Integration of triboluminescent EuD4TEA crystals to transparent polymers: Impact sensor application

Lanthanide-based organometallic materials are well-known candidate triboluminescent (TL) materials that can show bright emission when a mechanical force is applied. These materials are usually in the form of crystalline powders, and it is often useful to integrate these samples into a polymer matrix in order to achieve processability, enabling coating from a solution/molten state or fabrication as a complex-shaped matrix. In this work, micrometer-sized europium tetrakis (dibenzoylmethide) triethylammonium (EuD4TEA) crystals were synthesized and integrated with various transparent polymers (PMMA, PS, PVDF, and PU) using two approaches: (i) blending and (ii) surface impregnation. In the former method, the crystalline particles were molecularly dissolved; therefore, a TL response cannot be achieved. More than 10 wt % TL crystals in the composite is needed to obtain TL signals. However, TL signal was achieved at 2.5 wt % when a composite was prepared by the latter approach. TL intensity shows exponential decay with consecutive mechanical action. The TL emission of PU-based surface impregnated composite expires with long-lived emission, and maximum TL response with respect to applied force was measured between 2.45 and 42.0 N.Scientific and Technological Research Council of Turkey (TUBITAK KBAG-114Z292

A new method to extend the stress response of triboluminescent crystals by using hydrogels

Polyacrylamide hydrogel entrapment of EuD4TEA or Cu(NCS)(py)2(PPh3) radically extends the emission time of the triboluminescent (TL) crystalline particles by a factor of 103, optimized when matching the hydrophilic/hydrophobic characteristics of the TL/gel components. Triboluminescence intensity improves with hydration of the TL/hydrogel composite. The composites may be used in impact-related sensor applications

TL özelliğe sahip kırmızı ve mavi kristalin farklı polimer formlarına işlenmesi

Thesis (Master)--Izmir Institute of Technology, Materials Science and Engineering, Izmir, 2016Includes bibliographical references (leaves. 50-54)Text in English; Abstract: Turkish and Englishxii, 54 leavesTriboluminescence (TL) is known as the emission of light upon the application of any mechanical force. In this master thesis, two organometallic-based TL crystals, which are EuD4TEA and Cu(NCS)(py)2(PPh3) were obtained and they were integrated in the transparent polymers: poly (methylmetacrylate) (PMMA), poly (styrene) (PS), poly (urethane) (PU) and polyvinylidene fluoride (PVDF) for different end-use. In the development of composites, two different processes were carried out: i) embedding (or blending) and ii) surface impregnation. The different end-use polymers were used as transparent polymer film, electrospun nanofibers, and nanobeads. TL performance of composites were investigated by using drop tower system which was specficically designed for this research. Atomic force microscopy (AFM), scanning electron microscopy (SEM) were used to characterize the topographic and morphologic properties of both polymers and composites. Additionally, fluorescence microscopy helped to understand the signal of emitted light by composites. Lastly, piezoelectric properties of composite materials were invetigated by oscilloscope. According to results, type of process, particle size of crystal, surface property and form of host material (polymer), the concentration of crystalline particles in composites were determined as the main parameters and the results were estimated with respect to these parameters. PU-based composite film and fiber show better stability towards mechnical stress rather than PMMA, PS, and PVDF due to the roughness surface of thin-film surface for film-based composites, smallest wickerwork formation of electrospun mats for fiber-based composite, and the chemical affinity of PU with TL crystals.Tribolüminesans (TL) olarak bilinen kristal yapılar mekanik kuvvet altında ışık emisyonu yapma özelliğine sahiptirler. Bu yüksek lisans tezinde, organik ve metal yapıları bir arada bulunduran iki TL kristal elde edilmiş ve bu parçacıklar PMMA (poli metil metakrilat), PS (poli sitren), PU (poli üretan) ve PVDF (poli vinil florür) transparan özellikteki polimerler kullanılarak ince-katmanlı film, elektrospun fiber ve nano boyutundaki tanecikler elde edilen matrisler ile entegrasyona tabii tutulmuştur. Kompozit malzemelerin elde edilmesi için iki farklı deneysel metot geliştirilmiştir: i) yükleme işlemi ve ii) yüzeye depolama işlemi. Kompozit malzemelerin TL performansları bu tez için özel tasarlanan atış kule sistemi ile analiz edilmiştir. Bunun yanı sıra, atomik kuvvet mikroskobu (AFM), taramalı elektron mikroskobu (SEM) polimerlerin ve kompozit malzemelerin topografik ve morfolojik özellklerini değerlendirmek için kullanılmıştır. Ayrıca, flüoresans mikroskobu kullanılarak kompozit malzemelerin emisyon sırasındaki renk sinyalleri belirlenmiştir. Son olarak piezoelectrik özellikleri osiloskop kullanılarak tamamlanmıştır. Tüm bu cihazlardan elde edilen sonuçlar değerlendirildiğinde, deneysel prosedür, kristal parçacıkların boyutları, polimer malzemenin formu ve yüzey özelliği, kullanılan kristallerin kompozit içindeki miktarı bu çalışmada temel parametreler olarak belirlenmiştir. PU esaslı elde edilen film ve fiber kompozitler PMMA, PS, ve PVDF esaslı kompozitlerden daha iyi sonuç göstermiştir. Bunun nedeni olarak, film esaslı kompozitler için ince katmanlı PU filmin daha engebeli bir yüzey olması; fiber esaslı kompozitler için elektrospun PU fiberin daha küçük yapılardan oluşması, tüm bunlara ek olarak PU’nın kimyasal olarak TL özellikteki iki kristalle kimyasal etkileşim oluşturulması gösterilebilir

TL özelliğe sahip kırmızı ve mavi kristalin farklı polimer formlarına işlenmesi

Thesis (Master)--Izmir Institute of Technology, Materials Science and Engineering, Izmir, 2016Includes bibliographical references (leaves. 50-54)Text in English; Abstract: Turkish and Englishxii, 54 leavesTriboluminescence (TL) is known as the emission of light upon the application of any mechanical force. In this master thesis, two organometallic-based TL crystals, which are EuD4TEA and Cu(NCS)(py)2(PPh3) were obtained and they were integrated in the transparent polymers: poly (methylmetacrylate) (PMMA), poly (styrene) (PS), poly (urethane) (PU) and polyvinylidene fluoride (PVDF) for different end-use. In the development of composites, two different processes were carried out: i) embedding (or blending) and ii) surface impregnation. The different end-use polymers were used as transparent polymer film, electrospun nanofibers, and nanobeads. TL performance of composites were investigated by using drop tower system which was specficically designed for this research. Atomic force microscopy (AFM), scanning electron microscopy (SEM) were used to characterize the topographic and morphologic properties of both polymers and composites. Additionally, fluorescence microscopy helped to understand the signal of emitted light by composites. Lastly, piezoelectric properties of composite materials were invetigated by oscilloscope. According to results, type of process, particle size of crystal, surface property and form of host material (polymer), the concentration of crystalline particles in composites were determined as the main parameters and the results were estimated with respect to these parameters. PU-based composite film and fiber show better stability towards mechnical stress rather than PMMA, PS, and PVDF due to the roughness surface of thin-film surface for film-based composites, smallest wickerwork formation of electrospun mats for fiber-based composite, and the chemical affinity of PU with TL crystals.Tribolüminesans (TL) olarak bilinen kristal yapılar mekanik kuvvet altında ışık emisyonu yapma özelliğine sahiptirler. Bu yüksek lisans tezinde, organik ve metal yapıları bir arada bulunduran iki TL kristal elde edilmiş ve bu parçacıklar PMMA (poli metil metakrilat), PS (poli sitren), PU (poli üretan) ve PVDF (poli vinil florür) transparan özellikteki polimerler kullanılarak ince-katmanlı film, elektrospun fiber ve nano boyutundaki tanecikler elde edilen matrisler ile entegrasyona tabii tutulmuştur. Kompozit malzemelerin elde edilmesi için iki farklı deneysel metot geliştirilmiştir: i) yükleme işlemi ve ii) yüzeye depolama işlemi. Kompozit malzemelerin TL performansları bu tez için özel tasarlanan atış kule sistemi ile analiz edilmiştir. Bunun yanı sıra, atomik kuvvet mikroskobu (AFM), taramalı elektron mikroskobu (SEM) polimerlerin ve kompozit malzemelerin topografik ve morfolojik özellklerini değerlendirmek için kullanılmıştır. Ayrıca, flüoresans mikroskobu kullanılarak kompozit malzemelerin emisyon sırasındaki renk sinyalleri belirlenmiştir. Son olarak piezoelectrik özellikleri osiloskop kullanılarak tamamlanmıştır. Tüm bu cihazlardan elde edilen sonuçlar değerlendirildiğinde, deneysel prosedür, kristal parçacıkların boyutları, polimer malzemenin formu ve yüzey özelliği, kullanılan kristallerin kompozit içindeki miktarı bu çalışmada temel parametreler olarak belirlenmiştir. PU esaslı elde edilen film ve fiber kompozitler PMMA, PS, ve PVDF esaslı kompozitlerden daha iyi sonuç göstermiştir. Bunun nedeni olarak, film esaslı kompozitler için ince katmanlı PU filmin daha engebeli bir yüzey olması; fiber esaslı kompozitler için elektrospun PU fiberin daha küçük yapılardan oluşması, tüm bunlara ek olarak PU’nın kimyasal olarak TL özellikteki iki kristalle kimyasal etkileşim oluşturulması gösterilebilir

Smart phone assisted detection and quantification of cyanide in drinking water by paper based sensing platform

An organometallic dye, europium tetrakis dibenzoylmethide triethylammonium (EuD4TEA) and gold nanoparticles (Au NPs) impregnated paper based sensor platform have been utilized for development of fluorescence turn-on cyanide assay in aqueous media. The ordinary filter paper with 6 μ m pore size were employed as solid support that facilitates impregnation of EuD4TEA and gold nanoparticles and provides durability. Detection mechanism relying on two processes (i) dissolution of gold nanoparticles causing fluorescence recovery and (ii) ligand exchange of triethyl amine with CN group stimulating cyanide specific fluorescence enhancement. The paper platform exhibit naked eye distinguishable color transition upon CN− addition from 10−2 to 10−12 M. To standardize the methodology a homemade image processing algorithm has been developed that enabling calibration of color change and quantify CN− concentration. The described algorithm is applicable to Android smart phones and facilitate transforming these devices into a quantitative cyanide detector. The overall methodology provides instrument free cyanide detection and therefore rapid control of water quality and safety at off-field conditions

Selective Enrichment of Histidine Phosphorylated Peptides Using Molecularly Imprinted Polymers

Protein histidine phosphorylation (pHis) is involved in molecular signaling networks in bacteria, fungi, plants, and higher eukaryotes including mammals and is implicated in human diseases such as cancer. Detailed investigations of the pHis modification are hampered due to its acid-labile nature and consequent lack of tools to study this post-translational modification (PTM). We here demonstrate three molecularly imprinted polymer (MIP)-based reagents, MIP1-MIP3, for enrichment of pHis peptides and subsequent characterization by chromatography and mass spectrometry (LC-MS). The combination of MIP1 and β-elimination provided some selectivity for improved detection of pHis peptides. MIP2 was amenable to larger pHis peptides, although with poor selectivity. Microsphere-based MIP3 exhibited improved selectivity and was amenable to enrichment and detection by LC-MS of pHis peptides in tryptic digests of protein mixtures. These MIP protocols do not involve any acidic solvents during sample preparation and enrichment, thus preserving the pHis modification. The presented proof-of-concept results will lead to new protocols for highly selective enrichment of labile protein phosphorylations using molecularly imprinted materials