Highly Stable Luminous "snakes" from CsPbX3 Perovskite Nanocrystals Anchored on Amine-Coated Silica Nanowires

CsPbX3 (X = Cl, Br, and I) perovskite nanocrystals (NCs) are known for their exceptional optoelectronic properties, yet the material's instability toward polar solvents, heat, or UV irradiation greatly limits its further applications. Herein, an efficient in situ growing strategy has been developed to give highly stable perovskite NC composites (abbreviated CsPbX3@CA-SiO2) by anchoring CsPbX3 NCs onto silica nanowires (NWs), which effectively depresses the optical degradation of their photoluminescence (PL) and enhances stability. The preparation of surface-functionalized serpentine silica NWs is realized by a sol-gel process involving hydrolysis of a mixture of tetraethyl orthosilicate (TEOS), 3-aminopropyltriethoxysilane (APTES), and trimethoxy(octadecyl)silane (TMODS) in a water/oil emulsion. The serpentine NWs are formed via an anisotropic growth with lengths up to 8 μm. The free amino groups are employed as surface ligands for growing perovskite NCs, yielding distributed monodisperse NCs (∼8 nm) around the NW matrix. The emission wavelength is tunable by simple variation of the halide compositions (CsPbX3, X = Cl, Br, or I), and the composites demonstrate a high photoluminescence quantum yield (PLQY 32-69%). Additionally, we have demonstrated the composites CsPbX3@CA-SiO2 can be self-woven to form a porous 3D hierarchical NWs membrane, giving rise to a superhydrophobic surface with hierarchical micro/nano structural features. The resulting composites exhibit high stability toward water, heat, and UV irradiation. This work elucidates an effective strategy to incorporate perovskite nanocrystals onto functional matrices as multifunctional stable light sources

Does Size Matter? Comparing the Alpha-P and the Hyperion for FTIR Paint Analysis

In art and architectural conservation since the 1970s, Infrared Spectroscopy is often used to analyze historic pigments and their media. Fourier Transform Infrared (FTIR) was introduced in the 1980s, followed quickly by the development of the Infrared Microscope. Because the configuration of instruments costs over $100,000 with testing samples priced at hundreds of dollars, it is often cost prohibitive for many conservators, consultants and scientists. Recently, a less expensive and smaller FTIR instrument was introduced. At$15,000 the Brucker Alpha-P presents a much more approachable cost. In my thesis I wish to compare the results of the pigment and media analysis made with the Alpha-P, located at the institute of Fine Arts to those made on the much larger and more expensive Hyperion FTIR microscope in the Metropolitan Museum’s Objects Conservation Laboratory. In addition to investigating the accuracy of the Alpha-P’s results, I would also like to discern what the smallest sample size an operator may use before significantly altering the results. There is currently no published information available as to whether this machine performs to the same standards and levels as the larger FTIR microscopy with regard to pigment and media analysis. Because the Alpha-P generally analyses large samples, it may be better applied to architectural pigment testing because of the availability of a more invasive paint sampling than permitted in the world of art conservation. Should this test perform and produce comparable, if not better, results, then the conservation world may find pigment testing more cost effective and easier to execute. In addition to comparing and contrasting the performances of the aforementioned equipment, I would also like to begin to compile library of architectural pigments in media for the Infrared and Ramen Users Group (IRUG) as no such compilation has yet been made available

Raman spectra of adsorbed layers on space shuttle and AOTV thermal protection system surface

Surfaces of interest to space vehicle heat shield design were struck by a 2 W argon ion laser line while subjected to supersonic arc jet flow conditions. Emission spectra were taken at 90 deg to the angle of laser incidence on the test object. Results showed possible weak Raman shifts which could not be directly tied to any particular parameter such as surface temperature or gas composition. The investigation must be considered exploratory in terms of findings. Many undesirable effects were found and corrected as the project progressed. For instance, initial spectra settings led to ghosts which were eliminated by closing the intermediate of filter slit of the Spex from 8 to 3 mm. Further, under certain conditions, plasma lines from the laser were observed. Several materials were also investigated at room temperature for Raman shifts. Results showed Raman shifts for RCC and TEOS coated materials. The HRSI materials showed only weak Raman shifts, however, substantial efforts were made in studying these materials. Baseline materials showed the technique to be sound. The original goal was to find a Raman shift for the High-temperature Reusable Surface Insulation (HRSI) Reaction Cured borosilicate Glass (RCG) coated material and tie the amplitude of this peak to Arc jet conditions. Weak Raman shifts may be present, however, time limitations prevented confirmation

Raman spectroscopy in electrochermistry

Raman spectroscopy is a particularly useful technique for studying electrochemical surface reactions because it is a visible wavelength spectroscopy and permits in situ investigations. Most electrochemical systems can be studied by Surface Enhanced Raman Spectroscopy ISERS) which involves surface selection and preparation. The techniques involved in the preparation and observation of SERS signals have been highlighted in this review. Recent developments in the observation of SERS on non-SERS active substrates have also been rrported. Studies on the various material - substrate systems have been listed. The application of SERS to various electrochemical systems is also reviewe

SPM Methods Based On The Quartz Resonator Probes

Dizertační práce je zaměřena na vývoj systémů mikroskopů s rastrující sondou, zejména na vývoj a implementaci technologie sond založených na křemenných rezonátorech. Sondy založené na křemenných rezonátorech mají v porovnání s běžnými křemíkovými cantilevery několik výhod. Jsou to především jejich speciální mechanické parametry a možnost elektrického vyčítání signálu odpovídajícího průhybu raménka. Díky elektrickému vyčítání lze sondy založené na křemenných rezonátorech snadno implementovat i do komplexnějších SPM aparatur. Práce pojednává o vývoji elektroniky univerzálního, jednoduše upravitelného řídicího systému pro měření SPM. Systém obsahuje komerční řídicí a oscilační jednotku, ostatní elektronické prvky (např. VN zesilovač a předzesilovače signálů pro měření SPM) jsou předmětem vývoje popsaného v této dizertační práci. Dále je v práci prezentován vývoj systému mikroskopu UHV LT SPM se sondou qPlus, který byl uskutečněn na Universität Hamburg. V rámci jeho vývoje byl navržen předzesilovač určený pro práci na teplotách kapalného helia. Třetím tématem dizertační práce je implementace technologie qPlus do mikroskopu UHV VT SPM určeného pro práci v UHV komoře s elektronovým rastrovacím mikroskopem. Navrženy byly sondy qPlus a univerzální předzesilovač pro zpracování signálů z křemenných rezonátorů. Na všech vyvinutých systémech byla provedena testovací měření.The thesis is focused on development of scanning probe microscope systems, especially development and implementation of quartz resonator probes. The quartz resonator probes, compared to the standard silicon cantilevers, have several advantages. It is in particular their mechanical properties and possibility of direct electrical readout of the deflection signal. Due to the fact, the probes are easy to implement even into more complex SPM systems. The thesis deals with development of universal and open SPM control system electronics. The electronics consist of the commercial SPM control and oscillation units, the development of the other electronic parts (such as the high voltage amplifier and the preamplifier units) is described in the thesis. Further, the thesis reports on development of the qPlus UHV LT SPM microscope system that was carried out at Universität Hamburg. Part of it was development of the qPlus preamplifier able to operate at liquid helium temperature. The third topic of the thesis is the implementation of qPlus technology into the UHV VT SPM microscope suitable to operate in situ with a scanning electron microscope. The qPlus sensors and the universal UHV preamplifier were designed and manufactured. Test measurements were conducted on all of the developed systems.

Laser Based Mid-Infrared Spectroscopic Imaging – Exploring a Novel Method for Application in Cancer Diagnosis

A number of biomedical studies have shown that mid-infrared spectroscopic images can provide both morphological and biochemical information that can be used for the diagnosis of cancer. Whilst this technique has shown great potential it has yet to be employed by the medical profession. By replacing the conventional broadband thermal source employed in modern FTIR spectrometers with high-brightness, broadly tuneable laser based sources (QCLs and OPGs) we aim to solve one of the main obstacles to the transfer of this technology to the medical arena; namely poor signal to noise ratios at high spatial resolutions and short image acquisition times. In this thesis we take the first steps towards developing the optimum experimental configuration, the data processing algorithms and the spectroscopic image contrast and enhancement methods needed to utilise these high intensity laser based sources. We show that a QCL system is better suited to providing numerical absorbance values (biochemical information) than an OPG system primarily due to the QCL pulse stability. We also discuss practical protocols for the application of spectroscopic imaging to cancer diagnosis and present our spectroscopic imaging results from our laser based spectroscopic imaging experiments of oesophageal cancer tissue

Present and future of surface-enhanced Raman scattering

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article

Chiral emergence in multistep hierarchical assembly of achiral conjugated polymers

Intimately connected to the rule of life, chirality remains a long-time fascination in biology, chemistry, physics and materials science. Chiral structures, e.g., nucleic acid and cholesteric phase developed from chiral molecules are common in nature and synthetic soft materials. While it was recently discovered that achiral but bent core mesogens can also form chiral helices, the assembly of chiral microstructures from achiral polymers has rarely been explored. Here, we reveal chiral emergence from achiral conjugated polymers for the first time, in which hierarchical helical structures are developed through a multistep assembly pathway. Upon increasing concentration beyond a threshold volume fraction, pre-aggregated polymer nanofibers form lyotropic liquid crystalline (LC) mesophases with complex, chiral morphologies. Combining imaging, X-ray and spectroscopy techniques with molecular simulations, we demonstrate that this structural evolution arises from torsional polymer molecules which induce multiscale helical assembly, progressing from nano- to micron scale helical structures as the solution concentration increases. This study unveils a previously unknown complex state of matter for conjugated polymers that can pave way to a new field of chiral (opto)electronics. We anticipate that hierarchical chiral helical structures can profoundly impact how conjugated polymers interact with light, transport charges, and transduce signals from biomolecular interactions and even give rise to properties unimagined before.Comment: 47 pages, 7 figure

A novel AAS atomizer based on a dielectric barrier plasma discharge

Byla provedena podrobná optimalizace podmínek atomizace arsenovodíku v novém typu atomizátoru pro atomovou absorpční spektrometrii s generováním hydridů (HG-AAS). Jedná se o plasmový atomizátor pracující na principu plasmového výboje s dielektrickou bariérou (DBD). Použití Ar jako plasmového plynu o průtoku 60 ml min-1 při výkonu DBD atomizátoru 17 W jsou optimální podmínky pro atomizaci arsenovodíku. Citlivost (0,48 s ng-1 As) i detekční limit (0,16 ng ml-1 ) dosažené v DBD jsou srovnatelné s externě vyhřívaným křemenným multiatomizátorem (MMQTA), který byl zvolen jako model běžně používaných atomizátorů hydridotvorných prvků v HG-AAS. Byl zkoumán vliv hydridotvorných prvků (Se, Sb, Bi) na stanovení As v MMQTA a DBD. DBD atomizátor vykazuje lepší odolnost vůči interferencím než MMQTA. Dále byl optimalizován a validován způsob prekoncentrace arsenu přímo v DBD atomizátoru, kdy je dosaženo záchytu analytu přídavkem kyslíku do DBD plazmatu a následně je zachycený analyt uvolněn po uzavření přívodu kyslíku. Bylo dosaženo 100 % účinnosti prekoncentrace a dosaženo řádového zlepšení detekčního limitu (0,01 ng ml-1 As, doba prekoncentrace 300 s).Atomization of arsine in a novel hydride atomizer for atomic absorption spectrometry (HG-AAS) was thoroughly optimized. This plasma atomizer is based on a dielectric barrier discharge (DBD). Sensitivity and detection limit reached 0.48 s ng-1 As and 0.16 ng ml-1 As, respectively, under optimum atomization conditions (Ar discharge using a flow rate of 60 ml min-1 Ar, DBD power 17 W). Analytical figures of merit reached in DBD are comparable to those found in an externally heated quartz tube multiatomizer (MMQTA) that was chosen as a model of conventional approach to hydride atomization in HG-AAS. An extent of interferences (Se, Sb, Bi) during As determination was investigated comparing both MMQTA and DBD atomizers. The later one was found to be more resistant towards interferences. A simple preconcentration of As in a DBD atomizer was reached after oxygen introduction into the Ar plasma in the DBD resulting in analyte retention in the atomizer followed by its volatilization once the oxygen flow is switched off. Preconcentration efficiency of 100 % was reached and detection limit improvement by a factor of ten was achieved (0.01 ng ml-1 As, preconcentration period 300 s).Department of Analytical ChemistryKatedra analytické chemieFaculty of SciencePřírodovědecká fakult