• Quantified Hole Concentration in AlGaN Nanowires for High-Performance Ultraviolet Emitters

      Zhao, Chao; Ebaid, Mohamed; Zhang, Huafan; Priante, Davide; Janjua, Bilal; Zhang, Daliang; Wei, Nini; Alhamoud, Abdullah; Shakfa, M. Khaled; Ng, Tien Khee; Ooi, Boon S. (Royal Society of Chemistry (RSC), 2018-05-29)
      P-type doping in wide bandgap and new classes of ultra-wide bandgap materials has long been a scientific and engineering problem. The challenges arise from the large activation energy of dopants and high densities of dislocations in materials. We report here, a significantly enhanced p-type conduction using high-quality AlGaN nanowires. For the first time, the hole concentration in Mg-doped AlGaN nanowires is quantified. The incorporation of Mg into AlGaN was verified by correlation with photoluminescence and Raman measurements. The open-circuit potential measurements further confirmed the p-type conductivity; while Mott-Schottky experiments measured a hole concentration of 1.3×1019 cm-3. These results from photoelectrochemical measurements allow us to design prototype ultraviolet (UV) light-emitting diodes (LEDs) incorporating the AlGaN quantum-disks-in-nanowire and optimized p-type AlGaN contact layer for UV-transparency. The ~335-nm LEDs exhibited a low turn-on voltage of 5 V with a series resistance of 32 Ω, due to the efficient p-type doping of the AlGaN nanowires. The bias-dependent Raman measurements further revealed the negligible self-heating of devices. This study provides an attractive solution to evaluate electrical properties of AlGaN, which is applicable to other wide bandgap nanostructures. Our results are expected to open doors to new applications for wide and ultra-wide bandgap materials.
    • Carrier dynamics of InxGa1-xN/GaN multiple quantum wells grown on (−201) β-Ga2O3 for bright vertical light emitting diodes

      Mumthaz Muhammed, Mufasila; Xu, Jian; Wehbe, Nimer; Roqan, Iman S. (The Optical Society, 2018-05-30)
      High-quality InxGa1-xN/GaN multi-quantum well (MQW) structures (0.05≤x≤0.13), are successfully grown on transparent and conductive (−201)-oriented β-Ga2O3 substrate. Scanning-transmission electron microscopy and secondary ion mass spectrometry (SIMS) show well-defined high quality MQWs, while the In and Ga compositions in the wells and the barriers are estimated by SIMS. Temperature-dependant Photoluminescence (PL) confirms high optical quality with a strong bandedge emission and negligble yellow band. time-resolved PL measurements (via above/below-GaN bandgap excitations) explain carrier dynamics, showing that the radiative recombination is predominant. Our results demonstrate that (−201)-oriented β-Ga2O3 is a strong candidate as a substrate for III-nitride-based vertical- emitting devices.
    • Ti/TaN Bilayer for Efficient Injection and Reliable AlGaN Nanowires LEDs

      Priante, Davide; Janjua, Bilal; Prabaswara, Aditya; Subedi, Ram Chandra; Elafandy, Rami T.; Lopatin, Sergei; Anjum, Dalaver H.; Zhao, Chao; Ng, Tien Khee; Ooi, Boon S. (OSA, 2018-05-07)
      Reliable operation of UV AlGaN-based nanowires-LED at high injection current was realized by incorporating a Ti-pre-orienting/TaN-diffusion-barrier bilayer, thus enhancing external quantum efficiency, and resolving the existing device degradation issue in group-III-nanowires-on-silicon devices.
    • Morphology control of anatase TiO2 for well-defined surface chemistry

      Jeantelot, Gabriel; Ould-Chikh, Samy; Sofack-Kreutzer, Julien; Abou-Hamad, Edy; Anjum, Dalaver H.; Lopatin, Sergei; Harb, Moussab; Cavallo, Luigi; Basset, Jean-Marie (Royal Society of Chemistry (RSC), 2018-05-16)
      A specific allotrope of titanium dioxide (anatase) was synthesized both with a standard thermodynamic morphology ({101}-anatase) and with a highly anisotropic morphology ({001}-anatase) dominated by the {001} facet (81%). The surface chemistry of both samples after dehydroxylation was studied by 1H NMR and FT-IR. The influence of surface fluorides on the surface chemistry was also studied by 1H NMR, FT-IR and DFT. Full attribution of the IR spectra of anatase with dominant {001} facets could be provided based on experimental data and further confirmed by DFT. Our results showed that chemisorbed H2O molecules are still present on anatase after dehydroxylation at 350 °C, and that the type of surface hydroxyls present on the {001} facet is dependent on the presence of fluorides. They also provided general insight into the nature of the surface species on both fluorinated and fluorine-free anatase. The use of vanadium oxychloride (VOCl3) allowed the determination of the accessibility of the various OH groups spectroscopically observed.
    • Artificial 3D hierarchical and isotropic porous polymeric materials

      Chisca, Stefan; Musteata, Valentina-Elena; Sougrat, Rachid; Behzad, Ali Reza; Nunes, Suzana Pereira (American Association for the Advancement of Science (AAAS), 2018-05-11)
      Hierarchical porous materials that replicate complex living structures are attractive for a wide variety of applications, ranging from storage and catalysis to biological and artificial systems. However, the preparation of structures with a high level of complexity and long-range order at the mesoscale and microscale is challenging. We report a simple, nonextractive, and nonreactive method used to prepare three-dimensional porous materials that mimic biological systems such as marine skeletons and honeycombs. This method exploits the concurrent occurrence of the self-assembly of block copolymers in solution and macrophase separation by nucleation and growth. We obtained a long-range order of micrometer-sized compartments. These compartments are interconnected by ordered cylindrical nanochannels. The new approach is demonstrated using polystyrene-b-poly(t-butyl acrylate), which can be further explored for a broad range of applications, such as air purification filters for viruses and pollution particle removal or growth of bioinspired materials for bone regeneration.
    • Understanding of the structure activity relationship of PtPd bimetallic catalysts prepared by surface organometallic chemistry and ion exchange during the reaction of iso-butane with hydrogen

      Al-Shareef, Reem A.; Harb, Moussab; Saih, Youssef; Ould-Chikh, Samy; Roldan, Manuel A.; Anjum, Dalaver H.; Guyonnet, Elodie Bile; Candy, Jean-Pierre; Jan, Deng-Yang; Abdo, Suheil F.; Aguilar-Tapia, Antonio; Proux, Olivier; Hazemann, Jean-Louis; Basset, Jean-Marie (Elsevier BV, 2018-04-25)
      Well-defined silica supported bimetallic catalysts Pt100-x Pdx were prepared by Surface Organometallic Chemistry (SOMC) and Ionic-Exchange (IE) methods. For all investigated catalysts, iso-butane reaction with hydrogen under differential conditions led to the formation of methane and propane, n-butane, and traces of iso-butylene. The total reaction rate decreased with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the experimental results in combination with DFT calculations suggested a selective coverage of Pt (1 0 0) surface by agglomerated Pd atoms like “islands”, assuming that each metal roughly keeps its intrinsic catalytic properties with relatively small electron transfer from Pt to Pd in the case of Pt-rich sample and from Pd to Pt in the case of Pd-rich sample. For the PtPd catalysts prepared by IE, the catalytic behavior could be explained by the formation of a surface alloy between Pt and Pd in the case of Pd-rich sample and by the segregation of a small amount of Pd on the surface in the case of Pt-rich sample, as demonstrated by TEM, EXAFS and DFT. The catalytic results were explained by a structure activity relationship based on the proposed mechanism of CH bond and CC bond activation and cleavage for iso-butane hydrogenolysis, isomerization, cracking and dehydrogenation.
    • Thin porphyrin composite membranes with enhanced organic solvent transport

      Phuoc, Duong; Anjum, Dalaver H.; Peinemann, Klaus-Viktor; Nunes, Suzana Pereira (Elsevier BV, 2018-05-01)
      Extending the stability of polymeric membranes in organic solvents is important for applications in chemical and pharmaceutical industry. Thin-film composite membranes with enhanced solvent permeance are proposed, using porphyrin as a building block. Hybrid polyamide films are formed by interfacial polymerization of 5,10,15,20-(tetra-4-aminophenyl)porphyrin/m-phenylene diamine (MPD) mixtures with trimesoyl chloride. Porphyrin is a non-planar molecule, containing a heterocyclic tetrapyrrole unit. Its incorporation into a polyamide film leads to higher free volume than that of a standard polyamide film. Polyamide films derived from porphyrin and MPD amines with a fixed total amine concentration of 1wt% and various porphyrin/MPD ratios were fabricated and characterized. The porphyrin/MPD polyamide film was complexed with Cu(II), due to the binding capacity of porphyrin to metal ions. By coupling scanning transmission electron microscopy (STEM) with electron energy-loss spectroscopy (EELS), Cu mapping was obtained, revealing the distribution of porphyrin in the interfacial polymerized layer. By using porphyrin as amine-functionalized monomer a membrane with thin selective skin and enhanced solvent transport is obtained, with good dye selectivity in the nanofiltration range. For instance, an ultra-fast hexane permeance, 40-fold increased, was confirmed when using 0.5/0.5 porphyrin/MPD mixtures, instead of only MPD as amine monomer. A rejection of 94.2% Brilliant Blue R (826g/mol) in methanol was measured.
    • Predicting octane number using nuclear magnetic resonance spectroscopy and artificial neural networks

      Abdul Jameel, Abdul Gani; Oudenhoven, Vincent Van; Emwas, Abdul-Hamid M.; Sarathy, Mani (American Chemical Society (ACS), 2018-04-17)
      Machine learning algorithms are attracting significant interest for predicting complex chemical phenomenon. In this work, a model to predict research octane number (RON) and motor octane number (MON) of pure hydrocarbons, hydrocarbon-ethanol blends and gasoline-ethanol blends has been developed using artificial neural networks (ANN) and molecular parameters from 1H nuclear Magnetic Resonance (NMR) spectroscopy. RON and MON of 128 pure hydrocarbons, 123 hydrocarbon-ethanol blends of known composition and 30 FACE (fuels for advanced combustion engines) gasoline-ethanol blends were utilized as a dataset to develop the ANN model. The effect of weight % of seven functional groups including paraffinic CH3 groups, paraffinic CH2 groups, paraffinic CH groups, olefinic -CH=CH2 groups, naphthenic CH-CH2 groups, aromatic C-CH groups and ethanolic OH groups on RON and MON was studied. The effect of branching (i.e., methyl substitution), denoted by a parameter termed as branching index (BI), and molecular weight (MW) were included as inputs along with the seven functional groups to predict RON and MON. The topology of the developed ANN models for RON (9-540-314-1) and MON (9-340-603-1) have two hidden layers and a large number of nodes, and was validated against experimentally measured RON and MON of pure hydrocarbons, hydrocarbon-ethanol and gasoline-ethanol blends; a good correlation (R2=0.99) between the predicted and the experimental data was obtained. The average error of prediction for both RON and MON was found to be 1.2 which is close to the range of experimental uncertainty. This shows that the functional groups in a molecule or fuel can be used to predict its ON, and the complex relationship between them can be captured by tools like ANN.
    • Porous Porphyrin-Based Organosilica Nanoparticles for NIR Two-Photon Photodynamic Therapy and Gene Delivery in Zebrafish

      Mauriello Jimenez, Chiara; Aggad, Dina; Croissant, Jonas G.; Tresfield, Karen; Laurencin, Danielle; Berthomieu, Dorothée; Cubedo, Nicolas; Rossel, Mireille; Alsaiari, Shahad K.; Anjum, Dalaver H.; Sougrat, Rachid; Roldan-Gutierrez, Manuel A.; Richeter, Sébastien; Oliviero, Erwan; Raehm, Laurence; Charnay, Clarence; Cattoën, Xavier; Clément, Sébastien; Wong Chi Man, Michel; Maynadier, Marie; Chaleix, Vincent; Sol, Vincent; Garcia, Marcel; Gary-Bobo, Magali; Khashab, Niveen M.; Bettache, Nadir; Durand, Jean-Olivier (Wiley-Blackwell, 2018-03-30)
      Periodic mesoporous organosilica nanoparticles emerge as promising vectors for nanomedicine applications. Their properties are very different from those of well-known mesoporous silica nanoparticles as there is no silica source for their synthesis. So far, they have only been synthesized from small bis-silylated organic precursors. However, no studies employing large stimuli-responsive precursors have been reported on such hybrid systems yet. Here, the synthesis of porphyrin-based organosilica nanoparticles from a large octasilylated metalated porphyrin precursor is described for applications in near-infrared two-photon-triggered spatiotemporal theranostics. The nanoparticles display unique interconnected large cavities of 10-80 nm. The framework of the nanoparticles is constituted with J-aggregates of porphyrins, which endows them with two-photon sensitivity. The nanoparticle efficiency for intracellular tracking is first demonstrated by the in vitro near-infrared imaging of breast cancer cells. After functionalization of the nanoparticles with aminopropyltriethoxysilane, two-photon-excited photodynamic therapy in zebrafish is successfully achieved. Two-photon photochemical internalization in cancer cells of the nanoparticles loaded with siRNA is also performed for the first time. Furthermore, siRNA targeting green fluorescent protein complexed with the nanoparticles is delivered in vivo in zebrafish embryos, which demonstrates the versatility of the nanovectors for biomedical applications.
    • Carrier Transport and Recombination in Efficient “All-Small-Molecule” Solar Cells with the Nonfullerene Acceptor IDTBR

      Liang, Ru-Ze; Babics, Maxime; Savikhin, Victoria; Zhang, Weimin; Le Corre, Vincent M.; Lopatin, Sergei; Kan, Zhipeng; Firdaus, Yuliar; Liu, Shengjian; McCulloch, Iain; Toney, Michael F.; Beaujuge, Pierre (Wiley-Blackwell, 2018-04-03)
      Reaching device efficiencies that can rival those of polymer-fullerene Bulk Heterojunction (BHJ) solar cells (>10%) remains challenging with the
    • A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

      Maity, Niladri; Barman, Samir; Minenkov, Yury; Ould-Chikh, Samy; Abou-Hamad, Edy; Ma, Tao; Qureshi, Ziyauddin; Cavallo, Luigi; D'Elia, Valerio; Gates, Bruce C.; Basset, Jean-Marie (American Chemical Society (ACS), 2018-02-15)
      A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)(CH-Bu)] was prepared by treatment of highly dehydroxylated silica (SiO: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt][W(=O)(CH-Bu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.
    • Current Controlled Magnetization Switching in Cylindrical Nanowires for High-Density 3D Memory Applications

      Mohammed, Hanan; Corte-León, Hector; Ivanov, Yurii P.; Lopatin, Sergei; Moreno, Julian A.; Chuvilin, Andrey; Salimath, Akshaykumar; Manchon, Aurelien; Kazakova, Olga; Kosel, Jürgen (arXiv, 2018-04-18)
      A next-generation memory device utilizing a three-dimensional nanowire system requires the reliable control of domain wall motion. In this letter, domain walls are studied in cylindrical nanowires consisting of alternating segments of cobalt and nickel. The material interfaces acting as domain wall pinning sites, are utilized in combination with current pulses, to control the position of the domain wall, which is monitored using magnetoresistance measurements. Magnetic force microscopy results further confirm the occurrence of current assisted domain wall depinning. Data bits are therefore shifted along the nanowire by sequentially pinning and depinning a domain wall between successive interfaces, a requirement necessary for race-track type memory devices. We demonstrate that the direction, amplitude and duration of the applied current pulses determine the propagation of the domain wall across pinning sites. These results demonstrate a multi-bit cylindrical nanowire device, utilizing current assisted data manipulation. The prospect of sequential pinning and depinning in these nanowires allows the bit density to increase by several Tbs, depending on the number of segments within these nanowires.
    • High Dehumidification Performance of Amorphous Cellulose Composite Membranes prepared from Trimethylsilyl Cellulose

      Puspasari, Tiara; Akhtar, Faheem Hassan; Ogieglo, Wojciech; Alharbi, Ohoud; Peinemann, Klaus-Viktor (Royal Society of Chemistry (RSC), 2018-04-11)
      Cellulose is widely regarded as an environmentally friendly, natural and low cost material which can significantly contribute the sustainable economic growth. In this study, cellulose composite membranes were prepared via regeneration of trimethylsilyl cellulose (TMSC), an easily synthesized cellulose derivative. The amorphous hydrophilic feature of the regenerated cellulose enabled fast permeation of water vapour. The pore-free cellulose layer thickness was adjustable by the initial TMSC concentration and acted as an efficient gas barrier. As a result, a 5,000 GPU water vapour transmission rate (WVTR) at the highest ideal selectivity of 1.1 x 106 was achieved by the membranes spin coated from a 7% (w/w) TMSC solution. The membranes maintained a 4,000 GPU WVTR with selectivity of 1.1 x 104 in the mixed-gas experiments, surpassing the performances of the previously reported composite membranes. This study provides a simple way to not only produce high performance membranes but also to advance cellulose as a low-cost and sustainable membrane material for dehumidification applications.
    • Atomic Scale Modulation of Self-Rectifying Resistive Switching by Interfacial Defects

      Wu, Xing; Yu, Kaihao; Cha, Dong Kyu; Bosman, Michel; Raghavan, Nagarajan; Zhang, Xixiang; Li, Kun; Liu, Qi; Sun, Litao; Pey, Kinleong (Wiley, 2018-04-14)
      Higher memory density and faster computational performance of resistive switching cells require reliable array‐accessible architecture. However, selecting a designated cell within a crossbar array without interference from sneak path currents through neighboring cells is a general problem. Here, a highly doped n++ Si as the bottom electrode with Ni‐electrode/HfOx/SiO2 asymmetric self‐rectifying resistive switching device is fabricated. The interfacial defects in the HfOx/SiO2 junction and n++ Si substrate result in the reproducible rectifying behavior. In situ transmission electron microscopy is used to quantitatively study the properties of the morphology, chemistry, and dynamic nucleation–dissolution evolution of the chains of defects at the atomic scale. The spatial and temporal correlation between the concentration of oxygen vacancies and Ni‐rich conductive filament modifies the resistive switching effect. This study has important implications at the array‐level performance of high density resistive switching memories.
    • Ni–Sn-Supported ZrO2 Catalysts Modified by Indium for Selective CO2 Hydrogenation to Methanol

      Hengne, Amol Mahalingappa; Samal, Akshaya Kumar; Enakonda, Linga Reddy; Harb, Moussab; Gevers, Lieven; Anjum, Dalaver H.; Hedhili, Mohamed N.; Saih, Youssef; Huang, Kuo-Wei; Basset, Jean-Marie (American Chemical Society (ACS), 2018-04-02)
      Ni and NiSn supported on zirconia (ZrO2) and on indium (In)-incorporated zirconia (InZrO2) catalysts were prepared by a wet chemical reduction route and tested for hydrogenation of CO2 to methanol in a fixed-bed isothermal flow reactor at 250 °C. The mono-metallic Ni (5%Ni/ZrO2) catalysts showed a very high selectivity for methane (99%) during CO2 hydrogenation. Introduction of Sn to this material with the following formulation 5Ni5Sn/ZrO2 (5% Ni-5% Sn/ZrO2) showed the rate of methanol formation to be 0.0417 μmol/(gcat·s) with 54% selectivity. Furthermore, the combination NiSn supported on InZrO2 (5Ni5Sn/10InZrO2) exhibited a rate of methanol formation 10 times higher than that on 5Ni/ZrO2 (0.1043 μmol/(gcat·s)) with 99% selectivity for methanol. All of these catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy, CO2-temperature-programmed desorption, and density functional theory (DFT) studies. Addition of Sn to Ni catalysts resulted in the formation of a NiSn alloy. The NiSn alloy particle size was kept in the range of 10–15 nm, which was evidenced by HRTEM study. DFT analysis was carried out to identify the surface composition as well as the structural location of each element on the surface in three compositions investigated, namely, Ni28Sn27, Ni18Sn37, and Ni37Sn18 bimetallic nanoclusters, and results were in agreement with the STEM and electron energy-loss spectroscopy results. Also, the introduction of “Sn” and “In” helped improve the reducibility of Ni oxide and the basic strength of catalysts. Considerable details of the catalytic and structural properties of the Ni, NiSn, and NiSnIn catalyst systems were elucidated. These observations were decisive for achieving a highly efficient formation rate of methanol via CO2 by the H2 reduction process with high methanol selectivity.
    • Phosphine Plasma Activation of α-Fe 2 O 3 for High Energy Asymmetric Supercapacitors

      Liang, Hanfeng; Xia, Chuan; Emwas, Abdul-Hamid M.; Anjum, Dalaver H.; Miao, Xiaohe; Alshareef, Husam N. (Elsevier BV, 2018-04-12)
      We report a phosphine (PH3) plasma activation strategy for significantly boosting the electrochemical performance of supercapacitor electrodes. Using Fe2O3 as a demonstration, we show that the plasma activation simultaneously improves the conductivity, creates atomic-scale vacancies (defects), as well as increases active surface area, and thus leading to a greatly enhanced performance with a high areal capacitance of 340 mF cm-2 at 1 mA cm-2, compared to 66 mF cm-2 of pristine Fe2O3. Moreover, the asymmetric supercapacitor devices based on plasma-activated Fe2O3 anodes and electrodeposited MnO2 cathodes can achieve a high stack energy density of 0.42 mWh cm-3 at a stack power density of 10.3 mW cm-3 along with good stability (88% capacitance retention after 9000 cycles at 10 mA cm-2). Our work provides a simple yet effective strategy to greatly enhance the electrochemical performance of Fe2O3 anodes and to further promote their application in asymmetric supercapacitors.
    • Impacts of doping on epitaxial germanium thin film quality and Si-Ge interdiffusion

      Zhou, Guangnan; Lee, Kwang Hong; Anjum, Dalaver H.; Zhang, Qiang; Zhang, Xixiang; Tan, Chuan Seng; Xia, Guangrui (The Optical Society, 2018-04-03)
      Ge-on-Si structures with three different dopants (P, As and B) and those without intentional doping were grown, annealed and characterized by several different material characterization methods. All samples have a smooth surface (roughness < 1.5 nm), and the Ge films are almost entirely relaxed. B doped Ge films have threading dislocations above 1 × 10 cm, while P and As doping can reduce the threading dislocation density to be less than 10 cm without annealing. The interdiffusion of Si and Ge of different films have been investigated experimentally and theoretically. A quantitative model of Si-Ge interdiffusion under extrinsic conditions across the full x range was established including the dislocationmediated diffusion. The Kirkendall effect has been observed. The results are of technical significance for the structure, doping, and process design of Ge-on-Si based devices, especially for photonic applications.
    • Exploiting the interactions between the ruthenium Hoveyda–Grubbs catalyst and Al-modified mesoporous silica: the case of SBA15 vs. KCC-1

      Werghi, Baraa; Pump, Eva; Tretiakov, Mykyta; Abou-Hamad, Edy; Gurinov, Andrei; Doggali, Pradeep; Anjum, Dalaver H.; Cavallo, Luigi; Bendjeriou-Sedjerari, Anissa; Basset, Jean-Marie (Royal Society of Chemistry (RSC), 2018-03-05)
      Immobilization of the 2 generation Hoveyda-Grubbs catalyst HG-II onto well-ordered 2D hexagonal (SBA15) and 3D fibrous (KCC-1) mesostructured silica, which contained tetra-coordinated Al, has been investigated through the Surface Organometallic Chemistry (SOMC) methodology. The main interest of this study lies in the peculiarity of the silica supports, which display a well-defined tetrahedral aluminum hydride site displaying a strong Lewis acid character, [(Si-O-Si)(Si-O-)Al-H]. The resulting supported Hoveyda-Grubbs catalysts have been fully characterized by advanced solid state characterization techniques (FT-IR, H and C solid state NMR, DNP-SENS, EF-TEM...). Together with DFT calculations, the immobilization of HG-II does not occur through the formation of a covalent bond between the complex and the Al-modified mesoporous silica as expected, but through an Al⋯Cl-[Ru]-coordination. It is not surprising that in functionalized olefin metathesis of diethyldiallyl malonate, DEDAM (liquid phase), leaching of the catalyst is observed which is not the case in non-functionalized olefin metathesis of propene (gas phase). Besides, the results obtained in propene metathesis with HG-II immobilized either on SBA15 (d = 6 nm) or KCC-1 (d = 4 or 8 nm) highlight the importance of the accessibility of the catalytic site. Therefore, we demonstrate that KCC-1 is a promising and suitable 3D mesoporous support to overcome the diffusion of reactants into the porous network of heterogeneous catalysts.
    • A minimalist functional group (MFG) approach for surrogate fuel formulation

      Abdul Jameel, Abdul Gani; Naser, Nimal; Issayev, Gani; Touitou, Jamal; Ghosh, Manik Kumer; Emwas, Abdul-Hamid M.; Farooq, Aamir; Dooley, Stephen; Sarathy, Mani (Elsevier BV, 2018-03-20)
      Surrogate fuel formulation has drawn significant interest due to its relevance towards understanding combustion properties of complex fuel mixtures. In this work, we present a novel approach for surrogate fuel formulation by matching target fuel functional groups, while minimizing the number of surrogate species. Five key functional groups; paraffinic CH, paraffinic CH, paraffinic CH, naphthenic CH–CH and aromatic C–CH groups in addition to structural information provided by the Branching Index (BI) were chosen as matching targets. Surrogates were developed for six FACE (Fuels for Advanced Combustion Engines) gasoline target fuels, namely FACE A, C, F, G, I and J. The five functional groups present in the fuels were qualitatively and quantitatively identified using high resolution H Nuclear Magnetic Resonance (NMR) spectroscopy. A further constraint was imposed in limiting the number of surrogate components to a maximum of two. This simplifies the process of surrogate formulation, facilitates surrogate testing, and significantly reduces the size and time involved in developing chemical kinetic models by reducing the number of thermochemical and kinetic parameters requiring estimation. Fewer species also reduces the computational expenses involved in simulating combustion in practical devices. The proposed surrogate formulation methodology is denoted as the Minimalist Functional Group (MFG) approach. The MFG surrogates were experimentally tested against their target fuels using Ignition Delay Times (IDT) measured in an Ignition Quality Tester (IQT), as specified by the standard ASTM D6890 methodology, and in a Rapid Compression Machine (RCM). Threshold Sooting Index (TSI) and Smoke Point (SP) measurements were also performed to determine the sooting propensities of the surrogates and target fuels. The results showed that MFG surrogates were able to reproduce the aforementioned combustion properties of the target FACE gasolines across a wide range of conditions. The present MFG approach supports existing literature demonstrating that key functional groups are responsible for the occurrence of complex combustion properties. The functional group approach offers a method of understanding the combustion properties of complex mixtures in a manner which is independent, yet complementary, to detailed chemical kinetic models. The MFG approach may be readily extended to formulate surrogates for other complex fuels.
    • Proteome-level assessment of origin, prevalence and function of Leucine-Aspartic Acid (LD) motifs

      Alam, Tanvir; Alazmi, Meshari; Naser, Rayan Mohammad Mahmoud; Huser, Franceline; Momin, Afaque Ahmad Imtiyaz; Walkiewicz, Katarzyna Wiktoria; Canlas, Christian; Huser, Raphaël; Ali, Amal J.; Merzaban, Jasmeen; Bajic, Vladimir B.; Gao, Xin; Arold, Stefan T. (Cold Spring Harbor Laboratory, 2018-03-11)
      Short Linear Motifs (SLiMs) contribute to almost every cellular function by connecting appropriate protein partners. Accurate prediction of SLiMs is difficult due to their shortness and sequence degeneracy. Leucine-aspartic acid (LD) motifs are SLiMs that link paxillin family proteins to factors controlling (cancer) cell adhesion, motility and survival. The existence and importance of LD motifs beyond the paxillin family is poorly understood. To enable a proteome-wide assessment of these motifs, we developed an active-learning based framework that iteratively integrates computational predictions with experimental validation. Our analysis of the human proteome identified a dozen proteins that contain LD motifs, all being involved in cell adhesion and migration, and revealed a new type of inverse LD motif consensus. Our evolutionary analysis suggested that LD motif signalling originated in the common unicellular ancestor of opisthokonts and amoebozoa by co-opting nuclear export sequences. Inter-species comparison revealed a conserved LD signalling core, and reveals the emergence of species-specific adaptive connections, while maintaining a strong functional focus of the LD motif interactome. Collectively, our data elucidate the mechanisms underlying the origin and adaptation of an ancestral SLiM.