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Exploiting Dissent: Towards Fuzzing-based Differential Black Box Testing of TLS Implementations
(2017)
The Transport Layer Security (TLS) protocol is one of the most widely used security protocols on the internet. Yet do implementations of TLS keep on suffering from bugs and security vulnerabilities. In large part is this due to the protocol's complexity which makes implementing and testing TLS notoriously difficult. In this paper, we present our work on using differential testing as effective means to detect issues in black-box implementations of the TLS handshake protocol. We introduce a novel fuzzing algorithm for generating large and diverse corpuses of mostly-valid TLS handshake messages. Stimulating TLS servers when expecting a ClientHello message, we find messages generated with our algorithm to induce more response discrepancies and to achieve a higher code coverage than those generated with American Fuzzy Lop, TLS-Attacker, or NEZHA. In particular, we apply our approach to OpenssL, BoringSSL, WolfSSL, mbedTLS, and MatrixSSL, and find several real implementation bugs; among them a serious vulnerability in MatrixSSL 3.8.4. Besides do our findings point to imprecision in the TLS specification. We see our approach as present in this paper as the first step towards fully interactive differential testing of black-box TLS protocol implementations. Our software tools are publicly available as open source projects.
There is increasing evidence of central hyperexcitability in chronic whiplash-associated disorders (cWAD). However, little is known about how an apparently simple cervical spine injury can induce changes in cerebral processes. The present study was designed (1) to validate previous results showing alterations of regional cerebral blood flow (rCBF) in cWAD, (2) to test if central hyperexcitability reflects changes in rCBF upon non-painful stimulation of the neck, and (3) to verify our hypothesis that the missing link in understanding the underlying pathophysiology could be the close interaction between the neck and midbrain structures. For this purpose, alterations of rCBF were explored in a case-control study using H215O positron emission tomography, where each group was exposed to four different conditions, including rest and different levels of non-painful electrical stimulation of the neck. rCBF was found to be elevated in patients with cWAD in the posterior cingulate and precuneus, and decreased in the superior temporal, parahippocampal, and inferior frontal gyri, the thalamus and the insular cortex when compared with rCBF in healthy controls. No differences in rCBF were observed between different levels of electrical stimulation. The alterations in regions directly involved with pain perception and interoceptive processing indicate that cWAD symptoms might be the consequence of a mismatch during the integration of information in brain regions involved in pain processing.
Im Eurocode 3 wird im Gegensatz zu DIN 18800 die Bemessung von Verbindungen nicht in der Grundnorm DIN EN 1993‐1‐1, sondern in anderen Normenteilen geregelt. Dieser Beitrag behandelt die Bemessung geschweißter Verbindungen nach DIN EN 1993‐1‐8, die auch Hohlprofile, aber weder dünnwandige Bauteile noch Stähle höherer Festigkeit als S460 einschließt, vergleicht diese Bemessung mit der nach DIN 18800‐1, erläutert sie an Beispielen und hebt die wesentlichen Änderungen hervor. Da diese Änderungen auch die im Vergleich zu DIN 18800 viel stärkere Verknüpfung der in der Tragwerksplanung ansetzbaren Beanspruchbarkeiten mit dem Aufwand der Prüfung und Qualitätsüberwachung bei der Herstellung betreffen, werden abschließend wichtige Regelungen der DIN EN 1090‐2 zur Ausführung und Prüfung von Schweißnähten beschrieben, die auch der Tragwerksplaner kennen muss.
Optimization of energetic refurbishment roadmaps for multi-family buildings utilizing heat pumps
(2023)
A novel methodology for calculating optimized refurbishment roadmaps is developed in this paper. The aim of the roadmaps is to determine when and how should which component of the building envelope and heat generation system be refurbished to achieve the lowest net present value. The integrated optimization approach couples a particle swarm optimization algorithm with a dynamic building simulation of the building envelope and the heat supply system. Due to a free selection of implementation times and refurbishment depth, the optimization method achieves the lowest net present value and high CO2 reduction and is therefore an important contribution to achieve climate neutrality in the building stock.
The method is exemplarily applied to a multi-family house built in 1970. In comparison to a standard refurbishment roadmap, cost savings of 6–16 % and CO2 savings of 6–59 % are possible. The sensitivity of the refurbishment roadmap measures is analyzed on the basis of a parametric analysis. Robust optimization results are obtained with a mean refurbishment level of approx. 50 kWh/m2/a of the building envelope. The preferred heat generation system is a bivalent brine-heat pump system with a share of 70 % of the heat load being covered by the electric heat pump.
Predictive control has great potential in the home energy management domain. However, such controls need reliable predictions of the system dynamics as well as energy consumption and generation, and the actual implementation in the real system is associated with many challenges. This paper presents the implementation of predictive controls for a heat pump with thermal storage in a real single-family house with a photovoltaic rooftop system. The predictive controls make use of a novel cloud camera-based short-term solar energy prediction and an intraday prediction system that includes additional data sources. In addition, machine learning methods were used to model the dynamics of the heating system and predict loads using extensive measured data. The results of the real and simulated operation will be presented.
There is an increasing demand by an ever-growing number of mobile customers for transfer of rich media content. This requires very high bandwidth which either cannot be provided by the current cellular systems or puts pressure on the wireless networks, affecting customer service quality. This study introduces COARSE – a novel cluster-based quality-oriented adaptive radio resource allocation scheme, which dynamically and adaptively manages the radio resources in a cluster-based two-hop multi-cellular network, having a frequency reuse of one. COARSE is a cross-layer approach across physical layer, link layer and the application layer. COARSE gathers data delivery-related information from both physical and link layers and uses it to adjust bandwidth resources among the video streaming end-users. Extensive analysis and simulations show that COARSE enables a controlled trade-off between the physical layer data rate per user and the number of users communicating using a given resource. Significantly, COARSE provides 25–75% improvement in the computed user-perceived video quality compared with that obtained from an equivalent single-hop network.
Amorphous In-Ga-Zn-O (IGZO) is a high-mobility semiconductor employed in modern thin-film transistors for displays and it is considered as a promising material for Schottky diode-based rectifiers. Properties of the electronic components based on IGZO strongly depend on the manufacturing parameters such as the oxygen partial pressure during IGZO sputtering and post-deposition thermal annealing. In this study, we investigate the combined effect of sputtering conditions of amorphous IGZO (In:Ga:Zn=1:1:1) and post-deposition thermal annealing on the properties of vertical thin-film Pt-IGZO-Cu Schottky diodes, and evaluated the applicability of the fabricated Schottky diodes for low-frequency half-wave rectifier circuits. The change of the oxygen content in the gas mixture from 1.64% to 6.25%, and post-deposition annealing is shown to increase the current rectification ratio from 10 5 to 10 7 at ±1 V, Schottky barrier height from 0.64 eV to 0.75 eV, and the ideality factor from 1.11 to 1.39. Half-wave rectifier circuits based on the fabricated Schottky diodes were simulated using parameters extracted from measured current-voltage and capacitance-voltage characteristics. The half-wave rectifier circuits were realized at 100 kHz and 300 kHz on as-fabricated Schottky diodes with active area of 200 μm × 200 μm, which is relevant for the near-field communication (125 kHz - 134 kHz), and provided the output voltage amplitude of 0.87 V for 2 V supply voltage. The simulation results matched with the measurement data, verifying the model accuracy for circuit level simulation.
We generalize the fluid flow problem of an oscillating flat plate (II. Stokes problem) in two directions. We discuss first the oscillating porous flat plate with superimposed blowing or suction. The second generalization is concerned with an increasing or decreasing velocity amplitude of the oscillating flat plate. Finally we show that a combination of both effects is possible as well.
Cardiac resynchronization therapy (CRT) is an established therapy for heart failure patients and improves quality of life in patients with sinus rhythm, reduced left ventricular ejection fraction (LVEF), left bundle branch block and wide QRS duration. Since approximately sixty percent of heart failure patients have a normal QRS duration they do not benefit or respond to the CRT. Cardiac contractility modulation (CCM) releases nonexcitatoy impulses during the absolute refractory period in order to enhance the strength of the left ventricular contraction. The aim of the investigation was to evaluate differences in cardiac index between optimized and nonoptimized CRT and CCM devices versus standard values. Impedance cardiography, a noninvasive method was used to measure cardiac index (CI), a useful parameter which describes the blood volume during one minutes heart pumps related to the body surface. CRT patients indicate an increase of 39.74 percent and CCM patients an improvement of 21.89 percent more cardiac index with an optimized device.
In this article, we present a taxonomy in Robot-Assisted Training; a growing body of research in Human–Robot Interaction which focuses on how robotic agents and devices can be used to enhance user’s performance during a cognitive or physical training task. Robot-Assisted Training systems have been successfully deployed to enhance the effects of a training session in various contexts, i.e., rehabilitation systems, educational environments, vocational settings, etc. The proposed taxonomy suggests a set of categories and parameters that can be used to characterize such systems, considering the current research trends and needs for the design, development and evaluation of Robot-Assisted Training systems. To this end, we review recent works and applications in Robot-Assisted Training systems, as well as related taxonomies in Human–Robot Interaction. The goal is to identify and discuss open challenges, highlighting the different aspects of a Robot-Assisted Training system, considering both robot perception and behavior control.
During the coronavirus crisis, labs had to be offered in digital form in mechanical engineering at short notice. For this purpose, digital twins of more complex test benches in the field of fluid energy machines were used in the mechanical engineering course, with which the students were able to interact remotely to obtain measurement data. The concept of the respective lab was revised with regard to its implementation as a remote laboratory. Fortunately, real-world labs were able to be fully replaced by remote labs. Student perceptions of remote labs were mostly positive. This paper explains the concept and design of the digital twins and the lab as well as the layout, procedure, and finally the results of the accompanying evaluation. However, the implementation of the digital twins to date does not yet include features which address the tactile experience of working in real-world labs.
Seit den ersten Projekten der 90er Jahre arbeiten Hochschulen daran, geeignete Servicestrukturen für E-Learning zu etablieren, die die erforderliche technische, didaktische und organisatorische Unterstützung hochschulweit zur Verfügung stellen. Ging es zunächst darum, Services überhaupt dauerhaft zu sichern, steht heute die Frage des „wie“ im Vordergrund. Dabei wird am Bereich E-Learning ein eigentlich viel allgemeineres Problem deutlich: Die bisher überwiegende Organisation der Hochschule nach funktionellen Einheiten stößt an ihre Grenzen. Wir schlagen eine stärker prozessorientierte Sichtweise vor, analog zu Entwicklungen bei der Organisation von Unternehmen.
Titanium and stainless steel are commonly known as osteosynthesis materials with high strength and good biocompatibility. However, they have the big disadvantage that a second operation for hardware removal is necessary. Although resorbable systems made of polymers or magnesium are increasingly used, they show some severe adverse foreign body reactions or unsatisfying degradation behavior. Therefore, we started to investigate molybdenum as a potential new biodegradable material for osteosynthesis in craniomaxillofacial surgery. To characterize molybdenum as a biocompatible material, we performed in vitro assays in accordance with ISO Norm 10993-5. In four different experimental setups, we showed that pure molybdenum and molybdenum rhenium alloys do not lead to cytotoxicity in human and mouse fibroblasts. We also examined the degradation behavior of molybdenum by carrying out long-term immersion tests (up to 6 months) with molybdenum sheet metal. We showed that molybdenum has sufficient mechanical stability over at least 6 months for implants on the one hand and is subject to very uniform degradation on the other. The results of our experiments are very promising for the development of new resorbable osteosynthesis materials for craniomaxillofacial surgery based on molybdenum.
Crystal structures of two metal–organic frameworks (MFU‐1 and MFU‐2) are presented, both of which contain redox‐active CoII centres coordinated by linear 1,4‐bis[(3,5‐dimethyl)pyrazol‐4‐yl] ligands. In contrast to many MOFs reported previously, these compounds show excellent stability against hydrolytic decomposition. Catalytic turnover is achieved in oxidation reactions by employing tert‐butyl hydroperoxide and the solid catalysts are easily recovered from the reaction mixture. Whereas heterogeneous catalysis is unambiguously demonstrated for MFU‐1, MFU‐2 shows catalytic activity due to slow metal leaching, emphasising the need for a deeper understanding of structure–reactivity relationships in the future design of redox‐active metal–organic frameworks. Mechanistic details for oxidation reactions employing tert‐butyl hydroperoxide are studied by UV/Vis and IR spectroscopy and XRPD measurements. The catalytic process accompanying changes of redox states and structural changes were investigated by means of cobalt K‐edge X‐ray absorption spectroscopy. To probe the putative binding modes of molecular oxygen, the isosteric heats of adsorption of O2 were determined and compared with models from DFT calculations. The stabilities of the frameworks in an oxygen atmosphere as a reactive gas were examined by temperature‐programmed oxidation (TPO). Solution impregnation of MFU‐1 with a co‐catalyst (N‐hydroxyphthalimide) led to NHPI@MFU‐1, which oxidised a range of organic substrates under ambient conditions by employing molecular oxygen from air. The catalytic reaction involved a biomimetic reaction cascade based on free radicals. The concept of an entatic state of the cobalt centres is proposed and its relevance for sustained catalytic activity is briefly discussed.
Hintergrund
In diesem Artikel wird ein Überblick und Vergleich der am häufigsten verwendeten zementierten Hüftschäfte, gruppiert in die verschiedenen Schafttypen und Zementmanteldicken, gegeben, um zu sehen, welche Kombination gut abschneidet.
Methodik
Aus dem Endoprothesenregister Deutschland wurden die Revisionsraten zementierter Schaftarten kategorisiert und die Revisionsraten von 3 und 5 Jahren erfasst und analysiert. Für die Recherche lag die Konzentration auf den Schäften Exeter, C‑Stem, MS-30, Excia, Bicontact, Charnley, Müller Geradschaft, Twinsys, Corail, Avenir, Quadra und dem Lubinus SP II. Ein wichtiger Aspekt lag darin, welcher Schaft favorisiert implantiert wird und welche Zementiertechnik in Hinblick auf die geplante Zementmanteldicke angewendet wird. Um einen Trend in der zementierten Hüftendoprothetik herauszufinden, wurden zusätzlich die Daten des dänischen, schwedischen, norwegischen, schweizerischen, neuseeländischen, englischen und australischen Endoprothesenregister verglichen.
Ergebnisse und Schlussfolgerung
Die meisten Länder nutzen zementierte Prothesen nach dem Kraftschlussprinzip (Exeter, MS30, C‑Stem etc.) oder dem Formschlussprinzip (Charnley, Excia, Bicontact), welche mit einer Zementmanteldicke von 2–4 mm implantiert werden. Jedoch hat sich in Deutschland und der Schweiz ein Trend zur Line-to-Line-Technik, mit einer geplanten Zementmanteldicke von 1 mm (Twinsys, Corail, Avenir, Quadra) aufgezeigt, dem Prinzip der Müller-Geradschaft-Prothese und der Kerboul-Charnley-Prothese folgend, auch wenn diese an sich als „french paradoxon“ postuliert werden. In den EPRD-5-Jahres-Ergebnissen scheinen die neueren Line-to-Line-Prothesen etwas schlechter abzuschneiden. Die besten Ergebnisse erzielt der „MS 30“ in Deutschland und der „Exeter“ in England. Hierbei handelt es sich um polierte Geradschäfte mit Zentraliser und Subsidence-Raum an der Spitze mit einem 2–4 mm Zementmantel in guter Zementiertechnik.
Purpose: Participation and accessibility issues faced by gamers with multi-sensory disabilities are themes yet to be fully understood by accessible technology researchers. In this work, we examine the personal experiences and perceptions of individuals with deafblindness who play games despite their disability, as well as the reasons that lead some of them to stop playing games.
Materials and methods: We conducted 60 semi-structured interviews with individuals living with deafblindness in five European countries: United Kingdom, Germany, Netherlands, Greece and Sweden.
Results: Participants stated that reasons for playing games included them being a fun and entertaining hobby, for socialization and meeting others, or for occupying the mind. Reasons for stop playing games included essentially accessibility issues, followed by high cognitive demand, changes in gaming experience due their disability, financial reasons, or because the accessible version of a specific game was not considered as fun as the original one.
Conclusions: We identified that a considerable number of individuals with deafblindness enjoy playing casual mobile games such as Wordfeud and Sudoku as a pastime activity. Despite challenging accessibility issues, games provide meaningful social interactions to players with deafblindness. Finally, we introduce a set of user-driven recommendations for making digital games more accessible to players with a diverse combination of sensory abilities.
IMPLICATIONS FOR REHABILITATION
- Digital games were considered a fun and entertaining hobby by participants with deafblindness. Furthermore, participants play games for socialization and meeting others, or for occupying the mind.
- Digital games provide meaningful social interactions and past time to persons with deafblindness.
- On top of accessibility implications, our findings draw attention to the importance of the social element of gaming for persons with deafblindness.
- Based on interviews, we introduce a set of user-driven recommendations for making digital games more accessible to players with a diverse combination of sensory abilities.
Transcatheter aortic valve implantation is a therapy for patients with reduced left ventricular ejection fraction and symptomatic aortic stenosis. The aim of the study was to compare the pre-and post- transcatheter aortic valve implantation procedures to determine the QRS and QT ventricular conduction times as a potential predictor of permanent pacemaker therapy requirement after transcatheter aortic valve implantation. QRS and QT ventricular conduction times were prolonged after transcatheter aortic valve implantation in heart failure patients with permanent dual chamber pacemaker therapy after transcatheter aortic valve implantation. QRS and QT ventricular conduction times may be useful parameters to evaluate the risk of post-procedural ventricular conduction block and permanent pacemaker therapy in transcatheter aortic valve implantation.
Making innovation, trade, investment and environment policy goals mutually supportive creates challenges for internationally‐oriented firms, financial institutions, governments and other stakeholders. Will the Ukraine war derail the green energy transition? How can governments and the financial system work together to broaden, deepen, and accelerate the global transition to net‐zero? What are innovation, trade and investment opportunities for green growth? How to refocus government financing instruments to support countries and trade partners meet their climate targets in times of crisis? The IfTI Global Symposium 2022 hosted by the Institute of Trade and Innovation (IfTI) at Offenburg University discussed challenges to trade in a new global order, as well as opportunities and threats of the green transition. This Special Section brings together practitioner commentaries of key symposium speakers.
Featherweight Generic Go (FGG) is a minimal core calculus modeling the essential features of the programming language Go. It includes support for overloaded methods, interface types, structural subtyping, and generics. The most straightforward semantic description of the dynamic behavior of FGG programs is to resolve method calls based on runtime type information of the receiver. This article shows a different approach by defining a type-directed translation from FGG− to an untyped lambda-calculus. FGG− includes all features of FGG but type assertions. The translation of an FGG− program provides evidence for the availability of methods as additional dictionary parameters, similar to the dictionary-passing approach known from Haskell type classes. Then, method calls can be resolved by a simple lookup of the method definition in the dictionary. Every program in the image of the translation has the same dynamic semantics as its source FGG− program. The proof of this result is based on a syntactic, step-indexed logical relation. The step index ensures a well-founded definition of the relation in the presence of recursive interface types and recursive methods. Although being non-deterministic, the translation is coherent.
Silicon (Si) has turned out to be a promising active material for next‐generation lithium‐ion battery anodes. Nevertheless, the issues known from Si as electrode material (pulverization effects, volume change etc.) are impeding the development of Si anodes to reach market maturity. In this study, we are investigating a possible application of Si anodes in low‐power printed electronic applications. Tailored Si inks are produced and the impact of carbon coating on the printability and their electrochemical behavior as printed Si anodes is investigated. The printed Si anodes contain active material loadings that are practical for powering printed electronic devices, like electrolyte gated transistors, and are able to show high capacity retentions. A capacity of 1754 mAh/gSi is achieved for a printed Si anode after 100 cycles. Additionally, the direct applicability of the printed Si anodes is shown by successfully powering an ink‐jet printed transistor.
The Future of FDI: Achieving the Sustainable Development Goals 2030 through Impact Investment
(2019)
Publicized as a global call for action in 2015, the United Nations General Assembly passed a resolution on the Sustainable Development Goals 2030 (SDGs). Before issuing the SDGs in 2015, the United Nations Conference on Trade and Development (UNCTAD) has already identified in 2014, as part of their World Investment Report, that especially developing countries are facing an estimated USD 2.5 trillion funding gap annually in the efforts to achieve the SDGs. Yet, the investment opportunities and challenges for investors, when contributing to the closure of this funding gap while benefiting from its economic potential have not been widely discussed. Despite that Foreign Direct Investments (FDI) are a key driver to sustainable economic growth and prosperity of a nation, policies and a holistic framework linking the 2030 Agenda to actionable investment opportunities for private investors are missing. Furthermore, a global platform capturing, channeling and promoting investment projects aiming to achieve the SDGs through impact investment has not been established. Utilizing global financial resources more effectively while developing new approaches and tools to promote impact investments, which demonstrate the benefits for investors to tap into the funding gap of the 2030 Agenda, will have the potential to significantly shape and influence the future of FDI.
Purpose
This work presents a new monocular peer-to-peer tracking concept overcoming the distinction between tracking tools and tracked tools for optical navigation systems. A marker model concept based on marker triplets combined with a fast and robust algorithm for assigning image feature points to the corresponding markers of the tracker is introduced. Also included is a new and fast algorithm for pose estimation.
Methods
A peer-to-peer tracker consists of seven markers, which can be tracked by other peers, and one camera which is used to track the position and orientation of other peers. The special marker layout enables a fast and robust algorithm for assigning image feature points to the correct markers. The iterative pose estimation algorithm is based on point-to-line matching with Lagrange–Newton optimization and does not rely on initial guesses. Uniformly distributed quaternions in 4D (the vertices of a hexacosichora) are used as starting points and always provide the global minimum.
Results
Experiments have shown that the marker assignment algorithm robustly assigns image feature points to the correct markers even under challenging conditions. The pose estimation algorithm works fast, robustly and always finds the correct pose of the trackers. Image processing, marker assignment, and pose estimation for two trackers are handled in less than 18 ms on an Intel i7-6700 desktop computer at 3.4 GHz.
Conclusion
The new peer-to-peer tracking concept is a valuable approach to a decentralized navigation system that offers more freedom in the operating room while providing accurate, fast, and robust results.
The use of a TLC scanner can be regarded as a key step in high performance thin layer chromatography (HPTLC). Densitometric measurements transform the substance distribution on a TLC plate into digital computer data. Systems that allow quantitative measurements have been available for many years for either fluorescence or ultraviolet absorption measurements, while lately the reflection analysis mode for both types is the most common application. New scanning approaches are designed to aid the analyst who has common demands for TLC-densitometry without using special data, such as scanned images. Two examples that have been developed lately in the laboratories of the authors are described in this paper. These approaches were developed on the basis of current needs for analysts who employ TLC as a tool in research, as well as in routine analysis. One approach is aimed to support analysts in economically disadvantaged areas, where cost intensive apparatus is unsuitable but trace analysis by simple means is required. The other system, allows the spectral determination of chromatographic spots on TLC plates covering the ultraviolet and visible range, thus, revealing highly desired information for the analyst.
Gas Analysis and Optimization of Debinding and Sintering Processes for Metallic Binder-Based AM*
(2022)
Binder-based additive manufacturing processes for metallic
AM components in a wide range of applications usually use
organic binders and process-related additives that must be
thermally removed before sintering. Debinding processes are
typically parameterized empirically and thus far from the optimum.
Since debinding based on thermal decomposition processes
of organic components and the subsequent thermochemical
reactions between process atmosphere and metal
powder materials make uncomplicated parameterization difficult,
in-situ instrumentation was introduced at Fraunhofer
IFAM. This measurement method relies on infrared spectroscopy
and mass spectrometry in various furnace concepts to
understand the gas processes of decomposition of organic
components and the subsequent thermochemical reactions
between the carrier gas atmosphere and the metal part, as well
as their kinetics. This method enables an efficient optimization
of the temperature-time profiles and the required atmosphere
composition to realize dense AM components with low contamination.
In the paper, the optimization strategy is presented,
and the achievable properties are illustrated using a fused
filament fabrication (FFF) component example made of 316L
stainless steel.
In recent years, both the Internet of Things (IoT) and blockchain technologies have been highly influential and revolutionary. IoT enables companies to embrace Industry 4.0, the Fourth Industrial Revolution, which benefits from communication and connectivity to reduce cost and to increase productivity through sensor-based autonomy. These automated systems can be further refined with smart contracts that are executed within a blockchain, thereby increasing transparency through continuous and indisputable logging. Ideally, the level of security for these IoT devices shall be very high, as they are specifically designed for this autonomous and networked environment. This paper discusses a use case of a company with legacy devices that wants to benefit from the features and functionality of blockchain technology. In particular, the implications of retrofit solutions are analyzed. The use of the BISS:4.0 platform is proposed as the underlying infrastructure. BISS:4.0 is
intended to integrate the blockchain technologies into existing enterprise environments. Furthermore, a security analysis of IoT and blockchain present attacks and countermeasures are presented that are identified and applied to the mentioned use case.
The production of potable water in dry areas nowadays is mainly done by the desalination of seawater. State of the art desalination plants usually are built with high production capacities and consume a lot of electrical energy or energy from primary resources such as oil. This causes difficulties in rural areas, where no infrastructure is available neither for the plants’ energy supply nor the distribution of the produced potable water. To address this need, small, self-sustaining and locally operated desalination plants came into the focus of research. In this work, a novel flash evaporator design is proposed which can be driven either by solar power or by low temperature waste heat. It offers low operation costs as well as easy maintenance. The results of an experimental setup operated with water at a feed flow rate of up to 1,600 l/h are presented. It is shown that the proof of concept regarding efficient evaporation as well as efficient gas-liquid separation is provided successfully. The experimental evaporation yield counts for 98 % of the vapor content that is expected from the vapor pressure curve of water. Neither measurements of the electrical conductivity of the gained condensate, nor the analysis of the vapor flow by optical methods show significant droplet entrainment, so there are no concerns regarding the purity of the produced condensate for the use as drinking water.
A new formula is presented for transforming fluorescence measurements in accordance with Kubelka-Munk theory. The fluorescence signals, the absorption signals, and data from a selected reference are combined in one expression. Only diode-array techniques can measure all the required data simultaneously to linearize fluorescence data correctly. To prove the new theory HPTLC quantification of the analgesic flupirtine was performed over the mass range 300 to 5000 ng per spot. The fluorescence calibration curve was linear over the whole range. The transformation of fluorescence measurements into linear mass-dependent data extends the technique of in-situ fluorescence analysis to the high concentration range. It also extends Kubelka-Munk theory from absorption to fluorescence analysis. The results presented also emphasize the importance of Kubelka-Munk theory for in-situ measurements in scattering media, especially in planar chromatography.
A Simple and Reliable HPTLC Method for the Quantification of the Intense Sweetener Sucralose®
(2003)
This paper describes a simple and fast thin layer chromatography (TLC) method for the monitoring of the relatively new intense sweetener Sucralose® in various food matrices. The method requires little or no sample preparation to isolate or concentrate the analyte. The Sucralose® extract is separated on amino‐TLC‐plates, and the analyte is derivatized “reagent‐free” by heating the developed plate for 20 min at 190°C. Spots can be measured either in the absorption or fluorescence mode. The method allows the determination of Sucralose® at the levels of interest regarding foreseen European legislation (>50 mg/kg) with excellent repeatability (RSD = 3.4%) and recovery data (95%).
High-performance thin-layer chromatography (HPTLC), as the modern form of TLC (thin-layer chromatography), is suitable for detecting pharmaceutically active compounds over a wide polarity range using the gradient multiple development (GMD) technique. Diode-array detection (DAD) in conjunction with HPTLC can simultaneously acquire ultraviolet‒visible (UV‒VIS) and fluorescence spectra directly from the plate. Visualization as a contour plot helps to identify separated zones. An orange peel extract is used as an example to show how GMD‒DAD‒HPTLC in seven different developments with seven different solvents can provide an overview of the entire sample. More than 50 compounds in the extract can be separated on a 6-cm HPTLC plate. Such separations take place in the biologically inert stationary phase of HPTLC, making it a suitable method for effect-directed analysis (EDA). HPTLC‒EDA can even be performed with living organism, as confirmed by the use of Aliivibrio fischeri bacteria to detect bioluminescence as a measure of toxicity. The combining of gradient multiple development planar chromatography with diode-array detection and effect-directed analysis (GMD‒DAD‒HPTLC‒EDA) in conjunction with specific staining methods and time-of-flight mass spectrometry (TOF‒MS) will be the method of choice to find new chemical structures from plant extracts that can serve as the basic structure for new pharmaceutically active compounds.
High performance thin layer chromatography (HPTLC) is a frequently used separation technique which works well for quantification of caffeine and quinine in beverages. Competing separation techniques, e.g. high-performance liquid chromatography (HPLC) or gas chromatography (GC), are not suitable for sugar-containing samples, because these methods need special pretreatment by the analyst. In HPTLC, however, it is possible to separate ‘dirty’ samples without time-consuming pretreatment, because disposable HPTLC plates are used. A convenient method for quantification of caffeine and quinine in beverages, without sample pretreatment, is presented below. The basic theory of in-situ quantification in HPTLC by use of remitted light is introduced and discussed. Several linearization models are discussed.
A home-made diode-array scanner has been used for quantification; this, for the first time, enables simultaneous measurements at different wavelengths. The new scanner also enables fluorescence evaluation without further equipment. Simultaneous recording at different wavelengths improves the accuracy and reliability of HPTLC analysis. These aspects result in substantial improvement of in-situ quantitative densitometric analysis and enable quantification of compounds in beverages.
Fluorescence Enhancement of Pyrene Measured by Thin-Layer Chromatography with Diode-Array Detection
(2003)
In-situ densitometry for qualitative or quantitative purposes is a key step in thin-layer chromatography. It offers a simple way of quantifying by measuring the optical density of the separated spots directly on the plate. A new TLC scanner has been developed which is able to measure TLC plates or HPTLC plates, at different wavelengths simultaneously, without destroying the plate surface. The system enables absorbance and fluorescence measurements in one run. Fluorescence measurements are possible without filters or other adjustments.
The measurement of fluorescence from a TLC plate is a versatile means of making TLC analysis more sensitive. Fluorescence measurements with the new scanner are possible without filters or special lamps. Improvement of the signal-to-noise ratio is achieved by wavelength bundling. During plate scanning the scattered light and the fluorescence are both emitted from the surface of the TLC plate and this emitted light provides the desired spectral information from substances on the TLC plate. The measurement of fluorescence spectra and absorbance spectra directly from a TLC plate is based on differential measurement of light emerging from sample-free and sample-containing zones.
The literature recommends dipping TLC plates in viscous liquids to enhance fluorescence. Measurement of the fluorescence and absorbance spectra of pyrene spots reveals the mechanism of enhancement of plate dipping in viscous liquids—blocked contact of the fluorescent molecules with the stationary phase or other sample molecules is responsible for the enhanced fluorescence at lower concentrations.
In conclusion, dipping in TLC analysis is no miracle. It is based on similar mechanisms observable in liquids. The measured TLC spectra are also very similar to liquid spectra and this makes TLC spec-troscopy an important tool in separation analysis.
A new diode-array scanner in combination with a computer-controlled application system meets all the demands of modern HPTLC measurement. Automatic application, simultaneous measurements at different wavelengths, and different linearization models enable appropriate evaluation of all analytical questions. The theory of error propagation recommends quantification at reflectance values smaller than 0.8; this can be verified only by use of diode-array scanning. The same theory also recommends quantification by use of peak height data, because the theory predicts best precision only for peak height evaluation. Diode-array scanning with reflectance monitoring enables appropriate validation in TLC and HPTLC analysis. All these aspects result in substantial improvement of in-situ quantitative densitometric analysis, and simultaneous recording at different wavelengths opens the way for chemometric evaluation, e.g. peak purity monitoring, which improves the accuracy and reliability of HPTLC analysis.
In-situ densitometry for qualitative or quantitative purposes is a key step in thin-layer chromatography (TLC). It is a simple means of quantification by measurement of the optical density of the separated spots directly on the plate. A new scanner has been developed which is capable of measuring TLC or HPTLC (high-performance thin-layer chromatography) plates simultaneously at different wavelengths without damaging the plate surface. Fiber optics and special fiber interfaces are used in combination with a diode-array detector. With this new scanner sophisticated plate evaluation is now possible, which enables use of chemometric methods in HPTLC. Different regression models have been introduced which enable appropriate evaluation of all analytical questions. Fluorescent measurements are possible without filters or special lamps and signal-to-noise ratios can be improved by wavelength bundling. Because of the richly structured spectra obtained from PAH, diode-array HPTLC enables quantification of all 16 EPA PAH on one track. Although the separation is incomplete all 16 compounds can be quantified by use of suitable wavelengths. All these aspects are enable substantial improvement of in-situ quantitative densitometric analysis.
In this paper a high-performance thin-layer chromatography (HPTLC) scanner is presented in which a special fibre arrangement is used as HPTLC plate scanning interface. Measurements are taken with a set of 50 fibres at a distance of 400 to 500 μm above the HPTLC plate. Spatial resolutions on the HPTLC plate of better than 160 μm are possible. It takes less than 2 min to scan 450 spectra simultaneously in a range of 198 to 610 nm. The basic improvement of the item is the use of highly transparent glass fibres which provide excellent transmission at 200 nm and the use of a special fibre arrangement for plate illumination and detection.
We present a video-densitometric high-performance thin-layer chromatography (HPTLC) quantification method for patulin in apple juice, developed in a vertical chamber from the starting point to a distance of 50 mm, using MTBE, n-pentane (9 + 5, v/v) as mobile phase. After separation the plate is sprayed with methyl-benzothiazolinone hydrazone hydrochloride monohydrate (MBTH) solution (40 mg in 20 mL methanol) and heated at 105 °C for 15 min. Patulin zones are transformed into yellow spots. The quantification is based on direct measurements using an inexpensive 48-bit flatbed scanner for color measurements (in red, green, and blue). Evaluation of the blue channel makes the measurements very specific. Quantification in fluorescence was also done by use of a 16-bit CCD-camera and UV-366 nm illumination as well as using a HPTLC DAD-scanner. For linearization the extended Kubelka–Munk expression for data transformation was used. The range of linearity covers more than two magnitudes and lies between 5 and 800 ng patulin. The extraction of 20 g apple juice and an extract application on plate up to 50 µL allows statistically defined checking the limit of detection (LOD) of 50 ng patulin per track, which is equivalent to 50 µg patulin per kg apple juice.
An Extraction Method for 17α-Ethinylestradiol from Water using a new kind of monolithic Stir-bar
(2015)
We present a densitometric quantification method for triclosan in toothpaste, separated by high-performance thin-layer chromatography (HPTLC) and using a 48-bit flatbed scanner as the detection system. The sample was band-wise applied to HPTLC plates (10 × 20 cm), with fluorescent dye, Merck, Germany (1.05554). The plates were developed in a vertical developing chamber with 20 min of chamber saturation over 70 mm, using n-heptane–methyl tert-butyl ether–acetic acid (92:8:0.1, V/V) as solvent. The RF value of triclosan is hRF = 22.4, and quantification is based on direct measurements using an inexpensive 48-bit flatbed scanner for color measurements (in red, green, and blue) after plate staining with 2,6-dichloroquinone-4-chloroimide (Gibbs' reagent). Evaluation of the red channel makes the measurements of triclosan very specific. For linearization, an extended Kubelka–Munk expression was used for data transformation. The range of linearity covers more than two orders of magnitude and is between 91 and 1000 ng. The separation method is inexpensive, fast and reliable.
A 2D-separation of 16 polyaromatic hydrocarbons (PAHs) according to the Environmental Protecting Agency (EPA) standard was introduced. Separation took place on a TLC RP-18 plate (Merck, 1.05559). In the first direction, the plate was developed twice using n-pentane at −20°C as the mobile phase. The mixture acetonitrile-methanol-acetone-water (12:8:3:3, v/v) was used for developing the plate in the second direction. Both developments were carried out over a distance of 43 mm. Further on in this publication, a specific and very sensitive indication method for benzo[a]pyrene and perylene was presented. The method can detect these hazardous compounds even in complicated PAH mixtures. These compounds can be quantified by a simple chemiluminescent reaction with a limit of detection (LOD) of 48 pg per band for perylene and 95 pg per band for benzo[a]pyrene. Although these compounds were separated from all other PAHs in the standard, a separation of both compounds was not possible from one another. The method is suitable for tracing benzo[a]pyrene and/or perylene. The proposed chemiluminescence screening test on PAHs is extremely sensitive but may indicate a false positive result for benzo[a]pyrene.
Two solvent mixtures for high-performance thin-layer chromatographic (HPTLC) separation of some compounds showing estrogenic activity in the yeast estrogen screen (YES) assay are presented. The new method, planar yeast estrogen screen (pYES) combines the YES assay and a chromatographic separation on silica gel HPTLC plates with the performance of the YES assay. For separation, the analytes were applied bandwise to HPTLC plates (10 × 20 cm) with fluorescent dye (Merck, Germany). The plates were developed in a vertical developing chamber after 30 min of chamber saturation over a separation distance of 70 mm, using cyclohexane‒methyl-ethyl ketone (2:1, V/V) or cyclohexane‒CPME (3:2, V/V) as solvents. Both solvents allow separation of estriol, daidzein, genistein, 17β-estradiol, 17α-ethinyl estradiol, estrone, 4-nonylphenol and bis(2-ethylhexyl) phthalate.
An algorithm is presented that has successfully been utilized in practice for several years. It improves data analysis in chromatography. The program runs in an extremely reliable way and evaluates chromatographic raw data with an acceptable error. The algorithm requires a minimum of preliminaries and integrates even unsmoothed noisy data correctly.
Improved separation of highly toxic contact herbicides paraquat (1,1′-dimethyl-4-4′-bipyridinium), diquat (6,7-dihydrodipyridol[ 1,2-a:2′,1′-c]pyrazine-5,8-di-ium), difenzoquat (1,2-dimethyl-3,5-diphenyl-1H-pyrazolium-methyl sulfate), mepiquat (1,1-dimethyl-piperidinium), and chloromequat (2-chloroethyltrimethylammonium) were presented by high-performance thin-layer chromatography (HPTLC). The quantification is based on a derivatization reaction, using sodium tetraphenylborate. Measurements were made in the wavelength range from 500 to 535 nm, using a light-emitting diode (LED) for excitation purposes, which emits very dense light at 365 nm. For calculations, a new theory of standard addition method was used, thus leading to a minimal error if exactly the same amount of sample content is added as a standard. The method provides a fast and inexpensive approach to quantification of the five most important quats used for plant protection purposes. The method works reliably because it takes into account losses during pre-treatment procedure. The method meets the European legislation limits for paraquat and diquat in drinking water according to United States Environmental Protection Agency (US EPA) method 549.2 which are 680 ng L−1 for paraquat and 720 ng L−1 for diquat. The method of standard addition in planar chromatography can be beneficially used to reduce systematic errors. Although recovery rates of 33.7% to 65.2% are observed, calculated contents according to the method of standard addition lie between 69% and 127% of the theoretical amounts.
Umgang mit Lebenskrisen
(2015)
Fully Printed Inverters using Metal‐Oxide Semiconductor and Graphene Passives on Flexible Substrates
(2020)
Printed and flexible metal‐oxide transistor technology has recently demonstrated great promise due to its high performance and robust mechanical stability. Herein, fully printed inverter structures using electrolyte‐gated oxide transistors on a flexible polyimide (PI) substrate are discussed in detail. Conductive graphene ink is printed as the passive structures and interconnects. The additive printed transistors on PI substrates show an on/off ratio of 106 and show mobilities similar to the state‐of‐the‐art printed transistors on rigid substrates. Printed meander structures of graphene are used as pull‐up resistances in a transistor–resistor logic to create fully printed inverters. The printed and flexible inverters show a signal gain of 3.5 and a propagation delay of 30 ms. These printed inverters are able to withstand a tensile strain of 1.5% following more than 200 cycles of mechanical bending. The stability of the electrical direct current (DC) properties has been observed over a period of 5 weeks. These oxide transistor‐based fully printed inverters are relevant for digital printing methods which could be implemented into roll‐to‐roll processes.
Development of Fully Printed Oxide Field-Effect Transistors using Graphene Passive Structures
(2019)
During the past decade to the present time, the topic of printed electronics has gained a lot of attention for their potential use in a number of practical applications, including biosensors, photovoltaic devices, RFIDs, flexible displays, large-area circuits, and so on. To fully realize printed electronic components and devices, effective techniques for the printing of passive structures and electrically and chemically compatible materials in the printed devices need to be developed first. The opportunity of using electrically conducting graphene inks will enable the integration of passive structures into active devices, as for example, printed electrolyte-gated transistors (EGTs). Accordingly, in this study, we present the parametric results obtained on fully printed electrolyte-gated transistors having graphene as the passive electrodes, an inorganic oxide semiconductor as the active channel, and a composite solid polymer electrolyte (CSPE) as the gate insulating material. This configuration offers high chemical and electrical stability while at the same time allowing EGT operation at low potentials, implying the distinct advantage of operation at low input voltages. The printed in-plane EGTs we developed exhibit excellent performance with device mobility up to 16 cm2 V–1 s–1, an ION/IOFF ratio of 105, and a subthreshold slope of 120 mV dec–1.