On graphical and numerical characterization of proteomics maps

We outlined a mathematical approach suitable for characterization of experimental data given by 2-D densitograms. In particular we consider numerical characterization of proteomics maps. The basis of our approach is to order "spots" of a 2-D map and assign them unique labels (that in general will depend on the criteria used for ordering). In this way a map is "translated" into a sequence. In the next step one associates with the generated sequence a geometrical path and views such a path as a mathematical object that needs characterization. We have ordered spots representing proteins in 2-D gel plates according to their relative intensities which results in a zigzag path that produces a complicated "fingerprint" pattern. Mathematical characterization of zigzag pattern follows similar mathematical characterizations of embedded patterns based on matrices, the elements of which are given as quotients of Euclidean distance between spots and the distance along the zigzag path. The leading eigenvalue of constructed matrices is taken to represent characterization of the original 2-D map. Comparison of different 2-D maps (simulated by using random generator) allows one to construct partial order, which although qualitative in nature gives some insight into perturbation induced by foreign agents to the proteome of the control cell.     

小分子有机电致发光器件和材料的研究及应用

有机电致发光器件(OLED)是在电场作用下,以有机材料为活性发光层的器件.由于OLED具有亮度高、响应快、视角宽、工艺简单、可柔性等优点,在现代科学研究及技术应用中备受关注.其商业化应用,诸如平板显示(FPD)和固体照明(SSL)等,正在不断向前推进.本文综述了小分子OLED的各种器件结构和功能材料研究进展以及该领域存...     

On the dependence of a characterization of proteomics maps on the number of protein spots considered

We have reexamined the numerical characterization of proteomics maps based on the construction of novel distance matrices associated with the nearest neighbor graph for the protein spots. In particular we consider dependence of a characterization of proteomics map on the number of proteins considered in the analysis. We examined a collection of proteomics maps in which we approximately doubled the number of spots to be used for quantitative analysis, considering cases of maps having 30, 50, 100, 250, 500, and 1054 protein spots. For each case we have compared the similarity-dissimilarity results for five proteomics maps of rat liver cells associated with the control group and four proliferators administrated by intraperitoneal injection. We found that proteins maps based on a set of about the 250 most abundant proteins spots suffice for a satisfactory numerical characterization of such maps.     

Neoteric Advances in Oxygen Bridged Triaryl Boron-based Delayed Fluorescent Materials for Organic Light Emitting Diodes

Since their first demonstration, thermally activated delayed fluorescence (TADF) materials have been emerged as the most promising emitters because of their promising applications in optoelectronics, typified by organic light-emitting diodes (OLEDs). In which, the rigid oxygen bridged boron acceptor-featured ( DOBNA ) emitters have gained tremendous impetus for OLEDs, which is ascribed to their excellent external quantum efficiency (EQE). However, these materials often displayed severe efficiency roll-off and poor operational stability. Therefore, there needs to be a comprehensive understanding of the aspect of the molecular design and structure-property relationship. To the best of our knowledge, there is no detailed review on the structure-function outlook of DOBNA -based emitters emphasizing the effect of the nature of donor units, their number density, and substitution pattern on the physicochemical properties, excited state dynamics and OLED performance were reported. To fill this gap, herein we presented the recent advancements in DOBNA -based acceptor featured TADF materials by classifying them into several subgroups based on the molecular design i. e. donor-acceptor (D−A), D−A-D, A−D-A, and multi-resonant TADF (MR-TADF) emitters. The detailed design concepts, along with their respective physicochemical and OLED performances were summarized. Finally, the prospective of this class of materials in forthcoming OLED displays is also discussed.     

Highly efficient blue-emissive electroluminescence: nondestructive color regulation effect of orthogonal cyano-substitution in hybrid locally-excited and charge-transfer (HLCT) backbone emitters

Blue-emissive materials are crucial in organic light emitting diodes (OLED). In this work, we report two highly efficient donor-acceptor materials PPIPO and PPIPOCN. PPIPO is constructed with phenanthroimidazole (PI) and oxadiazole groups, which is blue-emissive with high photoluminescent quantum yield (PLQY) of 86.2%. Furthermore, the cyano-substituted PPIPOCN realize more blue-shifted emission and equal PLQY comparing to PPIPO, which can be assigned to the formation of hybridized local and charge-transfer (HLCT) excited state. Significantly, the OLED based on the two materials both demonstrated decent performances, such as high external quantum efficiency (EQE) of 12.5% in PPIPO and nice blue purity of Commission Internationale de l'Eclairage y-coordinate (CIEy) of＜0.15 in PPIPOCN. This work provides a potential strategy for the designing of the high-efficiency and low-cost next-generation electro-fluorescent materials.     

Research Progress on Triarylmethyl Radical-Based High-Efficiency OLED

Perchlorotrityl radical (PTM), tris (2,4,6-trichlorophenyl) methyl radical (TTM), (3,5-dichloro-4-pyridyl) bis (2,4,6 trichlorophenyl) methyl radical (PyBTM), (N-carbazolyl) bis (2,4,6-trichlorophenyl) methyl radical (CzBTM), and their derivatives are stable organic radicals that exhibit light emissions at room temperature. Since these triarylmethyl radicals have an unpaired electron, their electron spins at the lowest excited state and ground state are both doublets, and the transition from the lowest excited state to the ground state does not pose the problem of a spin-forbidden reaction. When used as OLED layers, these triarylmethyl radicals exhibit unique light-emitting properties, which can increase the theoretical upper limit of the OLED’s internal quantum efficiency (IQE) to 100%. In recent years, research on the luminescent properties of triarylmethyl radicals has attracted increasing attention. In this review, recent developments in these triarylmethyl radicals and their derivatives in OLED devices are introduced.     

Molecular Orientation Effects in Organic Light‐Emitting Diodes

It is well known that by horizontally aligning the transition dipole moments of exciton dipoles in the emitter films of organic light‐emitting diodes (OLEDs), a larger fraction of the radiative power can escape from the OLED stack, increasing the light outcoupling efficiency by up to 50 % compared to the isotropic counterparts. In this account, we review recent advances in understanding this phenomenon, with a special focus on the practical strategies to control the molecular orientation in vacuum‐deposited films of thermally activated delayed fluorescent (TADF) dyes. The role of molecular orientation in efficient OLED design is discussed, which has been experimentally proven to increase the external quantum efficiency exceeding 30 %. We outline the future challenges and perspectives in this field, including the potential to extend the concept to the solution‐processed films. Finally, the development of multiscale computer simulations is reviewed to assess their potential as a complementary approach to systematically screening OLED molecules in silico.     

Multivalence and spot heterogeneity in microarray-based measurement of binding constants

Microarray technology is increasingly used for a miniaturised and parallel measurement of binding constants. In microarray experiments heterogeneous functionalization of surfaces with capture molecules is a problem commonly encountered. For multivalent ligands, especially, however, binding is strongly affected by receptor density. Here we show that high-resolution imaging of microarrays followed by image segmentation and separate analysis of bright and dark parts provides valuable information about ligand binding. Binding titrations were conducted with monovalent and bivalent fluorescent ligand peptides for the model receptor vancomycin. Microarrays were scanned with a confocal microscope and inhomogeneous spots were evaluated either as a whole or after segmentation into bright and dark areas. Whereas the binding constant for the monovalent ligand was hardly affected by spot heterogeneity, for the bivalent ligand affinity was higher for the parts of the spots with a greater density of receptors. This information was lost if the spots were analysed as a whole. These results reveal that imaging resolution may be a key factor in miniaturised binding assays, emphasising the importance of high-resolution images and image segmentation for new techniques, for example SPR imaging.     

Quantitative comparison and evaluation of two commercially available,two-dimensional electrophoresis image analysis software packages,Z3 and Melanie

While a variety of software packages are available for analyzing two-dimensional electrophoresis (2-DE) gel images, no comparisons between these packages have been published, making it difficult for end users to determine which package would best meet their needs. The goal here was to develop a set of tests to quantitatively evaluate and then compare two software packages, Melanie 3.0 and Z3, in three of the fundamental steps involved in 2-DE image analysis: (i) spot detection, (ii) gel matching, and (iii) spot quantitation. To test spot detection capability, automatically detected protein spots were compared to manually counted, "real" protein spots. Spot matching efficiency was determined by comparing distorted (both geometrically and nongeometrically) gel images with undistorted original images, and quantitation tests were performed on artificial gels with spots of varying Gaussian volumes. In spot detection tests, Z3 performed better than Melanie 3.0 and required minimal user intervention to detect approximately 89% of the actual protein spots and relatively few extraneous spots. Results from gel matching tests depended on the type of image distortion used. For geometric distortions, Z3 performed better than Melanie 3.0, matching 99% of the spots, even for extreme distortions. For nongeometrical distortions, both Z3 and Melanie 3.0 required user intervention and performed comparably, matching 95% of the spots. In spot quantitation tests, both Z3 and Melanie 3.0 predicted spot volumes relatively well for spot ratios less than 1:6. For higher ratios, Melanie 3.0 did much better. In summary, results suggest Z3 requires less user intervention than Melanie 3.0, thus simplifying differential comparison of 2-DE gel images. Melanie 3.0, however, offers many more optional tools for image editing, spot detection, data reporting and statistical analysis than Z3. All image files used for these tests and updated information on the software are available on the internet (http://www.umbc.edu/proteome), allowing similar testing of other 2-DE image analysis software packages.     

A Unique Blend of 2-Fluorenyl-2-anthracene and 2-Anthryl-2-anthracence Showing White Emission and High Charge Mobility

White-light-emitting materials with high mobility are necessary for organic white-light-emitting transistors, which can be used for self-driven OLED displays or OLED lighting. In this study, we combined two materials with similar structures—2-fluorenyl-2-anthracene (FlAnt) with blue emission and 2-anthryl-2-anthracence (2A) with greenish-yellow emission—to fabricate OLED devices, which showed unusual solid-state white-light emission with the CIE coordinates (0.33, 0.34) at 10 V. The similar crystal structures ensured that the OTFTs based on mixed FlAnt and 2A showed high mobility of 1.56 cm² V⁻¹ s⁻¹. This simple method provides new insight into the design of high-performance white-emitting transistor materials and structures.     

不对称刚性扭曲菲并咪唑分子的设计合成及其深蓝电致发光性能研究

本研究通过不对称、刚性扭曲的分子设计理念,合成了高效深蓝有机电致发光材料MBTPI。该化合物具有很高的分解温度(496℃)与玻璃转化温度(190℃),有利于提高器件的稳定性;不对称刚性扭曲的分子构型有效控制了分子的整体共轭程度,使发光波长在深蓝光区,固体发光量子产率高达74%。理论计算验证了分子不对称扭曲的构型,并且发现甲基的引入对前线轨道分布影响不大,分子保留了较好的双极性质。基于MBTPI的非掺杂器件发射出非常高效的深蓝光。色纯度为(0.15,0.07),非常接近NTSC的蓝光标准(0.14,0.08)。最大外量子效率为4.91%,并且效率滚降很小,为性能最好的非掺杂深蓝光器件之一。     

Thermally Activated Delayed Fluorescence Materials: Towards Realization of High Efficiency through Strategic Small Molecular Design

Thermally activated delayed fluorescence (TADF) is one of the most intriguing and promising discoveries towards realization of highly-efficient organic light emitting diodes (OLED) utilizing small molecules as emitters. It has the capability of manifesting all excitons generated during the electroluminescent processes, consequently achieving 100 % of internal quantum efficiency. Since the report of the first efficient OLED based on a TADF small molecule in 2012 by Adachi et al., the quest for optimal TADF materials for OLED application has never stopped. Various TADF molecules bearing different design concepts and strategies have been designed and produced, with the aim to boost the overall performances of corresponding OLEDs. In this minireview, the general principles of TADF molecular design based on three basic categories of TADF species: twisted intramolecular charge transfer (TICT), through-space charge transfer (TSCT) and multi-resonance induced TADF (MR-TADF) are discussed in detail. Several key aspects with respect to each category, as well as some effective methods to enhance the efficiency of TADF materials and corresponding OLEDs from the molecular engineering perspectives, are summarized and discussed to exhibit a general landscape of TADF molecular design to a wide variety of scientific researchers within this particular disciplinary area.     

A simple method for assigning multiple immunogens to their protein on a two-dimensional blot and its application to asthma-causing allergens

A "one-step" procedure, that not only removes the color and blocking proteins used in the colorimetric immunodetection step but also stains the proteins originally on the blot, is presented. Following immunostaining and recording of immunoreactive spots, the blot was allowed to air-dry overnight (or longer) at room temperature and then counterstained with a colloidal gold solution. This "air-drying" process apparently altered the affinity of the blocking proteins (and possibly other proteins added subsequently to the blotting step) towards the nitrocellulose membrane causing them to be removed by the acidic colloidal gold solution while the "blotted" proteins were being stained. The sensitivity of this counterstained blot was comparable to that of the blot without going through the immunodetection process. Since both immunodetection and protein staining were carried out on the same blot, this allowed easy identification of many immunoreactive spots to their corresponding proteins when the two profiles were superimposed. Using this procedure, we have detected 25 immunoreactive spots (or allergens) from the whole body extract of the German cockroach (Blattella germanica) that contribute to asthma and assigned them to their corresponding proteins on a two-dimensional (2-D) protein map. The apparent Mr and pI for each of the allergens were determined. We have also located one of the major cockroach allergens, Bla g 5 (glutathione S-transferase). Two-dimensional zymography revealed the presence of ten gelatinase-type proteolytic enzymes. Only one of the ten proteases comigrated with the immunoreactive proteins indicating that unlike other allergen-producing systems, most of the cockroach allergens do not possess protease activity.     

A Unique Blend of 2‐Fluorenyl‐2‐anthracene and 2‐Anthryl‐2‐anthracence Showing White Emission and High Charge Mobility

White‐light‐emitting materials with high mobility are necessary for organic white‐light‐emitting transistors, which can be used for self‐driven OLED displays or OLED lighting. In this study, we combined two materials with similar structures—2‐fluorenyl‐2‐anthracene (FlAnt) with blue emission and 2‐anthryl‐2‐anthracence (2A) with greenish‐yellow emission—to fabricate OLED devices, which showed unusual solid‐state white‐light emission with the CIE coordinates (0.33, 0.34) at 10 V. The similar crystal structures ensured that the OTFTs based on mixed FlAnt and 2A showed high mobility of 1.56 cm² V⁻¹ s⁻¹. This simple method provides new insight into the design of high‐performance white‐emitting transistor materials and structures.     

A comparative study of proteomics maps using graph theoretical biodescriptors

This paper reports the development of new methods for mathematical characterization of effects of different toxic agents on the cellular proteome. We describe numerical characterization of proteomics maps based on mathematical invariants. A graph is first associated with a proteomics map by considering partial ordering of spots on 2-D gels by ordering proteins with respect to the mass and the charge, the two properties by which proteins are separated. The graph is then embedded over the map, and several graph theoretical invariants have been constructed. In particular we consider invariants that can be extracted from the Euclidean distance-adjacency matrix of the embedded graph, in which only Euclidean distances between adjacent vertices of a graph are considered. The approach is illustrated using proteomics patterns of normal liver cells of rats and those derived from liver cells of animals exposed to four peroxisome proliferators. In contrast to direct comparison of spot abundance our approach incorporates information on spots locations. The difference between the two approaches is that in the first case only changes in abundances are considered as a measure of perturbation of the proteome map, but in the second case not only the charge but also the mass of proteins are used for ordering protein spots.     

Development of Materials for Blue Organic Light Emitting Devices

The success of organic light emitting diodes (OLED) has been witnessed by the commercialization of this technology for manufacturing the vivid and colorful displays used in our daily life now. The prospective growth of OLED technology on display industry will be optimistic. Over the last three decades, many different approaches on material and device designs have been implemented for improving the efficiency and stability of OLED devices. These efforts install main cornerstones to support the great achievement of OLED technology. However, until now, the performance and stability of blue OLEDs still have some concerns. This troublesome issue should be totally conquered before the large‐scale manufactures dominated over other display technologies, particularly liquid crystal‐based displays, takes place. Though significant progress has already been made to achieve high performance and long lifetime blue OLEDs, this topic still remains as one of the hot researches in OLEDs. We have been working on this area for about two decades and made some notable contributions. Consequently, in this personal account we have outlined our efforts to obtain better performing blue OLEDs by utilizing a range of emitters based on fluorescence, phosphorescence, delayed fluorescence and exciplex systems. We have also developed some novel host materials for blue OLEDs, which are worth mentioning in this account.     

Direct evidence of molecular aggregation and degradation mechanism of organic light-emitting diodes under joule heating: an STM and photoluminescence study

The Joule heating effect on electroluminescent efficiency is important in the degradation origin of organic light-emitting diodes (OLED). Scanning tunneling microscopy (STM) and photoluminescence (PL) measurements were performed on the guest molecule BT (1,4-bis(benzothiazole-vinyl) benzene), host molecule TPBI (2, 2',2' '-(1,3,5-phenylene)tris-[1-phenyl-1H-benzimidazole]), and their mixture deposited on an HOPG surface to study the OLED degradation mechanism due to thermal heating. At room temperature, BT and TPBI in the mixed layer show good compatibility and high PL intensity, but at higher temperatures, they show phase separation and aggregation into their own domains and a concomitant decrease in PL intensity. The PL intensity loss suggests ineffective energy transfer from TPBI to BT due to phase separation, which may cause OLED degradation. Scanning tunneling spectroscopy (STS) results show that the band gaps of TPBI and BT remain unchanged with the annealing temperature, suggesting that the heat-induced decay of OLED is related to the interfacial structural change rather than the respective molecular band gap. The results provide direct evidence showing how the molecular structures of the mixed layer vary and affect the PL intensity due to temperature.     

Relationship between Hot Spot Residues and Ligand Binding Hot Spots in Protein-Protein Interfaces

In the context of protein-protein interactions, the term "hot spot" refers to a residue or cluster of residues that makes a major contribution to the binding free energy, as determined by alanine scanning mutagenesis. In contrast, in pharmaceutical research, a hot spot is a site on a target protein that has high propensity for ligand binding and hence is potentially important for drug discovery. Here we examine the relationship between these two hot spot concepts by comparing alanine scanning data for a set of 15 proteins with results from mapping the protein surfaces for sites that can bind fragment-sized small molecules. We find the two types of hot spots are largely complementary; the residues protruding into hot spot regions identified by computational mapping or experimental fragment screening are almost always themselves hot spot residues as defined by alanine scanning experiments. Conversely, a residue that is found by alanine scanning to contribute little to binding rarely interacts with hot spot regions on the partner protein identified by fragment mapping. In spite of the strong correlation between the two hot spot concepts, they fundamentally differ, however. In particular, while identification of a hot spot by alanine scanning establishes the potential to generate substantial interaction energy with a binding partner, there are additional topological requirements to be a hot spot for small molecule binding. Hence, only a minority of hot spots identified by alanine scanning represent sites that are potentially useful for small inhibitor binding, and it is this subset that is identified by experimental or computational fragment screening.     

Dried Blood Spot Proteomics: Surface Extraction of Endogenous Proteins Coupled with Automated Sample Preparation and Mass Spectrometry Analysis

Dried blood spots offer many advantages as a sample format including ease and safety of transport and handling. To date, the majority of mass spectrometry analyses of dried blood spots have focused on small molecules or hemoglobin. However, dried blood spots are a potentially rich source of protein biomarkers, an area that has been overlooked. To address this issue, we have applied an untargeted bottom-up proteomics approach to the analysis of dried blood spots. We present an automated and integrated method for extraction of endogenous proteins from the surface of dried blood spots and sample preparation via trypsin digestion by use of the Advion Biosciences Triversa Nanomate robotic platform. Liquid chromatography tandem mass spectrometry of the resulting digests enabled identification of 120 proteins from a single dried blood spot. The proteins identified cross a concentration range of four orders of magnitude. The method is evaluated and the results discussed in terms of the proteins identified and their potential use as biomarkers in screening programs.