Polyaniline as nonmetal catalyst for styrene synthesis by oxidative dehydrogenation of ethylbenzene

Polyaniline was used as a nonmetal catalyst in the oxidative dehydrogenation of ethylbenzene and yield of 22.9% at 573 K and similar to 40% at 673 K were obtained, respectively. An indirect oxidative dehydrogenation mechanism was proposed based on the results of pulse reactions.

One-step synthesis of graphene/SnO2 nanocomposites and its application in electrochemical supercapacitors

A one-step method was developed to fabricate conductive graphene/SnO2 (GS) nanocomposites in acidic solution. Graphite oxides were reduced by SnCl2 to graphene sheets in the presence of HCl and urea. The reducing process was accompanied by generation of SnO2 nanoparticles. The structure and composition of GS nanocomposites were confirmed by means of transmission electron microscopy, x-ray photoelectron and Raman spectroscopy. Moreover, the ultracapacitor characteristics of GS nanocomposites were studied by cyclic voltammograms (CVs) and electrical impedance spectroscopy (EIS). The CVs of GS nanocomposites are nearly rectangular in shape and the specific capacitance degrades slightly as the voltage scan rate is increased. The EIS of GS nanocomposites presents a phase angle close to p/2 at low frequency, indicating a good capacitive behavior.

Molecular gels for controlled formation of micro-/nano-structures

The preparation of nano structured materials such as nanoparticles, nanofiber and nanowires have been a focus of research in the last two decades. Due to their large surface-to-volume ration and superior properties compared to the conventional macroscopic materials, these materials promise to revolutionize many fields such as electronics, catalysis, and biomedicine. Hence, controlling the growth of these nanostructures has been a global interest. Although controlling the formation of macroscopically sized inorganic materials can be easily achieved, it is a challenge if the size of a material is reduced to a micrometer or nanometer scale. Synthesis of structures using organic templates has been demonstrated to be a simple and convenient approach, since the organic matter can be easily removed by calcination or suitable solvents. These organic templates include colloidal particles and fibers of polymers, aggregates of surfactants, carbon materials such as carbon nanotubes, organic crystals and fibers in small-molecule gels (SMGs) and polymer gels.

A self-supported, flexible, binder-free pseudo-supercapacitor electrode material with high capacitance and cycling stability from hollow, capsular polypyrrole fibers

Flexible energy devices with high performance and long-term stability are highly promising for applications in portable electronics, but remain challenging to develop. As an electrode material for pseudo-supercapacitors, conducting polymers typically show higher energy storage ability over carbon materials and larger conductivity than transition-metal oxides. However, conducting polymer-based supercapacitors often have poor cycling stability, attributable to the structural rupture caused by the large volume contrast between doping and de-doping states, which has been the main obstacle to their practical applications. Herein, we report a simple method to prepare a flexible, binder-free, self-supported polypyrrole (PPy) supercapacitor electrode with high cycling stability through using novel, hollow PPy nanofibers with porous capsular walls as a film-forming material. The unique fiber structure and capsular walls provide the PPy film with enough free-space to adapt to volume variation during doping/de-doping, leading to super-high cycling stability (capacitance retention > 90% after 11000 charge-discharge cycles at a high current density of 10 A g^-1) and high rate capability (capacitance retention ∼ 82.1% at a current density in the range of 0.25-10 A g^-1).

Synthesis and characterization of new discotic polycyclic aromatic hydrocarbons and related pyrolytic nanostructures

Diskotische Hexa-peri-hexabenzocoronene (HBC) als molekulare, definierte graphitische Substrukturen sind bereits seit langem Gegenstand von Untersuchungen zu der Delokalisierung von π-Elektronen. In dieser Arbeit wurden zusätzlich Platin-Komplexe in das periphere Substitutionsmuster von HBC eingeführt. Dies führte zu einer Verbesserung der Emission von dem angeregten Triplett-Zustand in den Singulett-Grundzustand mit einer zusätzlichen Verlängerung der Lebensdauer des angeregten Zustandes. Zusätzlich erlaubte diese Konfiguration ein schnelles Intersystem-Crossing mittels einer verstärkten Spin-Orbit Kopplung, die sowohl bei tiefen Temperaturen, als auch bei Raumtemperatur exklusiv zu Phosphoreszenz (T1→S0) führte. Das Verständniss über solche Prozesse ist auch essentiell für die Entwicklung verbesserter opto-elektronischer Bauteile. Die Erstellung von exakt definierten molekularen Strukturen, die speziell für spezifische Interaktionen hergestellt wurden, machten eine Inkorporation von hydrophoben-hydrophilen, wasserstoffverbrückten oder elektrostatischen funktionalisierten Einheiten notwendig, um damit den supramolekularen Aufbau zu kontrollieren. Mit Imidazolium-Salzen funktionalisierte HBC Derivate wurden zu diesem Zwecke hergestellt. Eine interessante Eigenschaft dieser Moleküle ist ihre Amphiphilie. Dies gestattete die Untersuchung ihrer Eigenschaften in einem polaren Solvens und sowohl der Prozessierbarkeit als auch der Faserbildung auf Siliziumoxid-Trägern. Abhängig vom Lösungsmittel und der gewählten Konditionen konnten hochkristalline Fasern erhalten werden. Durch eine Substitution der HBCs mit langen, sterisch anspruchsvollen Seitenketten, konnte durch eine geeignete Prozessierung eine homöotrope Ausrichtung auf Substraten erreicht werden, was dieses Material interessant für photovoltaische Applikationen macht. Neuartige Polyphenylen-Metall-Komplexe mit diskotischen, linearen und dendritischen Geometrien wurden mittels einer einfachen Reaktion zwischen Co2(CO)8 und Ethinyl-Funktionalitäten in Dichlormethan hergestellt. Nach der Pyrolyse dieser Komplexe ergaben sich unterschiedliche Kohlenstoff-Nanopartikel, inklusive Nanoröhren, graphitischen Nanostäben und Kohlenstoff/Metall Hybrid Komplexe, die durch Elektronenmikroskopie untersucht wurden. Die resultierenden Strukturen waren dabei abhängig von der Zusammensetzung und Struktur der Ausgangssubstanzen. Anhand dieser Resultate ergeben sich diverse Möglichkeiten, um den Mechanismus, der zur Herstellung graphitischer Nanopartikel führt, besser zu verstehen.

From large polycyclic aromatic hydrocarbons to extended aromate-rich networks

The common ground of this study is the development of novel synthetic strategies to extended one-, two- and three-dimensional aromate-rich systems for which a number of applications are envisaged. rnThe point of departure is the synthesis and characterization of highly symmetric macrocyclic PAHs (polycyclic aromatic hydrocarbons) for which various aspects of supramolecular chemistry will be investigated. The versatility of the Yamamoto macrocyclization will be demonstrated on the basis of a set of cyclic trimers that exhibit a rich supramolecular chemistry. 1,10-phenanthroline, triphenylene and ortho-terphenyl building blocks have been successfully assembled to the corresponding macrocycles following the newly developed synthetic route. Scanning-tunneling microscopy (STM) and two-dimensional wide-angle X-ray scattering (2D-WAXS) were used to study the two- and three-dimensional self-assembly, respectively.rnSecondly, the development of chemical approaches to highly shape-anisotropic graphene nanoribbons (GNRs) and related nanographene molecules shall be discussed. Aryl-aryl coupling was used for the bottom-up fabrication of dendronized monomers, polymers and model compounds. Subsequently, these structures were converted into the final graphene material using oxidative (Scholl-type) cyclodehydrogenation. The GNRs thus obtained are characterized by an unprecedented length and lateral extension. The relevance of structural tailoring in the field of well-defined graphene materials is discussed in detail as only the chemical approach provides full geometry control. rnLastly, novel pathways towards the synthesis of extended three-dimensional networks that are dominated by nitrogen-rich motifs will be presented. If porous, these materials hold a great potential in the fields of gas and energy storage as well as for applications in catalysis. Hence, poly(aminal) networks based on melamine as crosslinking unit were synthesized and characterized with respect to the applications mentioned above. As set of conjugated poly(azomethine) networks was investigated regarding their use as a novel class of organic semiconductors for photocatalytic water splitting. The network structures described in this chapter can also be subjected to a controlled pyrolysis yielding mesoporous, nitrogen-rich carbon materials that were evaluated as active component for supercapacitors.rn

PURIFICATION AND EFFECTIVENESS OF VACCINES AND ANTIVIRAL COMPOUNDS

Viral infections account for over 13 million deaths per year. Antiviral drugs and vaccines are the most effective method to treat viral diseases. Antiviral compounds have revolutionized the treatment of AIDS, and reduced the mortality rate. However, this disease still causes a large number of deaths in developing countries that lack these types of drugs. Vaccination is the most effective method to treat viral disease; vaccines prevent around 2.5 million deaths per year. Vaccines are not able to offer full coverage due to high operational costs in the manufacturing processes. Although vaccines have saved millions of lives, conventional vaccines often offer reactogenic effects. New technologies have been created to eliminate the undesired side effects. However, new vaccines are less immunogenic and adjuvants such as vaccine delivery vehicles are required. This work focuses on the discovery of new natural antivirals that can reduce the high cost and side effects of synthetic drugs. We discovered that two osmolytes, trimethylamine N-oxide (TMAO) and glycine reduce the infectivity of a model virus, porcine parvovirus (PPV), by 4 LRV (99.99%), likely by disruption of capsid assembly. These osmolytes have the potential to be used as drugs, since they showed antiviral activity after 20 h. We have also focused on improving current vaccine manufacturing processes that will allow fast, effective and economical vaccines to be produced worldwide. We propose virus flocculation in osmolytes followed by microfiltration as an economical alternative for vaccine manufacturing. Osmolytes are able to specifically flocculate hydrophobic virus particles by depleting a hydration layer around the particles and subsequently cause virus aggregation. The osmolyte mannitol was able to flocculate virus particles, and demonstrate a high virus removal, 81% for PPV and 98.1% for Sindbis virus (SVHR). Virus flocculation with mannitol, followed by microfiltration could be used as a platform process for virus purification. Finally, we perform biocompatibility studies on soft-templated mesoporous carbon materials with the aim of using these materials as vaccine delivery vehicles. We discovered that these materials are biocompatible, and the degree of biocompatibility is within the range of other biomaterials currently employed in biomedical applications.