Studio delle proprieta ottiche ed elettriche di dispositivi led a confinamento quantico

In questa tesi viene descritto il funzionamento delle sorgenti di luce LED (Light Emitting Diode) a confinamento quantico, che rappresentano la nuova frontiera dell'illuminazione ad alta efficienza e durata. Nei capitoli introduttivi è descritta brevemente la storia dei LEDs dalla loro invenzione agli sviluppi più recenti. Il funzionamento di tali dispositivi fotonici è spiegato a partire dal concetto di sorgente di luce per elettroluminescenza, con particolare riferimento alle eterostrutture a confinamento quantico bidimensionale (quantum wells). I capitoli centrali riguardano i nitruri dei gruppi III-V, le cui caratteristiche e proprietà hanno permesso di fabbricare LEDs ad alta efficienza e ampio spettro di emissione, soprattutto in relazione al fatto che i LEDs a nitruri dei gruppi III-V emettono luce anche in presenza di alte densità di difetti estesi, nello specifico dislocazioni. I capitoli successivi sono dedicati alla presentazione del lavoro sperimentale svolto, che riguarda la caratterizzazione elettrica, ottica e strutturale di LEDs a confinamento quantico basati su nitruri del gruppo III-V GaN e InGaN, cresciuti nei laboratori di Cambridge dal Center for Gallium Nitride. Lo studio ha come obiettivo finale il confronto dei risultati ottenuti su LEDs con la medesima struttura epitassiale, ma differente densità di dislocazioni, allo scopo di comprendere meglio il ruolo che tali difetti estesi ricoprono nella determinazione dell'effcienza delle sorgenti di luce LED. L’ultimo capitolo riguarda la diffrazione a raggi X dal punto di vista teorico, con particolare attenzione ai metodi di valutazioni dello strain reticolare nei wafer a nitruri, dal quale dipende la densità di dislocazioni.

Design, Synthesis and Characterization of N-Containing Organic Compounds

The needed of new intermediates/products for screening in the fields of drug discovery and material science is the driving force behind the development of new methodologies and technologies. Organic scaffolds are privileged targets for this scouting. Among them a priority place must be attributed to those including nitrogen functionalities in their scaffolds. It comes out that new methodologies, allowing the introduction of the nitrogen atom for the synthesis of an established target or for the curiosity driven researches, will always be welcome. The target of this PhD Thesis’ work is framed within this goal. Accordingly, Chapter 1 reports the preparation of new N-Heteroarylmethyl 3-carboxy-5-hydroxy piperidine scaffold, as potential and selective α-glucosidase inhibitors. The proposed reversible uncompetitive mechanism of inhibition makes them attractive as interesting candidate for drug development. Chapter 2 is more environmentally method-driven research. Eco-friendly studies on the synthesis of enantiomerically pure 1,4-dihydropyridines using “solid” ammonia (magnesium nitride) is reported via classical Hantzch method. Chapter 3 and Chapter 4 may be targeted as the core of the Thesis’s research work. Chapter 3 reports the studies addressed to the synthesis of N-containing heterocycles by using N-trialkylsilylimine/hetero-Diels–Alder (HAD) approach. New eco-friendly methodology as MAOS (Microwave Assisted Organic Synthesis) has been used as witness of our interest to a sustainable chemistry. Theoretical calculations were adopted to fully clarify the reaction mechanism. Chapter 4 is dedicated to picture the most recent studies performed on the application of N-Metallo-ketene imines (metallo= Si, Sn, Al), relatively new intermediates which are becoming very popular, in the preparation of highly functionalized N-containing derivatives, accordingly to the Thesis’ target. Derivatives obtained are designed in such a way that they could be of interest in the field of drug and new material chemistry.

Nonlinear Characterization and Modelling of GaN HEMTs for Microwave Power Amplifier Applications

Semiconductors technologies are rapidly evolving driven by the need for higher performance demanded by applications. Thanks to the numerous advantages that it offers, gallium nitride (GaN) is quickly becoming the technology of reference in the field of power amplification at high frequency. The RF power density of AlGaN/GaN HEMTs (High Electron Mobility Transistor) is an order of magnitude higher than the one of gallium arsenide (GaAs) transistors. The first demonstration of GaN devices dates back only to 1993. Although over the past few years some commercial products have started to be available, the development of a new technology is a long process. The technology of AlGaN/GaN HEMT is not yet fully mature, some issues related to dispersive phenomena and also to reliability are still present. Dispersive phenomena, also referred as long-term memory effects, have a detrimental impact on RF performances and are due both to the presence of traps in the device structure and to self-heating effects. A better understanding of these problems is needed to further improve the obtainable performances. Moreover, new models of devices that take into consideration these effects are necessary for accurate circuit designs. New characterization techniques are thus needed both to gain insight into these problems and improve the technology and to develop more accurate device models. This thesis presents the research conducted on the development of new charac- terization and modelling methodologies for GaN-based devices and on the use of this technology for high frequency power amplifier applications.

A biomimetic model membrane system on oxidic surfaces designed for the investigation of cytochrome c oxidase and other membrane proteins by fluorescence and waveguide spectroscopy

Die transmembrane Potenzialdifferenz Δφm ist direkt mit der katalytischen Aktivität der Cytochrom c Oxidase (CcO) verknüpft. Die CcO ist das terminale Enzym (Komplex IV) in der Atmungskette der Mitochondrien. Das Enzym katalysiert die Reduktion von O2 zu 2 H2O. Dabei werden Elektronen vom natürlichen Substrat Cytochrom c zur CcO übertragen. Der Eleltronentransfer innerhalb der CcO ist an die Protonentranslokation über die Membran gekoppelt. Folglich bildet sich über der inneren Membrane der Mitochondrien eine Differenz in der Protonenkonzentration. Zusätzlich wird eine Potenzialdifferenz Δφm generiert.rnrnDas Transmembranpotenzial Δφm kann mit Hilfe der Fluoreszenzspektroskopie unter Einsatz eines potenzialemfindlichen Farbstoffs gemessen werden. Um quantitative Aussagen aus solchen Untersuchungen ableiten zu können, müssen zuvor Kalibrierungsmessungen am Membransystem durchgeführt werden.rnrnIn dieser Arbeit werden Kalibrierungsmessungen von Δφm in einer Modellmembrane mit inkorporiertem CcO vorgestellt. Dazu wurde ein biomimetisches Membransystem, die Proteinverankerte Doppelschicht (protein-tethered Bilayer Lipid Membrane, ptBLM), auf einem transparenten, leitfähigem Substrat (Indiumzinnoxid, ITO) entwickelt. ITO ermöglicht den simultanen Einsatz von elektrochemischen und Fluoreszenz- oder optischen wellenleiterspektroskopischen Methoden. Das Δφm in der ptBLM wurde durch extern angelegte, definierte elektrische Spannungen induziert. rnrnEine dünne Hydrogelschicht wurde als "soft cushion" für die ptBLM auf ITO eingesetzt. Das Polymernetzwerk enthält die NTA Funktionsgruppen zur orientierten Immobilisierung der CcO auf der Oberfläche der Hydrogels mit Hilfe der Ni-NTA Technik. Die ptBLM wurde nach der Immobilisierung der CcO mittels in-situ Dialyse gebildet. Elektrochemische Impedanzmessungen zeigten einen hohen elektrischen Widerstand (≈ 1 MΩ) der ptBLM. Optische Wellenleiterspektren (SPR / OWS) zeigten eine erhöhte Anisotropie des Systems nach der Bildung der Doppellipidschicht. Cyklovoltammetriemessungen von reduziertem Cytochrom c bestätigten die Aktivität der CcO in der Hydrogel-gestützten ptBLM. Das Membranpotenzial in der Hydrogel-gestützten ptBLM, induziert durch definierte elektrische Spannungen, wurde mit Hilfe der ratiometrischen Fluoreszenzspektroskopie gemessen. Referenzmessungen mit einer einfach verankerten Dopplellipidschicht (tBLM) lieferten einen Umrechnungsfaktor zwischen dem ratiometrischen Parameter Rn und dem Membranpotenzial (0,05 / 100 mV). Die Nachweisgrenze für das Membranpotenzial in einer Hydrogel-gestützten ptBLM lag bei ≈ 80 mV. Diese Daten dienen als gute Grundlage für künftige Untersuchungen des selbstgenerierten Δφm der CcO in einer ptBLM.

Sintesi e caratterizzazione di nanoparticelle di ossido di stagno dopate

In the last years, new materials have been developed in the broad area of nanoscience. Among them, an emergent class characterized by excellent electrical conductivity properties as well as high optical transmittance in the visible region are TCOs (Transparent Conducting Oxides). Due to their versatile properties, they have found many applications in a lot of optoelectronic devices, such as solar cells, liquid crystal displays, touch-panel displays, gas sensors, to cite a few examples. Different research groups have studied and characterized the TCOs. In this context, a new synthetic method has been developed to produce FTO nanocrystals (Fluorine-doped Tin Oxide NCs) in Prof. Pinna’s lab at the Humboldt University in Berlin. FTO belongs to the TCO category, and they have been studied as a promising alternative to ITO NCs (Indium Tin Oxide) which represent the standard TCO material in terms of properties and performances. In this work, FTO NCs have been synthesized using the “benzyl alcohol route” (a non-aqueous sol-gel method) via microwave, which permits to produce FTO particles with good properties as revealed by the characterizations performed, employing a cheap, fast and clean method.

Polimeri metacrilici contenenti ferrocene: sintesi mediante ATRP e proprietà

An investigation on the synthesis and properties of ferrocene-containing methacrylate monomer and polymer was carried out. Block copolymers of Ferrocenylmethyl Methacrylate with methyl, butil and esil methacrylate, were also prepared. The side-chain ferrocene-containing polymers and copolymers were prepared via atom transfer radical polymerization (ATRP). The glass transition temperature (Tg) values of the polymers and copolymers were measured by differential scan calorimetry (DSC).The thermal degradation behavior of copolymers was also studied and compared with the respective homopolymers. Cyclic voltammetry was employed to study the electrochemical properties. Preliminar electrochemical studies with a glassy carbon and Indium Tin Oxide electrodes modified with ferrocene-polymer conducted in aqueous and organic media are reported.

Nanocrystalline Silicon Based Films for Renewable Energy Applications

The present thesis is focused on the study of innovative Si-based materials for third generation photovoltaics. In particular, silicon oxi-nitride (SiOxNy) thin films and multilayer of Silicon Rich Carbide (SRC)/Si have been characterized in view of their application in photovoltaics. SiOxNy is a promising material for applications in thin-film solar cells as well as for wafer based silicon solar cells, like silicon heterojunction solar cells. However, many issues relevant to the material properties have not been studied yet, such as the role of the deposition condition and precursor gas concentrations on the optical and electronic properties of the films, the composition and structure of the nanocrystals. The results presented in the thesis aim to clarify the effects of annealing and oxygen incorporation within nc-SiOxNy films on its properties in view of the photovoltaic applications. Silicon nano-crystals (Si NCs) embedded in a dielectric matrix were proposed as absorbers in all-Si multi-junction solar cells due to the quantum confinement capability of Si NCs, that allows a better match to the solar spectrum thanks to the size induced tunability of the band gap. Despite the efficient solar radiation absorption capability of this structure, its charge collection and transport properties has still to be fully demonstrated. The results presented in the thesis aim to the understanding of the transport mechanisms at macroscopic and microscopic scale. Experimental results on SiOxNy thin films and SRC/Si multilayers have been obtained at macroscopical and microscopical level using different characterizations techniques, such as Atomic Force Microscopy, Reflection and Transmission measurements, High Resolution Transmission Electron Microscopy, Energy-Dispersive X-ray spectroscopy and Fourier Transform Infrared Spectroscopy. The deep knowledge and improved understanding of the basic physical properties of these quite complex, multi-phase and multi-component systems, made by nanocrystals and amorphous phases, will contribute to improve the efficiency of Si based solar cells.

Pre-edge analysis of X-rays absorption spectra in TiO2 modified films

The thesis is mainly focused on the pre-edge analysis of XAS spectra of Ti HCF sample hexacyanocobaltate and hexacyanoferrate samples doped on a Indium Tin Oxide (ITO) thin film. The work is aimed at the determination of Ti oxidation state, as well as indication of various coordination number in the studied samples. The experiment have been conducted using XAFS (X-ray absorption fine structure)beamline at Elettra synchrotron, Trieste (Italy) under supervision of Professor Marco Giorgetti, Department of Industrial Chemistry, University of Bologna. The Master thesis accreditation to fullfill the ASC Master of Advanced Spectroscopy in Chemistry Degree requirement.

Kollineare Laserspektroskopie an radioaktiven Praseodymionen und Cadmiumatomen

Die Analyse optischer Spektren liefert einen kernmodellunabhängigen Zugang zur Bestimmung der Kernspins, Ladungsradien und elektromagnetischen Momente von Atomkernen im Grundzustand und von langlebigen Isomeren. Eine der vielseitigsten Methoden zur optischen Spektroskopie an kurzlebigen Isotopen ist die kollineare Laserspektroskopie. Im Rahmen dieser Arbeit wurde zum einen die TRIGA-LASER Strahlstrecke am Institut für Kernchemie der Universität Mainz durch die Implementierung einer neuen offline Oberflächenionenquelle für hohe Verdampfungstemperaturen und eines Strahlanalysesystems weiterentwickelt. Zum anderen wurde kollineare Laserspektroskopie an kurzlebigen Praseodym- und Cadmiumisotopen an ISOLDE/CERN durchgeführt. Die neue Ionenquelle ermöglichte dabei den Test der kollinearen Laserspektroskopie an Praseodymionen am TRIGA-LASER Experiment. Die Spektroskopie der Prasdeodymionen motivierte sich aus der Beobachtung einer zeitlichen Modulation der EC-Zerfallsrate von wasserstoffähnlichem 140Pr58+. Für die Erklärung dieser sogenannten GSI Oszillationen wird unter anderem das magnetische Moment des Kerns benötigt, welches bislang noch nicht experimentell bestimmt wurde. Zudem wurde für wasserstoffähnliches 140Pr58+ überraschenderweise eine kleinere EC-Zerfallskonstante gemessen als für heliumähnliches 140Pr57+. Die Erklärung dieses Phänomens setzt ein positives magnetisches Moment voraus. Bei der Spektroskopie am COLLAPS Experiment wurden erstmals die magnetischen Momente von 135Pr, 136Pr und 137Pr vermessen. Aufgrund zu geringer Produktionsraten war die Spektroskopie des gewünschten Isotops 140Pr jedoch nicht erfolgreich. Die Untersuchung der Cadmiumisotope ist kernphysikalisch motiviert. In der Zinnregion erstrecken sich die Isotope über die beiden magischen Zahlen N=50 und N=82 bei gleichzeitiger Nähe des Z=50 Schalenabschlusses. Hier können verschiedene Kernmodelle getestet werden, die sich beispielsweise hinsichtlich der Stärke des N=82 Schalenabschlusses widersprechen. Diese Arbeit berichtet über erste Ergebnisse der Spektroskopie an Cadmiumatomen, die sich über die Isotope 106−124,126Cd sowie die zugehörigen langlebigen I=11/2− Isomere erstreckt. Die zuvor experimentell bekannten oder aus dem erweiterten Schalenmodell abgeleiteten Kernspins konnten für alle Isotope bis auf 119Cd bestätigt werden. Der Kernspin von 119Cd wurde eindeutig zu I=1/2 bestimmt. Die elektrischen Quadrupolmomente der Isomere zeigen ein bemerkenswert lineares Verhalten in Abhängigkeit von der Neutronenzahl und dies über die eigentliche Kapazität der 1h11/2 Unterschale hinaus. Die Änderungen der mittleren quadratischen Ladungsradien zeigen den auch an Indium- und Zinnisotopen beobachteten stetigen Verlauf. Der lineare Anteil passt sehr gut zu den Berechnung des Tröpfchenmodells in der Parametrisierung nach Berchidevsky und Tondeur. Die Differenzen der mittleren quadratischen Ladungsradien zwischen Grund- und isomeren Zustand der ungeraden Cadmiumisotope zeigen einen interessanten parabolischen Verlauf mit einem Minimum zwischen A=117 und A=119.

Oversizing and Restenosis with Self-Expanding Stents in Iliofemoral Arteries

Uncoated self-expanding nitinol stents (NS) are commonly oversized in peripheral arteries. In current practice, 1-mm oversizing is recommended. Yet, oversizing of NS may be associated with increased restenosis. To provide further evidence, NS were implanted in porcine iliofemoral arteries with a stent-to-artery-ratio between 1.0 and 2.3. Besides conventional uncoated NS, a novel self-expanding NS with an antiproliferative titanium-nitride-oxide (TiNOX) coating was tested for safety and efficacy.

In-situ electrical, mechanical and electrochemical characterizations of one-dimensional nanostructures

One-dimensional nanostructures initiated new aspects to the materials applications due to their superior properties compared to the bulk materials. Properties of nanostructures have been characterized by many techniques and used for various device applications. However, simultaneous correlation between the physical and structural properties of these nanomaterials has not been widely investigated. Therefore, it is necessary to perform in-situ study on the physical and structural properties of nanomaterials to understand their relation. In this work, we will use a unique instrument to perform real time atomic force microscopy (AFM) and scanning tunneling microscopy (STM) of nanomaterials inside a transmission electron microscopy (TEM) system. This AFM/STM-TEM system is used to investigate the mechanical, electrical, and electrochemical properties of boron nitride nanotubes (BNNTs) and Silicon nanorods (SiNRs). BNNTs are one of the subjects of this PhD research due to their comparable, and in some cases superior, properties compared to carbon nanotubes. Therefore, to further develop their applications, it is required to investigate these characteristics in atomic level. In this research, the mechanical properties of multi-walled BNNTs were first studied. Several tests were designed to study and characterize their real-time deformation behavior to the applied force. Observations revealed that BNNTs possess highly flexible structures under applied force. Detailed studies were then conducted to understand the bending mechanism of the BNNTs. Formations of reversible ripples were observed and described in terms of thermodynamic energy of the system. Fracture failure of BNNTs were initiated at the outermost walls and characterized to be brittle. Second, the electrical properties of individual BNNTs were studied. Results showed that the bandgap and electronic properties of BNNTs can be engineered by means of applied strain. It was found that the conductivity, electron concentration and carrier mobility of BNNTs can be tuned as a function of applied stress. Although, BNNTs are considered to be candidate for field emission applications, observations revealed that their properties degrade upon cycles of emissions. Results showed that due to the high emission current density, the temperature of the sample was increased and reached to the decomposition temperature at which the B-N bonds start to break. In addition to BNNTs, we have also performed in-situ study on the electrochemical properties of silicon nanorods (SiNRs). Specifically, lithiation and delithiation of SiNRs were studied by our STM-TEM system. Our observations showed the direct formation of Li22Si5 phases as a result of lithium intercalation. Radial expansion of the anode materials were observed and characterized in terms of size-scale. Later, the formation and growth of the lithium fibers on the surface of the anode materials were observed and studied. Results revealed the formation of lithium islands inside the ionic liquid electrolyte which then grew as Li dendrite toward the cathode material.

Porous silicon technology for integrated microsystems

With the development of micro systems, there is an increasing demand for integrable porous materials. In addition to those conventional applications, such as filtration, wicking, and insulating, many new micro devices, including micro reactors, sensors, actuators, and optical components, can benefit from porous materials. Conventional porous materials, such as ceramics and polymers, however, cannot meet the challenges posed by micro systems, due to their incompatibility with standard micro-fabrication processes. In an effort to produce porous materials that can be used in micro systems, porous silicon (PS) generated by anodization of single crystalline silicon has been investigated. In this work, the PS formation process has been extensively studied and characterized as a function of substrate type, crystal orientation, doping concentration, current density and surfactant concentration and type. Anodization conditions have been optimized for producing very thick porous silicon layers with uniform pore size, and for obtaining ideal pore morphologies. Three different types of porous silicon materials: meso porous silicon, macro porous silicon with straight pores, and macro porous silicon with tortuous pores, have been successfully produced. Regular pore arrays with controllable pore size in the range of 2µm to 6µm have been demonstrated as well. Localized PS formation has been achieved by using oxide/nitride/polysilicon stack as masking materials, which can withstand anodization in hydrofluoric acid up to twenty hours. A special etching cell with electrolytic liquid backside contact along with two process flows has been developed to enable the fabrication of thick macro porous silicon membranes with though wafer pores. For device assembly, Si-Au and In-Au bonding technologies have been developed. Very low bonding temperature (~200 degrees C) and thick/soft bonding layers (~6µm) have been achieved by In-Au bondi ng technology, which is able to compensate the potentially rough surface on the porous silicon sample without introducing significant thermal stress. The application of the porous silicon material in micro systems has been demonstrated in a micro gas chromatograph system by two indispensable components: an integrated vapor source and an inlet filter, wherein porous silicon performs the basic functions of porous media: wicking and filtration. By utilizing a macro porous silicon wick, the calibration vapor source was able to produce a uniform and repeatable vapor generation for n-decane with less than a 0.1% variation in 9 hours, and less than a 0.5% variation in rate over 7 days. With engineered porous silicon membranes the inlet filter was able to show a depth filtration with nearly 100% collection efficiency for particles larger than 0.3µm in diameter, a low pressure-drop of 523Pa at 20sccm flow rate, and a filter capacity of 500µg/cm2.

Quantum modeling of bioconjugated nanomaterials

In recent years, the bio-conjugated nanostructured materials have emerged as a new class of materials for the bio-sensing and medical diagnostics applications. In spite of their multi-directional applications, interfacing nanomaterials with bio-molecules has been a challenge due to somewhat limited knowledge about the underlying physics and chemistry behind these interactions and also for the complexity of biomolecules. The main objective of this dissertation is to provide such a detailed knowledge on bioconjugated nanomaterials toward their applications in designing the next generation of sensing devices. Specifically, we investigate the changes in the electronic properties of a boron nitride nanotube (BNNT) due to the adsorption of different bio-molecules, ranging from neutral (DNA/RNA nucleobases) to polar (amino acid molecules). BNNT is a typical member of III-V compounds semiconductors with morphology similar to that of carbon nanotubes (CNTs) but with its own distinct properties. More specifically, the natural affinity of BNNTs toward living cells with no apparent toxicity instigates the applications of BNNTs in drug delivery and cell therapy. Our results predict that the adsorption of DNA/RNA nucleobases on BNNTs amounts to different degrees of modulation in the band gap of BNNTs, which can be exploited for distinguishing these nucleobases from each other. Interestingly, for the polar amino acid molecules, the nature of interaction appeared to vary ranging from Coulombic, van der Waals and covalent depending on the polarity of the individual molecules, each with a different binding strength and amount of charge transfer involved in the interaction. The strong binding of amino acid molecules on the BNNTs explains the observed protein wrapping onto BNNTs without any linkers, unlike carbon nanotubes (CNTs). Additionally, the widely varying binding energies corresponding to different amino acid molecules toward BNNTs indicate to the suitability of BNNTs for the biosensing applications, as compared to the metallic CNTs. The calculated I-V characteristics in these bioconjugated nanotubes predict notable changes in the conductivity of BNNTs due to the physisorption of DNA/RNA nucleobases. This is not the case with metallic CNTs whose transport properties remained unaltered in their conjugated systems with the nucleobases. Collectively, the bioconjugated BNNTs are found to be an excellent system for the next generation sensing devices.

Synthesis of novel solid materials from carbon dioxide and carbon monoxide

The increase of atmospheric CO2 has been identified as the primary cause for the observed global warming over the past century. The geological and oceanic sequestration of CO2 has issues, such as cost and leakage as well as effects on sea biota. The ideal solution should be the conversion of CO2 into useful materials. However, most processes require high energy input. Therefore, it is necessary to explore novel processes with low energy demands to convert CO2 to useful solid materials. Amorphous carbon nitride and graphone received much attention due to their unusual structures and properties as well as their potential applications. However, to date there has been no attempt to synthesize those solid materials from CO2. Lithium nitride (Li3N) and lithium imide (Li2NH) are important hydrogen storage materials. However, their optical properties and reactivity has not yet studied. This dissertation research is aimed at the synthesis of carbon nitrides and graphone from CO2 and CO via their reaction with Li3N and Li2NH. The research was focused on (1) the evaluation of Li3N and Li2NH properties, (2) thermodynamic analysis of conversion of carbon dioxide and carbon monoxide into carbon nitride and other solid materials, (3) synthesis of carbon nitride from carbon dioxide, and (4) synthesis of graphone from carbon monoxide. First, the properties of Li3N, Li2NH, and LiNH2 were investigated. The X-ray diffraction measurements revealed that heat-treatment at 500°C introduce a phase transformation of β-Li3N to α-Li3N. Furthermore, the UV-visible absorption evaluation showed that the energy gaps of α-Li3N and β-Li3N are 1.81 and 2.14 eV, respectively. The UV-visible absorption measurements also revealed that energy gaps are 3.92 eV for Li2NH and 3.93 eV for LiNH2. This thermodynamic analysis was performed to predict the reactions. It was demonstrated that the reaction between carbon dioxide and lithium nitride is thermodynamically favorable and exothermic, which can generate carbon nitride and lithium cyanamide. Furthermore, the thermodynamic calculation indicated that the reaction between carbon monoxide and lithium imide can produce graphone and lithium cyanamide along with releasing heat. Based on the above thermodynamic analysis, the experiment of CO2 and Li3N reaction and CO and Li2NH were carried out. It was found that the reaction between CO2 and Li3N is very fast and exothermic. The XRD and element analysis revealed that the products are crystal lithium cyanamide and amorphous carbon nitrides with Li2O and Li2CO3. Furthermore, TEM images showed that carbon nitrides possess layer-structure, namely, it is graphene-structured carbon nitride. It was found that the reaction between Li2NH and CO was also exothermic, which produced graphone instead of carbon nitride. The composition and structures of graphone were evaluated by XRD, element analysis, TEM observation, and Raman spectra.

Bacteriorhodopsin protein hybrids for chemical and biological sensing

Bacteriorhodopsin (bR), an optoelectric protein found in Halobacterium salinarum, has the potential for use in protein hybrid sensing systems. Bacteriorhodopsin has no intrinsic sensing properties, however molecular and chemical tools permit production of bR protein hybrids with transducing and sensing properties. As a proof of concept, a maltose binding protein-bacteriorhodopsin ([MBP]-bR) hybrid was developed. It was proposed that the energy associated with target molecule binding, maltose, to the hybrid sensor protein would provide a means to directly modulate the electrical output from the MBP-bR bio-nanosensor platform. The bR protein hybrid is produced by linkage between bR (principal component of purified purple membrane [PM]) and MBP, which was produced by use of a plasmid expression vector system in Escherichia coli and purified utilizing an amylose affinity column. These proteins were chemically linked using 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), which facilitates formation of an amide bond between a primary carboxylic acid and a primary amine. The presence of novel protein hybrids after chemical linkage was analyzed by SDSPAGE. Soluble proteins (MBP-only derivatives and unlinked MBP) were separated from insoluble proteins (PM derivatives and unlinked PM) using size exclusion chromatography. The putatively identified MBP-bR protein hybrid, in addition to unlinked bR, was collected. This sample was normalized for bR concentration to native PM and both were deposited onto indium tin oxide (ITO) coated glass slides by electrophoretic sedimentation. The photoresponse of both samples, activated using 100 Watt tungsten lamp at 10 cm distance, were equal at 175 mV. Testing of deposited PM with 1 mM sucrose or 1 mM maltose showed no change in the photoresponse of the xiv material, however addition of 1 mM maltose to the deposited MBP-bR linked hybrid material elicited a 57% decrease in photoresponse indicating a positive response for targeting of maltose. This chemically linked MBP-bR hybrid protein, with bacteriorhodopsin, as a photoresponsive transducing substrate, shows promise for creation of a universal sensing array by attachment of other pertinent sensing materials, in lieu of the maltose binding protein utilized. This strategy would allow significant reduction in sensor size, while increasing responsiveness and sensitivity at nano and picomolar levels.