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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
441

Precision Synthesis of Boron-Doped Graphene Nanoribbons: Recent Progress and Perspectives

Zhang, Jin-Jiang, Ma, Ji, Feng, Xinliang 19 January 2024 (has links)
Structurally precision graphene nanoribbons (GNRs) have attracted great interest considering their prospective applications as organic carbon materials for nanoelectronics. The electronic properties of GNRs not only critically depend on the edge structure and width but also on the heteroatom type, doping position, and concentration. Motivated by the recent undisputable progress in the synthesis of stable boron-doped polycyclic aromatic hydrocarbons (B-PAHs), considerable efforts have been devoted to the precision synthesis of the corresponding boron-doped GNRs (B-GNRs) via bottom-up synthesis approach in recent years in view of the extraordinary ability of boron doping on modulating their physiochemical properties. In this review, an overview of the bottom-up organic synthesis of B-GNRs, including the precursor design and synthesis, structure characterization of the resulting B-GNRs, and investigation of their electronic properties is provided. Moreover, the future challenges and perspectives regarding the bottom-up synthesis of B-GNRs are also discussed. The authors hope that this review will further stimulate the synthesis and device integrations of B-GNRs with a combined effort from different disciplines.
442

Editorial: Antimicrobial and Anticancer Peptides

O’Brien-Simpson, Neil M., Hoffmann, Ralf, Chia, C. S. Brian, Wade, John D. 03 April 2023 (has links)
Editorial on the Research Topic. Antimicrobial and Anticancer Peptides.
443

Silylated Zeolites With Enhanced Hydrothermal Stability for the Aqueous-Phase Hydrogenation of Levulinic Acid to g-Valerolactone

Vu, Hue-Ton, Harth, Florian M., Wilde, Nicole 03 April 2023 (has links)
A systematic silylation approach using mono-, di-, and trichlorosilanes with different alkyl chain lengths was employed to enhance the hydrothermal stability of zeolite Y. DRIFT spectra of the silylated zeolites indicate that the attachment of the silanes takes place at surface silanol groups. Regarding hydrothermal stability under aqueous-phase processing (APP) conditions, i.e., pH ≈ 2, 473 K and autogenous pressure, the selective silylation of the zeolite surface usingmonochlorosilanes has no considerable influence. By using trichlorosilanes, the hydrothermal stability of zeolite Y can be improved significantly as proven by a stability test in an aqueous solution of 0.2M levulinic acid (LA) and 0.6M formic acid (FA) at 473 K. However, the silylationwith trichlorosilanes results in a significant loss of total specific pore volume and total specific surface area, e.g., 0.35 cm3 g−1 and 507m2 g−1 for the silylated zeolite Y functionalized with n-octadecyltrichlorosilane compared to 0.51 cm3 g−1 and 788 m2 g−1 for the parent zeolite Y. The hydrogenation of LA to g-valerolactone (GVL) was conducted over 3 wt.-% Pt on zeolite Y (3PtY) silylated with either n-octadecyltrichlorosilane or methyltrichlorosilane using different reducing agents, e.g., FA or H2. While in the stability test an enhanced hydrothermal stability was found for zeolite Y silylated with n-octadecyltrichlorosilane, its stability in the hydrogenation of LA was far less pronounced. Only by applying an excess amount of methyltrichlorosilane, i.e., 10 mmol per 1 g of zeolite Y, presumably resulting in a high degree of polymerization among the silanes, a recognizable improvement of the stability of the 3 PtY catalyst could be achieved. Nonetheless, the pore blockage found for zeolite Y silylated with an excess amount of methyltrichlorosilane was reflected in a drastically lower GVL yield at 493 K using FA as reducing agent, i.e., 12 vs. 34% for 3PtY after 24 h.
444

Low-Cost Microwave-Assisted Partial Pseudomorphic Transformation of Biogenic Silica

Schneider, Denise, Kircheis, Ralf, Wassersleben, Susan, Einicke, Wolf-Dietrich, Gläser, Roger, Enke, Dirk 03 April 2023 (has links)
This work introduces a cost and time efficient procedure to specifically increase mesopore volume and specific surface area of biogenic silica (specific surface area: 147 m2 g−1 and mesopore volume: 0.23 cm3 g−1) to make it suitable for applications in adsorption or as catalyst support. The target values were a specific surface area of ∼500 m2 g−1 and a mesopore volume of ∼0.40–0.50 cm3 g−1 as these values are industrially relevant and are reached by potential concurring products such as precipitated silica, silica gel, and fumed silica. The applied process of partial pseudomorphic transformation was carried out as a single reaction step in a microwave reactor instead of commonly used convective heating. In addition, the conventionally used surfactant cetyltrimethylammonium bromide (CTABr) was substituted by the low-cost surfactant (Arquad® 16-29, cetyltrimethylammonium chloride (CTACl) aqueous solution). The influence of microwave heating, type of surfactant as well as the concentration of NaOH and CTACl on the textural and structural properties of the modified biogenic silica was investigated using nitrogen adsorption as well as scanning and transmission electron microscopy. The results show that the textural parameters of the modified biogenic silica can be exactly controlled by the amount of NaOH in the reaction solution. By variation of the NaOH concentration, specific surface areas in the range of 215–1,001m2 g−1 andmesopore volumes of 0.25–0.56 cm3 g−1 were achieved after reaction at 393 K for 10min. The presented microwave route using the low-cost surfactant solution decreases the reaction time by 99% and as shown in an example for German prices, lowers the costs for the surfactant by 76–99%.
445

Peptide-Drug Conjugates and Their Targets in Advanced Cancer Therapies

Hoppenz, Paul, Els-Heindl, Sylvia, Beck-Sickinger, Annette G. 03 April 2023 (has links)
Cancer became recently the leading cause of death in industrialized countries. Even though standard treatments achieve significant effects in growth inhibition and tumor elimination, they cause severe side effects as most of the applied drugs exhibit only minor selectivity for the malignant tissue. Hence, specific addressing of tumor cells without affecting healthy tissue is currently a major desire in cancer therapy. Cell surface receptors, which bind peptides are frequently overexpressed on cancer cells and can therefore be considered as promising targets for selective tumor therapy. In this review, the benefits of peptides as tumor homing agents are presented and an overview of the most commonly addressed peptide receptors is given. A special focus was set on the bombesin receptor family and the neuropeptide Y receptor family. In the second part, the specific requirements of peptide-drug conjugates (PDC) and intelligent linker structures as an essential component of PDC are outlined. Furthermore, different drug cargos are presented including classical and recent toxic agents as well as radionuclides for diagnostic and therapeutic approaches. In the last part, boron neutron capture therapy as advanced targeted cancer therapy is introduced and past and recent developments are reviewed.
446

OsB9 −: An Aromatic Osmium-Centered Monocyclic Boron Ring

Yu, Rui, Pan, Sudip, Cui, Zhong-hua 03 April 2023 (has links)
Transition-metal-centered monocyclic boron wheels are important candidates in the family of planar hypercoordinate species that show intriguing structure, stability and bonding situation. Through the detailed potential energy surface explorations of MB9 − (M Fe, Ru, Os) clusters, we introduce herein OsB9 − to be a new member in the transition-metalcentered borometallic molecular wheel gallery. Previously, FeB9 − and RuB9 − clusters were detected by photoelectron spectroscopy and the structures were reported to have singlet D9h symmetry. Our present results show that the global minimum for FeB9 − has a molecular wheel-like structure in triplet spin state with Cs symmetry, whereas its heavier homologues are singlet molecular wheels with D9h symmetry. Chemical bonding analyses show that RuB9 − and OsB9 − display a similar type of electronic structure, where the dual σ + π aromaticity, originated from three delocalized σ bonds and three delocalized π bonds, accounts for highly stable borometallic molecular wheels.
447

Testing and validating the improved estimation of the spectrometer-transmission function with UNIFIT 2022

Hesse, Ronald, Denecke, Reinhard, Radnik, Jörg 05 January 2024 (has links)
Recent developments of X-ray photoelectron spectroscopy using excitation energies different from the usual lab-sources Mg Kα and Al Kα, thus covering larger and different kinetic energy ranges, require more flexible approaches for determining the transmission function than the well-established ones using reference spectra. Therefore, the approach using quantified peak areas (QPA) was refined allowing a more precise estimation of the transmission function. This refinement was tested by comparing the results obtained with the new version with former calculations. Furthermore, the obtained transmission function was validated by comparing the results with a transmission function using the reference spectrum of polyethylene. Additionally, an ionic liquid was used as reference for estimating the transmission function at the energyresolved HE-SGM beamline at BESSY II. Comparison between the measured and stoichiometric composition shows that a transmission function was determined, which allows a reasonable quantification.
448

Direct Mechanocatalysis of Metal Catalysed Coupling Reactions in Ball Mills

Vogt, Christian 14 July 2022 (has links)
Sustainability is an urgent need to secure the progress of our civilization and to reach it is getting more and more into common conscious. From a chemists viewpoint, this means the customary practices of the last centuries have to be overcome, chemicals and chemical processes must be designed safe and environmentally friendly without long term consequences while at the same time conserving resources. A main part within this is the reduction of toxic waste, often originated in solvents. To accomplish this, new paths have to be discovered. One possible path is mechanochemistry, which describes chemical reactions initiated by mechanical forces like milling balls and vessels in a ball mill. In this environment solubility is not required and thus turns the use of solvents obsolete. However, in mechanochemical catalytic reactions for instance catalyst complexes with ligands are used, that originally ensured solubility in the former reaction medium. Since no solubility is required in this solvent free reaction environment, the complexes can be simplified to salts or further to pure metal powder catalysts. Complexes, salts and powders alike are difficult to recycle from the reaction mixture, thwarting the aim of sustainability. A concept to overcome this drawback is direct mechanocatalysis that uses milling materials themselves made of the catalytic metal, likewise accounting for the catalyst and the energy input. The aim of the thesis on hand was to expand the concept towards new direct mechanocatalytic reactions and gain insights beyond the mere phenomenology. In detail, the palladium catalysed Suzuki coupling as well as the copper catalysed Ullmann reaction/coupling, and Glaser coupling were investigated.
449

Ba(BO2OH) – A Monoprotonated Monoborate from Hydroflux Showing Intense Second Harmonic Generation

Li, Yuxi, Hegarty, Peter A., Rüsing, Michael, Eng, Lukas M., Ruck, Michael 30 May 2024 (has links)
Pure samples of colorless, air-stable Ba(BO2OH) crystals were obtained from Ba(NO3)2 and H3BO3 under the ultra-alkaline conditions of a KOH hydroflux at about 250 °C. The product formation depends on the water-base molar ratio and the molar ratio of the starting materials. B(OH)3 acts as a proton donor (Brønsted acid) rather than a hydroxide acceptor (Lewis acid). Ba(BO2OH) crystallizes in the non-centrosymmetric orthorhombic space group P212121. Hydrogen bonds connect the almost planar (BO2OH)2− anions, which are isostructural to HCO3−, into a syndiotactic chain. IR and Raman spectroscopy confirm the presence of hydroxide groups, which are involved in weak hydrogen bonds. Upon heating in air to about 450 °C, Ba(BO2OH) dehydrates to Ba2B2O5. Moreover, the non-centrosymmetric structure of Ba(BO2OH) crystals was verified with power-dependent confocal Second Harmonic Generation (SHG) microscopy indicating large conversion efficiencies in ambient atmosphere.
450

Iron-Catalyzed Cycloisomerization and C−C Bond Activation to Access Non-canonical Tricyclic Cyclobutanes: In memory of Professor Klaus Hafner

Kramm, Frederik, Ullwer, Franziska, Klinnert, Benedict, Zheng, Min, Plietker, Bernd 06 June 2024 (has links)
Cycloisomerizations are powerful skeletal rearrangements that allow the construction of complex molecular architectures in an atom-economic way. We present here an unusual type of cyclopropyl enyne cycloisomerization that couples the process of a cycloisomerization with the activation of a C−C bond in cyclopropanes. A set of substituted non-canonical tricyclic cyclobutanes were synthesized under mild conditions using [(Ph₃P)₂Fe(CO)(NO)]BF₄ as catalyst in good to excellent yields with high levels of stereocontrol.

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