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Immune checkpoint blockade (ICB) therapy has substantially improved the outcomes of patients with many types of cancers, including renal cell carcinoma (RCC). Initially studied as monotherapy, immunotherapy-based combination regimens have improved the clinical benefit achieved by ICB monotherapy and have revolutionized RCC treatment. While biomarkers like PD-L1 and tumor mutational burden (TMB) are FDA approved as biomarkers for ICB monotherapy, there are no known biomarkers for combination immunotherapies. Here, we describe the clinical outcomes and genomic determinants of response from a phase Ib/II clinical trial on patients with advanced RCC evaluating the efficacy of lenvatinib, a multi-kinase inhibitor mainly targeting VEGFR and FGFR plus pembrolizumab, an anti-PD1 immunotherapy. Concurrent treatment with lenvatinib and pembrolizumab resulted in an objective response rate of 79% (19/24) and tumor shrinkage in 96% (23/24) of patients. While tumor mutational burden (TMB) did not predict for clinical benefit, germline HLA-I diversity strongly impacted treatment efficacy. Specifically, HLA-I evolutionary divergence (HED), which measures the breadth of a patient's immunopeptidome, was associated with both improved clinical benefit and durability of response. Our results identify lenvatinib plus pembrolizumab as a highly active treatment strategy in RCC and reveal HLA-I diversity as a critical determinant of efficacy for this combination. HED also predicted better survival in a separate cohort of patients with RCC following therapy with anti-PD-1–based combination therapy. Implications: These findings have substantial implications for RCC therapy and for understanding immunogenetic mechanisms of efficacy and warrants further investigation.

Surface modification of Fe2O3 by adding BeO was synthesized and calcined at different temperatures of 200-600 °C. The adsorbents were characterized by using XRD, N2 adsorption-desorption isotherm prior to performing CO2 adsorption and desorption studies. The CO2 adsorption data were analyzed using adsorption isotherm models such as Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich. BeO/Fe2O3-300 that calcined at 300 °C showed the most efficient adsorbent with physisorption and chemisorption were measured at 5.85 and 45.88 mg/g respectively. The CO2 adsorption notably best fitted with Freundlich isotherm with R2 = 0.9897 and calculated adsorption capacity closest to experimental data. This implies the CO2 adsorption process was governed by multilayer adsorption on the heterogeneous surface of the adsorbent. The mean free energy of adsorption (E=3.536 kJ/mol) from Dubinin-Radushkevich and heat of adsorption (bT=3.219 kJ/mol) from the Temkin model support that the adsorption process is physical phenomena.

Composite materials made of micron-sized oxide particle fillers in an epoxy resin matrix that can be molded into desired shapes are widely used for packaging radiofrequency and microwave-integrated circuits (ICs). To potentially employ these materials with millimeter-wave ICs (MMICs), quantitative knowledge of the composites’ dielectric properties across a broad millimeter-wave band is necessary. Here, we present non-destructive measurements of the complex relative permittivity, er = e′ + je″, on some possible MMIC packaging composites consisting of silica and/or alumina microsphere fillers dispersed in an epoxy matrix. Measurements using phase-sensitive transmission over the WR3 and WR5 frequency bands (140 to 325 GHz) show that e′ ranged from 3.6 for pure silica filler to 7.2 for pure alumina filler, with very little frequency dispersion. In all materials, the loss tangent tanδ = e″/e′ was between 0.01 and 0.02 in this frequency range. An analysis using the theory of two-component composites is used to extract the real permittivity of the epoxy resin. The results could be used to model performance of packaged MMICs and to design composites having a tailored value of e′.

[C40H28F3IrN5O]PF6, monoclinic, P21/c (no. 14), a = 20.2282(19) Å, b = 14.5095(11) Å, c = 12.6091(10) Å, β = 96.937(3)°, V = 3673.7(5) Å3, Z = 4, Rgt(F) = 0.0498, wRref(F2) = 0.1250, T = 107(2) K.

Integrated circuit (IC) thermoelectric generators (TEGs) fabricated by standard “65 nm” Si processing have been shown to be potentially competitive with (Bi, Sb)2Te3 TEGs in terms of maximum power generated, ${P}_{\text {max}}$ , per conduction cross-sectional area at a given temperature difference. Optimization of ${P}_{\text {max}}$ in these Si IC TEGs with respect to design and processing parameters remains an open issue. Here the dependence of ${P}_{\text {max}}$ on dopant density in Si thermopiles is examined both experimentally and by developing a simple physics-based model using empirical material parameters. Experimentally, ${P}_{\text {max}}$ improved by $\sim 1.8\times $ with increasing dopant density from ${3} \times {10}^{{17}}$ to ${4} \times {10}^{{18}}$ cm−3. Modeling shows that ${P}_{\text {max}} \propto $ thermopile figure-of-merit ZT , which scales with dopant density approximately as (density)0.24 from 1017 to 1019 cm−3. A model extrapolation to 1020 cm−3 predicts that parasitic resistance and thermal conductance will cause ${Z}$ and ${P}_{\text {max}}$ to have a maximum at densities above 1019 cm−3 and then decline at higher densities. Without parasitics ${Z}$ and ${P}_{\text {max}}$ would continue to increase roughly as (density)0.4. The results emphasize the importance of minimizing parasitics.

C13H16N2O3S, triclinic, P 1 ‾ $P\bar{1}$ (no. 2), a = 8.1998(4) Å, b = 9.1320(4) Å, c = 10.7062(6) Å, α = 106.183(5)°, β = 111.506(5)°, γ = 97.589(4)°, V = 691.27(7) Å3, Z = 2, R gt(F) = 0.0346, wR ref(F 2) = 0.0957, T = 293(2) K.

Before entering the world of superconductivity, Ted Geballe, in the 1950s, investigated the thermoelectric (TE) properties of doped crystalline silicon. Ted’s results indicated that Si has very poor thermoelectric properties, primarily because near room temperature most of the heat transport through Si is carried via phonons rather than electrons and holes. These findings ended the role of Si in TE technologies for a half-century. A decade ago, it was proposed that Si in nanowire form can have good TE properties owing to suppression of phonon heat transport by surface scattering. However, no TE device made of Si nanowires has shown useful performance characteristics. Here, we present work showing integrated circuit Si TE generators that can generate power per unit area per applied temperature difference that is competitive with the best existing TE technologies using more exotic TE materials. Our devices surpass previous Si TE work not by increasing silicon’s intrinsic TE efficiency but by exploiting modern Si processing technology to fabricate a very large number of heat harvesters per unit area. While Ted’s old work buried Si in the TE world, our results may resurrect it as a viable TE material.

Microelectronic thermoelectric generators (TEGs), which can recycle waste heat into electrical power, have applications ranging from the on-chip thermal management of integrated circuits to environmental energy sources for Internet-of-things sensors. However, the incompatibility of TEGs with silicon integrated circuit technology has prevented their broad adoption in microelectronics. Here, we report TEGs created using nanostructured silicon thermopiles fabricated on an industrial silicon complementary metal–oxide–semiconductor (CMOS) process line. These TEGs exhibit a high specific power generation capacity (up to 29 μW cm−2 K−2) near room temperature, which is competitive with typical (Bi,Sb)2(Se,Te)3-based TEGs. The high power capacity results from the ability of CMOS processing to fabricate a very high areal density of thermocouples with low packing fraction and to carefully control electrical and thermal impedances. TEG power was also found to increase significantly when thermocouple width was decreased, providing a path to further improvements. Unlike (Bi,Sb)2(Se,Te)3 TEGs, our silicon integrated circuit TEGs could be seamlessly integrated into large-scale silicon CMOS microelectronic circuits at very low marginal cost. Thermoelectric generators based on nanostructured silicon thermopiles, which are fabricated on an industrial silicon CMOS process line and are thus compatible with integrated circuit technology, exhibit a high specific power generation capacity of up to 29 μW cm−2 K−2 near room temperature.

Nano-composite polymer electrolyte (NCPE), poly(vinylidenefluoride-hexafluoropropylene)-poly(methylmethacrylate) grafted natural rubber with lithium tetrafluoroborate and zirconia (PVdF-HFP/MG49-LiBF4-ZrO2) was prepared by a facile one-pot in situ sol–gel method. The influence of zirconia nano-fillers on the electrochemical, chemical and structural properties of polymer electrolyte was investigated. The interaction of polymer electrolyte and zirconia was explored via density functional theory (DFT). Electrochemical impedance spectroscopy study showed that the optimum ionic conductivity is 2.39 × 10−3 S cm−1 (6 wt% zirconia). X-ray diffractogram results revealed a decreasing trend of crystalline phases and no lithium salt peaks were observed upon the addition of zirconia. As a result, the LiBF4 salt was well-solvated in the polymer matrix with a one-fold increase in lithium transference number. Remarkably, a good electrochemical stability was achieved at 6.9 V from a linear sweep voltammetry (LSV) analysis. Observations from the infrared spectra indicate that chemical interactions occurred at the carbonyl and fluoride functional groups and is further corroborated by DFT studies. Micrograph images showed that the zirconia nano-particles were successfully produced (7–15 nm). The nanocomposite polymer electrolyte possesses promising charge/discharge performance and has the potential to be applied in lithium-ion polymer battery.

The functionalization of N-(benzo[d]thiazol-2-yl)benzamide with a nitro (NO2) substituent influences the solid-state arrangement, absorption and fluorescence properties of these compounds. Each of these compounds crystallised in a different crystal system or space group, namely a monoclinic crystal system with P21/n and C2/c space groups for o-NO2 and m-NO2 derivatives, respectively, and an orthorhombic crystal system (Pbcn space group) for p-NO2 derivative. The o-NO2 substituent with intrinsic steric hindrance engendered a distorted geometry. Conversely, the m-NO2 derivate displayed the most planar geometry among the analogues. The solid-state architectures of these compounds were dominated by the N&minus, H&middot, &middot, N and C&minus, O intermolecular hydrogen bonds and were further stabilised by other weak interactions. The dimer synthons of the compounds were established via a pair of N&minus, N hydrogen bonds. These findings were corroborated by a Hirshfeld surface analysis and two-dimensional (2D) fingerprint plot. The interaction energies within the crystal packing were calculated (CE-B3LYP/6-31G(d,p)) and the energy frameworks were modelled by CrystalExplorer17.5. The highly distorted o-NO2 congener synthon relied mainly on the dispersion forces, which included &pi, &ndash, &pi, interactions compared to the electrostatic attractions found in m-NO2. Besides, the latter possesses an elevated asphericity character, portraying a marked directionality in the crystal array. The electrostatic and dispersion forces were regarded as the dominant factors in stabilising the crystal packing.

According to World Health Organization (WHO), the leading cause of fatalities and injuries is rear-ending collision in vehicles. The critical challenge of the technologically rich transportation system is to reduce the chances of accidents between vehicles. For this purpose, it is especially important to analyze the factors that are the cause of accidents. Based on these factors’ results, this paper presents a driver assistance system for collision avoidance. There are many factors involved in collisions in the existing literature from which we identified some factors which can affect the accident occurrence probability. However, with advancements in the technologies of autonomous vehicles, these factors can be controlled using an onboard driver assistance system. We used MATLAB’s Fuzzy Inference System Tool to analyze the categories of accident contributing factors. Fuzzy results are validated using the VOMAS agent in the NetLogo simulation model. The proposed system can inform the vehicle’s automated system when chances of an accident are higher so that the vehicle may take control from the driver. The proposed research is extremely helpful in handling various kinds of factors involved in accidents. The results of the experiments demonstrated that multi-factor-enabled vehicles could better avoid collision as compared to other vehicles.

The Re(I) complex, [Re(PyPzH)(CO)3Cl] where PyPzH = 2-(1H-pyrazol-3-yl)pyridine, was successfully synthesised and characterised with an infrared (IR), ultraviolet-visible (UV-Vis), 1H and 13C nuclear magnetic resonance (NMR) spectroscopies and X-ray crystallography. The IR spectrum featured three n(C≡O), n(N-H), n(C=N) and n(C=C) signals at (1860-2020), 3137, 1614 and 1513 cm-1, respectively. The UV-Vis spectrum of the complex exhibited ligand-centred (π®>*) electronic excitations [λmax = 227 nm, e = 1.942 x 104 M-1cm-1; lmax = 292 nm, e = 0.853 x 104 M-1cm-1] and a metal-to-ligand charge transfer (MLCT) band [lmax = 331 nm, e = 0.467 x 104 M-1cm-1]. The 13C and 1H-NMR spectra exhibited the characteristic signals of the three C≡O (189.0 – 199.0 ppm) and NH (14.84 ppm), respectively. The X-ray structure of [Re(PyPzH)(CO)3Cl] showed the crystal adopted a monoclinic system with a C2/c space group [unit cell dimensions: a = 27.7422(14) A, b = 11.1456(5) A, c = 9.2461(4) A with α = γ = 90o and β = 92.552(2)o]. Density functional theory (DFT) and time-dependent (TD) DFT calculations were performed to investigate the optimised structural geometry and electronic properties of the title complex. The results showed that the highest-occupied molecular orbital (HOMO) was predominantly found on the dπ-orbitals of Re(I), Cl and CO. While the lowest-unoccupied molecular orbital (LUMO) was located on the PyPzH moiety. The structural and photophysical properties of the [Re(PyPzH)(CO)3Cl] were established and the reaction enthalpies for the dissociation of Cl atom in the formation of [Re(PyPzH)(CO)3]• were discussed in view of its potential application for photocatalytic CO2 reduction.

Bisphenol A (BPA) is an endocrine disruptor which can bind to the oestrogen receptor. It also possesses oestrogenic, antiandrogenic, inflammatory and oxidative properties. Since bone responds to changes in sex hormones, inflammatory and oxidative status, BPA exposure could influence bone health in humans. This review aimed to summarize the current evidence on the relationship between BPA and bone health derived from cellular, animal and human studies. Exposure to BPA (0.5-12.5 µM) decreased the proliferation of osteoblast and osteoclast precursor cells and induce their apoptosis. Bisphenol AF (10 nM) enhanced transforming growth factor beta signalling but bisphenol S (10 nM) inhibited Wnt signalling involved in osteoblast differentiation in vitro. In animals, BPA and its derivatives demonstrated distinct effects in different models. In prenatal/postnatal exposure, BPA increased femoral bone mineral content in male rats (at 25 ug/kg/day) but decreased femoral mechanical strength in female mice (at 10 µg/kg/day). In oestrogen deficiency models, BPA improved bone mineral density and microstructures in aromatase knockout mice (at very high dose, 0.1% or 1.0% w/w diet) but decreased trabecular density in ovariectomized rats (at 37 or 370 ug/kg/day). In contrast, bisphenol A diglycidyl ether (30 mg/kg/day i.p.) improved bone health in normal male and female rodents and decreased trabecular separation in ovariectomized rodents. Two cross-sectional studies have been performed to examine the relationship between BPA level and bone mineral density in humans but they yielded negligible association. As a conclusion, BPA and its derivatives could influence bone health and a possible gender effect was observed in animal studies. However, its effects in humans await verification from more comprehensive longitudinal studies in the future.

The presence of two different chromophores in benzothiazole molecule namely benzothiazole and aromatic rings lead to interesting chemical and biological properties that attract more researches on the compounds. Three new benzothiazolyl-benzoythiourea compounds namely 1-(1,3-benzothiazol-2-yl)-3-(benzoylthiourea) (BBT), 1-(1,3-benzothiazol-2-yl)-3-(4-chlorobenzoylthiourea) (BBT-4Cl) and 1-(1,3-benzothiazol-2-yl)-3-(4-methoxybenzoylthiourea) (BBT-4OCH3) with different electron withdrawing substituents (R) at the para positions on the benzene ring of benzoylthiourea ring have been synthesized from the reaction of R-benzoyl isothiocyanate (R= H, Cl, and OCH3) and 2-aminobenzothiazole. The compounds were characterized by spectroscopic techniques (infrared, 1H proton NMR and UV-Vis). The IR spectra showed the frequency signals of n (C=O), n (C=S), n (N-H) at 1664-1673, 1238-1249 and 3031-3055 cm-1, respectively. The 1H proton NMR spectra showed the presence of N-H amine and amide signals in the region of (12.14-12.35) and (14.17-14.43) ppm, respectively. The proton signals of the two benzothiazole and benzoylthiourea moieties appear at 7.08-8.16 ppm. A theoretical study based on Density Functional Theory (DFT) and Time-Dependent (TD) DFT was conducted to optimize the geometrical structure and investigate the electronic properties of title compounds. The highest occupied molecular orbital (HOMO) was found on the benzothiazole moiety; while, the lowest-unoccupied molecular orbital (LUMO) was located at the benzoylthiourea fragment. The DFT optimized structures possessed an intramolecular hydrogen bonding and the types of para substituents used influenced the properties of hydrogen bonding.

A benzoylthiourea molecule namely 1,1-dibenzyl-3-(2-bromobenzoyl)thiourea (2BrBT) was synthesized and characterized by C, H, N and S elemental, mass spectrometry and spectroscopic analyses (infrared, ultraviolet-visible and nuclear magnetic resonance). The 2BrBT compound crystallized in a tetragonal system with the space group P43 and exhibits an acentric crystalline packing due to the presence of intermolecular H-bonding network that forms a self-assembly of 1D helical motif. The asymmetric delocalisation of electrons in the molecule retains its transparency throughout the visible and near-infrared region and hence, essentially propagates the macroscopic helical motif in the solid state. The highest-occupied and lowest-unoccupied molecular orbital (HOMO/LUMO) are mainly found on the thiourea moiety and the benzoylthiourea fragment, respectively and shows an optical bandgap of 3.50 eV. The influence of its geometrical characteristics to the optical properties of 2BrBT is established and discussed in view of nonlinear optical (NLO) application.

A protective conductive polymer electrolyte (PE) composed of poly(vinylidenefluoride-co-hexafluoropropylene), 49% poly(methylmethacrylate)-grafted natural rubber and lithium tetrafluoroborate (PVdF-HFP-MG49-LiBF4, also referred as PHMLi) was used as a strategic method to improve the photocatalyst stability of the dye sensitiser on a TiO2 photoanode. PHMLi was fabricated onto a ruthenium dye-sensitised TiO2 photoanode (FTO/TiO2/Ru/PHMLi) using a dip-coating technique. The COOH anchoring groups in the ruthenium dye are known to undergo hydrolysis in photoelectrochemical cell (PEC) in a direct water-splitting reaction causing the ruthenium dye to desorb from the TiO2 photoanode. Thus, PHMLi was applied to sustain the physical, chemical and photostability properties of the ruthenium dye. The PEC properties of FTO/TiO2/Ru/PHMLi were investigated using a 0.5 M KOH electrolyte. The result indicated that PHMLi protective layer exhibited the ability to retain the ruthenium dye sensitiser on the TiO2 surface and improved the overall photocatalyst stability of the PEC photoanode.

In the effort to push the high-frequency performance of electronic circuits and signal interconnects from millimeter waves to beyond 1 THz, a quantitative knowledge of complex refraction index values and dispersion in potential dielectric substrate, encapsulation, waveguide, and packaging materials becomes critical. Here we present very broadband measurements of the real and imaginary index spectra of four polymeric dielectric materials considered for use in high-frequency electronics: benzocyclobutene (BCB), polyethylene naphthalate (PEN), the photoresist SU-8, and polydimethylsiloxane (PDMS). Reflectance and transmittance spectra from ~ 3 to 75 THz were made using a Fourier transform spectrometer on freestanding material samples. These data were quantitatively analyzed, taking into account multiple partial reflections from front and back surfaces and molecular bond resonances, where applicable, to generate real and imaginary parts of the refraction index as a function of frequency. All materials showed signatures of infrared active organic molecular bond resonances between 10 and 50 THz. Low-loss transmission windows as well as anti-window bands of high dispersion and loss can be readily identified and incorporated into high-frequency design models.

Antimycobacterial agents might shorten the course of treatment by reducing the number of phenotypically tolerant bacteria if they could kill M. tuberculosis in diverse metabolic states. Here we report two chemically disparate classes of agents that kill M. tuberculosis both when it is replicating and when it is not. Under replicating conditions, the tricyclic 4-hydroxyquinolines and a barbituric acid analogue deplete intrabacterial magnesium as a mechanism of action, and for both compounds, mutations in CorA, a putative Mg2+/Co2+ transporter, conferred resistance to the compounds when M. tuberculosis was under replicating conditions but not under nonreplicating conditions, illustrating that a given compound can kill M. tuberculosis in different metabolic states by disparate mechanisms. Targeting magnesium metallostasis represents a previously undescribed antimycobacterial mode of action that might cripple M. tuberculosis in a Mg2+-deficient intraphagosomal environment of macrophages., A defining characteristic of treating tuberculosis is the need for prolonged administration of multiple drugs. This may be due in part to subpopulations of slowly replicating or nonreplicating Mycobacterium tuberculosis bacilli exhibiting phenotypic tolerance to most antibiotics in the standard treatment regimen. Confounding this problem is the increasing incidence of heritable multidrug-resistant M. tuberculosis. A search for new antimycobacterial chemical scaffolds that can kill phenotypically drug-tolerant mycobacteria uncovered tricyclic 4-hydroxyquinolines and a barbituric acid derivative with mycobactericidal activity against both replicating and nonreplicating M. tuberculosis. Both families of compounds depleted M. tuberculosis of intrabacterial magnesium. Complete or partial resistance to both chemotypes arose from mutations in the putative mycobacterial Mg2+/Co2+ ion channel, CorA. Excess extracellular Mg2+, but not other divalent cations, diminished the compounds’ cidality against replicating M. tuberculosis. These findings establish depletion of intrabacterial magnesium as an antimicrobial mechanism of action and show that M. tuberculosis magnesium homeostasis is vulnerable to disruption by structurally diverse, nonchelating, drug-like compounds.

Objective: To review cases and increase awareness in clinicians treating patients who may be taking biotin.Methods: We describe the presentation and workup of a woman with secondary progressive multiple sclerosis on high-dose biotin, with laboratory studies suggestive of thyrotoxicosis.Results: Plasma samples showed laboratory evidence of elevated thyroid hormone levels, with elevated free thyroxine >7.8 ng/dL (reference interval [RI], 0.9 to 1.7 ng/dL) and decreased thyroid-stimulating hormone

3130 Background: IMpower150 is a phase 3 study measuring the effect of carboplatin and paclitaxel (CP) combined with atezolizumab (A) and/or bevacizumab (B) in patients with advanced nonsquamous NSCLC, testing the hypothesis that anti-PD-L1 therapy may be enhanced by the blockade of VEGF. Here, we apply a machine-learning based approach to quantify the tumor micro-environment (TME) and vasculature and identify associations with clinical outcome in IMpower150. Methods: Digitized H&E images were registered onto the PathAI research platform (n=1027). Over 200K annotations from 90 pathologists were used to train convolutional neural networks (CNNs) that classify human-interpretable features (HIFs) of cells and tissue structures from images. Blood vessel compression (BVC) indices were calculated using the long versus short axes for each predicted blood vessel. HIFs were clustered to reduce redundancy, and selected features were associated with progression free survival (PFS) within each arm (ABCP, ACP, and BCP) using Cox proportional hazard models. Results: We used the trained CNNs to generate 4,534 features summarizing each patient’s histopathology and TME. After association with survival and correction for multiple comparisons we identified clusters that were significantly associated with survival in at least one arm. Among patients receiving treatments that target PD-L1 (ABCP and ACP), high lymphocyte to fibroblast ratio (LFR) was associated with improved PFS (HR=0.64 (0.51, 0.81), p < 0.001) and showed no significant association with PFS among patients treated with BCP alone (HR=1.13 (0.85, 1.51), p=0.4). Among BCP treated patients, a higher average BVC within the tumor tissue was associated with improved PFS (HR=0.67 (0.50,0.90), p=0.01) and worse PFS among patients treated with ACP (HR=1.50 (1.10,2.06), p=0.009). Conclusions: We developed a deep learning-based assay for quantifying pathology features of the TME and vasculature from H&E images. Application of this system to Impower150 identified an association between high LFR and improved PFS among patients receiving PD-L1 targeting therapy, and between low BVC and improved PFS among patients receiving BCP. These findings support the importance of the TME and vasculature in determining response to PD-L1 and VEGF-targeting therapies.

Extending tungsten contact for the most advanced nodes (≤ 7 nm) is challenging due to the growing impact of contact resistance on the overall resistance of a device and to the increasing difficulty of gapfill in features with < 20 nm critical dimensions. The paper presents a gapfill material using metalorganic chemical vapor deposition (MO-CVD) cobalt for contact plug. Highlights of new gapfill material include proven seamless, voidless gapfill and contact resistance reduction. CVD Cobalt anneal parameters are discussed that can be optimized in combination with the deposition process to achieve desired gapfill. A proprietary electron-beam imaging technology was used to qualify the cobalt fill for void-free performance. Various process flows are discussed that lead to the best-known fill and resistance reduction values.

The crystal and molecular structures of two ReI tricarbonyl complexes, namely fac-tricarbonylchlorido[1-(4-fluorocinnamoyl)-3-(pyridin-2-yl-κN)pyrazole-κN 2]rhenium(I), [ReCl(C17H12FN3O)(CO)3], (I), and fac-tricarbonylchlorido[1-(4-nitrocinnamoyl)-3-(pyridin-2-yl-κN)pyrazole-κN 2]rhenium(I) acetone monosolvate, [ReCl(C17H12ClN4O3)(CO)3]·C3H6O, (II), are reported. The complexes form centrosymmetric dimers that are linked into one-dimensional columns by C—H...Cl and N—O...H interactions in (I) and (II), respectively. C—H...Cl interactions in (II) generate two R 2 1(7) loops that merge into a single R 2 1(10) loop. These interactions involve the alkene, pyrazole and benzene rings, hence restricting the ligand rotation and giving rise to a planar conformation. Unlike (II), complex (I) exhibits a twisted conformation of the ligand and a pair of molecules forms a centrosymmetric dimer with an R 2 2(10) loop via C—H...O interactions. The unique supramolecular structures of (I) and (II) are determined by their planarity and weak interactions. The planar conformation of (II) provides a base for appreciable π–π stacking interactions compared to (I). In addition, an N—O...π interaction stabilizes the supramolecular structure of (II). We report herein the first n→π* interactions of ReI tricarbonyl complexes, which account for 0.33 kJ mol−1. Intermolecular C—H...Cl and C—H...O interactions are present in both complexes, with (II) showing a greater preference for these interactions compared to (I), with cumulative contributions of 48.7 and 41.5%, respectively. The influence of inductive (fluoro) and/or resonance (nitro) effects on the π-stacking ability was further supported by LOLIPOP (localized orbital locator-integrated π over plane) analysis. The benzene ring of (II) demonstrated a higher π-stacking ability compared to that of (I), which is supported by the intrinsic planar geometry. The HOMA (harmonic oscillator model of aromaticity) index of (I) revealed more aromaticity with respect to (II), suggesting that NO2 greatly perturbed the aromaticity. The Hirshfeld fingerprint (FP) plots revealed the preference of (II) over (I) for π–π contacts, with contributions of 6.8 and 4.4%, respectively.

Ru(II) complexes, [Ru(bpy) 2 ( m - R -L)](PF 6 ) 2 where bpy = 2,2’-bipyridyl and m - R -L= 1-( meta - R )-benzoyl-3-(pyridine-2-yl)-1H-pyrazole derivatives ( R = H, CH 3 and Cl) abbreviated as RuL, Ru( m -CH 3 -L) and Ru( m -Cl-L) complexes, respectively, were synthesized and characterized with spectroscopic techniques namely, infrared, UV-Vis and nuclear magnetic resonance (NMR), photoluminescence and mass spectroscopy. Density functional theory (DFT) and time-dependent (TD) DFT calculations were carried out to study the structural and electronic features of the molecules. These Ru(II) complexes exhibit photo-electronic properties required for a photosensitiser in a TiO 2 -catalysed photoelectrochemical (PEC) cell. In-depth understanding of the R -L fragment functionality is important to tune the photo-electronic properties of the Ru(II) complex. The highest-occupied molecular orbital (HOMO) is mainly localized at the Ru(II) centre, while the LUMO is dominantly spread across the R -L ligand. The Ru(II) complexes showed favourable metal-to-ligand charge transfer (MLCT) energy levels, which are comparably higher than the conduction band of TiO 2 to facilitate electron injection process. Among the Ru(II) complexes, Ru( m -Cl-L) comparatively possesses the highest photoluminescence quantum yield and has the potential to be applied as photosensitiser in PEC systems.

Cobalt as a material promises to change the conductor landscape in many areas, particularly logic contact and interconnect. In this paper, we focus on Cobalt as the conductor for logic interconnect — a potential Cu replacement. We demonstrate Co fill capability down to 10nm CD, and show that Co-Cu resistivity cross-over will occur below 14nm CD. Single damascene Co-ULK structures are used to establish an optimized metallization stack with robust CMP performance that has electromigration and TDDB reliability better than copper interconnect.

Molybdenum dithiolene complexes with the general formula [MoTp*(NO)(L)], where Tp* = tris(3,5-dimethylpyrazolyl)hydroborate and L = toluene-3,4-dithiolate (L1), 1,2-benzenedithiolate (L2), or 3,6-dichloro-1,2-benzenedithiolate (L3), were found to exhibit the chemical and physical properties required for a photosensitiser in a photoelectrochemical cell. These complexes were characterised using micro-elemental, spectroscopic (IR and UV–vis) and electrochemical analyses. Cyclic voltammetry (CV) was used to determine the oxidation/reduction potentials and to calculate the energy band gap. All of the complexes had an energy band gap in the range 1.45–1.48 eV, which extends far into the visible light region. A TiO2 thin film to be used as a photoanode for photoelectrochemical cells was prepared using the paste technique on a Fluorine-doped Tin Oxide (FTO) plate and characterised using scanning electron microscope (SEM) and X-ray diffractometer (XRD). The [MoTp*(NO)(L)]-doped TiO2 photoanodes were analysed photochemically in a 1.0 M NaOH electrolyte solution using SCE reference and platinum counterelectrodes. The [MoTp*(NO)(L3)]-doped TiO2 photoanode exhibited an increased photoinduced current compared with the undoped TiO2 photoanode. The Cl atoms on the dithiolene group offered a better interaction between the photosensitiser molecule and the TiO2 photocatalyst by providing a means for halogen atom-induced chemical bonding. Based on the band edge calculations and the subsequent photocurrent results, these complexes may be potential photosensitisers for use in the preparation of photoelectrodes for photoelectrochemical cells.

Mononuclearmolybdenum complex with the general formula [MoTp*(NO)I(X)], where Tp* =tris(3,5-dimethylpyrazolyl)hidroborate and X =1,4-bis(pyridin-4-ylethynyl)benzene) was found to exhibit the required chemical and physical properties as a photosensitiser in photoelectrochemical cell. The complex was structurally characterised by infrared, UV-Vis and electrochemical analysis. TiO2 electrode films were prepared by paste technique and characterised by SEM and XRD. Photoelectrochemical properties of [MoTp*(NO)I(X)]-sensitisedTiO2 photoelectrode were carried out in 1.0 M NaOH electrolyte with a SCE reference electrode and a platinum counter electrode. The [MoTp*(NO)I(X)]-sensitised TiO2 photoelectrode showed positive photoinduced current compared to unsensitised TiO2 photoelectrode.

Object Intrathecal baclofen therapy has been used successfully for intractable spasticity in children with cerebral palsy. Infections are rare, but they are potentially life threatening if complicated by bacteremia or meningitis. Treatment without removal of the system is desirable if it can be done safely and effectively. Methods The authors reviewed the records of 207 patients ranging from 3 to 18 years of age with cerebral palsy who underwent placement or revision of a baclofen pump. They identified 38 patients with suspected or documented infectious complications. Initial attempts were made to eradicate infection with the devices in situ in all patients. Methods and effectiveness of pump salvage were evaluated. Results Of the 38 patients identified, 13 (34.2%) had documented infections; 11 had deep wound/pocket empyemas and 2 had meningitis. Eight patients with deep wound infections received intravenous antibiotics alone. All required pump explantation. The remaining 3 patients underwent a washout procedure as well; the infection was cured in 1 patient. Both patients with meningitis received intravenous and intrathecal antibiotics, and both required device explantation. In addition, 25 patients (65.8%) had excessive or increasing wound erythema. No objective criteria to document a superficial infection were present. The wounds were considered suspicious and were managed with serial examinations and oral antibiotics. The erythema resolved in 24 of the 25 patients. Conclusions In general, observation, wound care, and oral antibiotics are sufficient for wounds that are suspicious for superficial infection. For deep-seated infection, antibiotic therapy alone is generally insufficient and explantation is required. Washout procedures can be considered, but failures are common.

Mitragyna speciosa is a tropical plant with narcotic effects. The antinociceptive effects of its crude extracts, bioactive compounds and structurally modified derivatives have been examined in rodent models. This review aims to summarize the evidence on the antinociceptive effects of M. speciosa and its derivatives and explore whether they can offer an alternative to morphine in pain management. Methanolic and alkaloid extracts of M. speciosa were shown to attenuate the nociceptive response in rodents. Mitragynine and 7-hydroxymitragynine offered better antinociceptive effects than crude extracts. Structurally modified derivatives of 7-hydroxymitragynine, such as MGM-9, MGM- 15, MGM-16, demonstrated superior antinociceptive effects compared to morphine. M. speciosa and its derivatives mainly act on the opioid receptor, but receptor subtypes specificity differs between each compound. The tolerance and adverse side effects of M. speciosa and its derivatives are similar with morphine. The affinity of MGM-9 on kappa-opioid receptor could potentially limit the effects of drug dependence. In conclusion, M speciosa derivatives can offer alternatives to morphine in controlling chronic pain. Structural modification of mitragynine and 7-hydroxymitragynine can generate compounds with higher potency and lesser side-effects. Human clinical trials are required to validate the use of these compounds in clinical setting.

THz region of electromagnetic spectrum has unique features making it attractive in spectroscopic studies, material inspection, tera-bit/sec communication, and biological- and non-biological-imaging applications. Owing to challenges in producing sufficiently strong signals, this region of spectrum has been exclusively served by III–V electronics or bulky cryogenic-temperature technologies such as QCLs [1]. Recently, advanced half-THz SiGe technologies and multi-element spatial power-combining techniques to increase the output power were successfully used to generate 0dBm of power at 0.53THz and −17dBm peak EIRP at 0.82THz [2–4]. Both solutions, however, suffer from low realized bandwidths (3%), limiting their utility in a slew of imaging and communication applications. Alternatively, high-quality accumulation-mode symmetric MOS varactors (SVARs) [5] in standard CMOS have been demonstrated as efficient odd-harmonic generators in broadband tripler and quintupler operating around 0.4THz [6] and 0.7THz [7], respectively. In this work, a 1.4THz multiplier chain of 10th order using MOS VARs in a 65nm standard CMOS process is demonstrated. The multiplier incorporates a new asymmetric VAR (ASVAR) for multiplication by 2 in addition to an SVAR for frequency quintupling. The circuit produces −13dBm peak EIRP at 1.33THz and operates over a setup-limited bandwidth of more than 11%. The fully integrated multiplier chain does not require any silicon lens or substrate thinning making it a compact and affordable solution for emerging THz applications.

Ru(II) bipyridyl photocatalyst with the formula, [Ru(bpy)2(o-CH3-bzpypz)](PF6)2] (Ru01) and [Ru(bpy)2(o-Cl-bzpypz)](PF6)2] (Ru02), where bpy = 2,2’-bipyridyl, o-CH3-bzpypz = (3-(pyridin-2-yl)-1H-pyrazol-1-yl)(o-tolyl)methanone and o-Cl-bzpypz = (2-chlorophenyl)(3-(pyridin-2-yl)-1H-pyrazol-1-yl)methanone, has been successfully synthesized and characterized on the basis of C, H, N elemental analysis, IR, UV-Vis and NMR spectroscopy. Both Ru(II) complexes showed Infrared stretching frequencies at 1742-1736 cm−1 v(C=O), 1605 cm−1 v(C=N) and 842-837 cm−1 v(PF). Full geometry optimization of the complex structures were carried out using DFT method with B3LYP exchange-correlation functional and 6-31G (d,p) basis-set for H, C, N, O and Cl; and LAN2LDZ basis set as effective core potential for the ruthenium centre. The highest-occupied molecular orbital (HOMO) energy levels of Ru01 and Ru02 are −5.63 and −5.55 eV, respectively. The photocatalytic properties of the Ru(II) complexes were evaluated by studying the de...

The calcipotriene/betamethasone dipropionate two-compound scalp formulation has been shown to be safe and effective in the treatment of scalp psoriasis over 8 weeks, but the patients studied were mainly White and non-Hispanic. The aim of this study was to evaluate the efficacy and safety of the two-compound scalp formulation in the treatment of scalp psoriasis in Hispanic/Latino and Black/African American patients. A total of 99 Hispanic/Latino and 78 Black/African American patients were randomized double-blind in a 3:1 ratio to 8 weeks of once daily treatment of scalp psoriasis with either the two-compound scalp formulation (n=135) or its vehicle (n=42). In the two-compound group, 71.9% of patients had cleared or minimal disease at week 8 by the investigator's global assessment compared to 40.5% in the vehicle group (odds ratio 3.30; 95% CI 1.62-6.72; P

Random telegraph switching (RTS) noise showing a slow decay in the switching rate at cryogenic temperatures which leads to the eventual extinction of the discrete noise fluctuations has been observed in the drain-source current (IDS) of small area (

A novel method of achieving a negative index of refraction in the far-infrared region using intrinsic material properties is proposed. SrTiO3 has a dielectric resonance at ~100?cm?1 that can be lowered by lowering the temperature or with Ba doping. NiO has an antiferromagnetic resonance at ~35?cm?1 that can be raised with an applied field or with Co doping. These resonance frequencies can therefore be engineered to occur at the same frequency to achieve a negative index of refraction over an interval just above the coincident resonance. We show that SrTiO3 and NiO are readily chemically compatible and non-reacting at temperatures up to 1550??C and can be formed into polycrystalline composite bodies. Epitaxial thin film heterostructures of (SrTiO3/NiO)n/MgO with n = 1, 2 have also been fabricated with very high crystal quality.

Ferruginous lime is the name given to burnt lime (CaO) coated with di-calcium ferrite (2CaO.Fe 2 O 3 ). Its high degradation strength, its resistance to hydration and its capacity for fast and complete solution of fluxes in the BOF and EAF make it extremely attractive as a steelmaking flux. The objectives of the present work were to assess the feasibility of producing ferruginous lime in a rotary-kiln-type reactor and to determine the operating conditions favourable both for the formation of a hydration resistant product and the minimisation of problems such as accretions and agglomerations within the reactor. With respect to processing conditions, the trials suggest that ferruginous lime should be generated using a peak reaction temperature of 1260 °C and allowing 45 min at greater than 1200 °C. The optimal oxide addition is 10 % (referring to mass contents) of the limestone charge to the rotary lime kiln. When subjected to short duration hydrating conditions i.e. 30 min in contact with steam at 100 °C (as per ASTM specification X6) the ferruginous lime product exhibited good resistance to hydration (relative to pure CaO) and moderate physical degradation. Laboratory tests demonstrated the significantly enhanced rate and degree of dissolution of ferruginous lime (cf. uncoated lime) in a steelmaking slag.

Intrinsic gain (AV) measurements on Si quantum well (QW) n-channel metal-oxide-semiconductor (NMOS) transistors show that these devices can have |AV| > 1 in quantum transport negative transconductance (NTC) operation at room temperature. QW NMOS devices were fabricated using an industrial 45 nm technology node process incorporating ion implanted potential barriers to define a lateral QW in the conduction channel under the gate. While NTC at room temperature arising from transport through gate-controlled QW bound states has been previously established, it was unknown whether the quantum NTC mechanism could support gain magnitude exceeding unity. Bias conditions were found giving both positive and negative AV with |AV| > 1 at room temperature. This result means that QW NMOS devices could be useful in amplifier and oscillator applications.

A photocatalytic degradation of bromothymol blue (BTB) by a ruthenium(II) complex at basic buffer of 12 has been investigated. A novel ruthenium(II) complex, [Ru (bpy)2(Phen-pBrBT)](PF6)2, where bpy = 2,2'-bipyridine, (Phen-pBrBT) = N-(p-bromobenzoyl)-N'-(1,10-phenanthrolin-5-yl)thiourea was synthesized and characterized by spectroscopic techniques namely infrared, ultraviolet-visible (UV-Vis) and nuclear magnetic resonance. The photocatalytic performance of the ruthenium(II) complex was studied in two different concentrations of bromothymol blue (2.5 × 10-5 and 10.0 × 10-5 M). Upon exposure to light source, the optical absorption of bromothymol blue decreased gradually with time in the presence of [Ru(bpy)2(Phen-pBrBT)](PF6)2. The second order kinetic model of bromothymol blue photodegradation at pH=12.00 was established. The rate of photodegradation was found to be directly proportional to the concentration of bromothymol blue in aqueous solution.

WO3 thin film was prepared by simple electrodeposition while Fe2O3 was deposited onto the WO3 layer by chemical bath deposition. Post-annealing temperature was found to have drastic effect on the photoelectrochemical performance of these films. The light absorption range of the bilayer photoelectrodes was improved from 450 nm to 525 nm. Flat band potentials of the bilayer photoelectrodes were obtained from Mott-Schottky plot and they were shifted to higher potential. Photocurrent density produced by bilayer photoelectrode annealed at 450 °C was 1.89 times greater than monolayer WO3 photoelectrode under standard illumination conditions (AM 1.5, 100 mW/cm2).

Commercially-produced hot briquetted iron (HBI) contains considerably more phosphorus than scrap. This raises the question of how much dephosphorisation can be achieved when using HBI in an electric arc furnace (EAF), or in oxygen steelmaking, and what the cost of this dephosphorisation will be. A commonly held misconception amongst EAF operators who do not currently use HBI, is that the relatively high level of phosphorus in HBI will make dephosphorisation difficult, if not impossible. The experience of EAF operators who do currently use HBI is that dephosphorisation is easily achieved, with no cost penalty, when a conventional flush slag practice is employed. The production of low phosphorus steel from a high phosphorus HBI charge, with no associated cost penalty, has been demonstrated by trials conducted at BHP’s Sydney Steel Mill and routine practice at CASIMA in Venezuela and other EAF operators.

The dissolution kinetics of dense alumina discs in calcium aluminosilicate based melts was determined with a rotating disc technique at 1560 °C to 1590 °C, under a controlled atmosphere of Ar-CO-CO2. The effects of rotation speed and the concentration of iron and manganese oxides on the dissolution rate of alumina into slags were measured by monitoring the concentration of species in the slag. Analysis of the results obtained indicated that at low concentrations of these transition metal oxides in 53 pct CaO-5 pct MgO-12 pct SiO2-30 pct Al2O3 slags, the dissolution rate is most likely controlled by mass transfer in the slag phase. The rate data obtained also showed that the addition of iron oxide or manganese oxide results in considerable increase in the mass transfer by increasing the apparent diffusivities of species in the slag. Comparison of these results with published data on the diffusivities of species in similar slags are made and practical implications of the findings are briefly discussed.

The coupling between conduction charges and the vibrational modes of the molecular lattice plays a defining role in the transport characteristics of organic semiconductors. Using electron tunneling spectroscopy, we obtain the electron--optical-phonon coupling spectrum in photodoped pentacene crystals at energies $l30\phantom{\rule{0ex}{0ex}}\mathrm{meV}$. Comparison of the tunneling spectrum to infrared absorption data on the optical phonon density of states yields the energy dependence of the electron-phonon scattering matrix element. The integrated spectral weight of the electron-phonon coupling shows that superconductivity in pentacene is likely of electron-phonon origin.

CD40 ligand (CD40L), expressed on activated T cells, binds its receptor, CD40, on dendritic cells, B cells, and monocytes/ macrophages. Human immunodeficiency virus (HIV)-infected individuals exhibit normal B-cell CD40 expression but diminished expression of CD40L on CD4 + T cells. Thus, we studied recombinant human CD40L (huCD40L) in an in vitro rhesus macaque model of acquired immunodeficiency syndrome (AIDS). huCD40L induced peripheral blood mononuclear cell (PBMC) proliferation independent of mitogenic cytokines and led to a 70% reduction in p27 production by simian immunodeficiency virus (SIV) mac239 infected PBMCs (P0.05). Reverse transcriptase-polymerase chain reaction (RT-PCR) analysis showed reduced expression of SIV gag and increased expression of interleukin (IL)-16 mRNA. Supernatants from huCD40L-stimulated PBMC and control cultures contained similar amounts of IL-16, suggesting an intracellular antiviral effect by IL-16. Phytohemagglutinin (PHA)-stimulated PBMCs similarly cultured with huCD40L showed only slight increases in chemokine production (P0.05). These results suggest that huCD40L inhibits replication (antigen and mRNA production) of SIVmac239. This response involves huCD40L induction of IL16 mRNA expression and appears to be independent of beta-chemokines.

Using a near-field scanning optical microscope (NSOM), we found non-uniformly distributed microstructural defects near the fusion boundary of bicrystal substrates. These defects depict themselves as circular dark spots in the optical transmission images. We attribute these optical features to near-surface voids at the boundary previously found in transmission electron microscopy studies. Our results show a direct link between the presence of these defects and the superconducting properties of the YBa/sub 2/Cu/sub 3/O/sub 7/ (YBCO) grain boundary Josephson junctions (GBJJs). We find that junctions that are fabricated over highly defected regions of the bicrystal substrates have lower critical temperatures and currents. The positions of defects across a junction also play a role in determine the device characteristics. Strain fields associated with these defects are most likely responsible for affecting YBCO film growth locally and junction performance. We employ an NSOM to survey these microstructural defects in bicrystals of various tilt angles and of different materials that are commonly used for fabrication of YBCO GBJJs. We find that these defects and their strain fields are the result of the bicrystal fusion process and are not intrinsic to the materials.

We have demonstrated step-flow growth mode of InN, with monolayer height terrace steps (0.281 nm), using a production-style PA-MBE system, GEN200®. The surface morphology exhibits the step-flow features on relatively large areas and the RMS roughness over an area of 5 × 5 μm2 is 1.4 nm. We also investigated the consequences of In droplets formation during the growth and we have found that the vapor-liquid-solid growth mechanism generates defective layer areas underneath droplets that have been formed early in the growth process. The Hall mobility of 1µm thick InN layers, grown in such step-flow mode is slightly higher than 1400 cm2/Vs while for other growth conditions we have obtained mobility as high as 1904 cm2/Vs at room temperature. The samples exhibit high intensity photoluminescence spectra with a band edge that shifts with free-carrier concentration. For the lowest carrier concentration of 5.6 × 1017 cm-3 we observe PL emission at ∼0.64 eV. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Low-frequency voltage noise is used to probe stochastic charge dynamics in nonmetallic boron-doped silicon. A `` $1/f$'' noise spectrum is observed down to 0.1 Hz. The noise magnitude is suppressed and the frequency dependence strengthens at low temperature. The data are inconsistent with single-particle hopping fluctuations, but are compatible with thermally activated rearrangements of configurations involving many charges. Such configurational fluctuations indicate that many-electron excitations are important to charge dynamics in the interacting regime.

The clathrate hydrate-forming capabilities of 15 hydrofluorocarbon (HFC), fluorocarbon (FC), hydrochlorofluorocarbon (HCFC) and chlorofluorocarbon (CFC) guests are reported. These molecules form st...