Tailoring Ru(II) and Os(II) luminophores to their application: from bioimaging and sensing to cytotoxic tools.

Transition metal luminophores show significant potential as multifunctional probes with applications in many fields extending from medicinal chemistry to bioimaging and biosensing. Conjugation of Ru(II)/ Os(II) luminophores to signal peptides is a useful strategy to reliably deliver the probes intracellularly and to specific organelles such as the nucleus and mitochondria. While conventional microscopy methods are used for cellular-imaging, biosensing techniques, can range from fluorescence lifetime imaging microscopy (FLIM) to simple fluorescence intensity-based measurements. This thesis explores the design and photophysical properties of biocompatibleprobes for imaging and sensing within the cellular environment. Chapter 1 reviews the literature and background to the thesis. Chapter 2 describes an achiral Os(II) complex, [Os(tpybenzCOOH)2] 2+ conjugated to the mitochondrial targeting peptide, MPP, at two conjugation sites. The novel bis-MPP conjugate showed NIR emission coincident with the biological window and an interesting approach to theranostics was proposed whereby switch in cell death mechanism (dark toxicity) is reflected in specific probe localisation observed via confocal microscopy. Chapter 3 describes the preparation of two polyarginine-based Os(II) conjugates and their uptake in live cells. While confocal imaging revealed probe- membrane interactions, Os-bisR8 was not taken up by cells, attributed to the large arginine-chains resulting in a significantly high cationic charge. In order to balance lipophilicity and overall cationic charge, Os-bisR4 was prepared and shown to be taken up by A549 lung carcinoma cells. Chapter 4 presents the preparation and characterization of novel ratiometric Ru(II)/ BODIPY core- shell nanoparticles. Single excitation at 480 nm resulted in dual emission corresponding to the BODIPY and Ru(II) particle component. The poly-L-lysine coated particles were studied in two cancerous cell lines as oxygen sensors. The changes in oxygen levels under hypoxic conditions were monitored using xy-lamda (xyλ) scanning microscopy. Chapter 5 investigated a series of novel Ru(biq) 2 (trzbenzCOOH)-conjugates (NLS,R8,MPP,PEG) in CHO and HeLa cell lines. All conjugates exhibited dark cytotoxicity and the origin of toxicity was studied in detail using the mitochondrial depolarization and caspase activity assays. This chapterhighlighted the importance of balancing lipophilicity and targeting ability in order to reduce overall probe toxicity

Garment Recommendations for Online and Offline Consumers

Recommender Systems have obvious influence in environments where data size exceeds the capabilities of any user to fully explore the available choices in the store (physical or on-line). Many algorithms and techniques have been used to help recommending useful and interesting items to users. If the user is unidentified, the process is even harder as there are no historical or other data to use as input. Association rules is a popular technique used for many purposes in Recommender Systems such as for building more robust systems, improving quality of recommendations; and even addressing fundamental limitations of recommender systems and, generally, large datasets, e.g. sparsity and cold start. At the same time, efforts have been made to fully understand if and how differently customers are behaving in an online and in a physical environment.This work tries to combine the two efforts. We use association rules to provide recommendations to customers, as well as understand who the customer is, what her needs are and what is her mentality when entering a physical store or the corresponding e-shop. To fulfill our goal, we used descriptive statistics along with Association Rules analysis of the POS transactional data on basket data level and historical data level

Investigating the Role of Personality Traits and Influence Strategies on the Persuasive Effect of Personalized Recommendations

ABSTRACT Recommender systems provide suggestions for products, services, or information that match users' interests and/or needs. However, not all recommendations persuade users to select or use the recommended item. The Elaboration Likelihood Model (ELM) suggests that individuals with low motivation or ability to process the information provided with a recommended item could eventually get persuaded to select/use the item if appropriate peripheral cues enrich the recommendation. The purpose of this research is to investigate the persuasive effect of certain influence strategies and the role of personality in the acceptance of recommendations. In the present study, a movie Recommender System was developed in order to empirically investigate the aforementioned questions applying certain persuasive strategies in the form of textual messages alongside the recommended item. The statistical method of Fuzzy-Set Qualitative Comparative Analysis (fsQCA) was used for data analysis and the results revealed that motivating messages do change users' acceptance of the recommender item but not unconditionally since user's personality differentiates the effect of the persuasive strategies

Factors Affecting Recommendations\u27 Acceptance in Off-Line Environment

Recommender Systems are traditionally been used in online environments. The present study focuses on factors affecting consumers’ acceptance in recommendation systems that will be used in traditional stores. For this purpose, we have developed a garment recommendation system applying and evaluating the aforementioned factors through an experiment. The main insights of the study indicate that consumers’ personality affect consumers’ preferences and garments’ style. Additionally, when a consumer has high motivation to purchase a particular garment (s)he does not waste his/her time for looking around other types of garments. This means that if a garment provider wants to increase cross selling then he has to recommend products that are close to that event such as accessories

Developing Innovative Services: The Case of the Airport Environment

Part 7: Knowledge Management and Business ProcessesInternational audienceInnovative services consist the main point of interest so for academics as for the business world. The basic objective of this paper is to demonstrate the way that innovative services may change the “consumer experience” in the airport environment. In the following lines we describe the procedure of designing innovative services, so for consumers’ and visitors’ needs as for the needs of the firms which are operated in the airport environment. In order to achieve this goal, we used so the qualitative approach (such as focus groups), as the quantitative approach (collection of 1106 questionnaires)

Intelligent Predictive Analytics for Sustainable Business Investment in Renewable Energy Sources

Willingness to invest in renewable energy sources (RES) is predictable under data mining classification methods. Data was collected from the area of Evia in Greece via a questionnaire survey by using a sample of 360 respondents. The questions focused on the respondents’ perceptions and offered benefits for wind energy, solar photovoltaics (PVs), small hydro parks and biomass investments. The classification algorithms of Bayesian Network classifier, Logistic Regression, Support Vector Machine (SVM), C4.5, k-Nearest Neighbors (k-NN) and Long Short Term Memory (LSTM) were used. The Bayesian Network classifier was the best method, with a prediction accuracy of 0.7942. The most important variables for the prediction of willingness to invest were the level of information, the level of acceptance and the contribution to sustainable development. Future studies should include data on state incentives and their impact on willingness to invest

Ru(ii)/BODIPY core co-encapsulated ratiometric nanotools for intracellular O2 sensing in live cancer cells

Oxygen is a crucial reagent in many biochemical processes within living cells and its concentration can be an effective marker in disease, particularly in cancer where tissue hypoxia has been shown to indicate tumour growth. Probes that can reflect the oxygen concentration and distribution using ratiometric signals can be applied to a range of conventional methods without the need for specialised equipment and are particularly useful. The preparation and in cellulo study of luminescent ratiometric core–shell nanoparticles are presented. Here, a new lipophilic and oxygen-responsive Ru(II) tris-heteroleptic polypyridyl complex is co-encapsulated with a reference BODIPY dye into the core of poly-L-lysine-coated polystyrene particles. The co-core encapsulation ensures oxygen response but reduces the impact of the environment on both probes. Single wavelength excitation of the particles, suspended in aqueous buffer, at 480 nm, triggers well-resolved dual emission from both dyes with peak maxima at515 nm and 618 nm. A robust ratiometric oxygen response is observed from water, with a linear dynamic range of 3.6–262μM which matches well with typical biological ranges. The uptake of RuBDP NPs was found to be cell-line dependent, but in cancerous cell lines, the particles were strongly permeable with late endosomal and partial lysosomal co-staining observed within 3 to 4 hours, eventually leading to extensive staining of the cytoplasm. The co-localisation of the ruthenium and BODIPY emission confirms that the particles remain intact in cellulo with no indication of dye leaching. The ratiometric O2sensing response of the particles in cellulo was demonstrated using a plate-based assay and by confocal xyλ scanning of cells exposed to hypoxic conditions</p