibular joint, both associated with floating knee injuries. Their diagnoses are mainly based on the presence of neurovascular injuries.

Spontaneous emission rate enhancement with aperiodic Thue-Morse multilayer.

The emergence of multilayer metamaterials in the research field of enhancing spontaneous emission rates has recently received extensive attention. Previous research efforts mostly focus on periodic metal-dielectric multilayers in hyperbolic dispersion region; however, the influence of lattice order in subwavelength multilayers on spontaneous emission is rarely studied. Here, we observe the stronger Purcell enhancement of quantum dots coupled to the aperiodic metal-dielectric multilayer with Thue-Morse lattice order from elliptical to hyperbolic dispersion regions, compared to the periodic multilayer with the same metal filling ratio. This work demonstrates the potential of utilizing quasiperiodic metamaterial nanostructures to engineer the local density of states for various nanophotonic applications.