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This contribution describes how to improve privacy and security for the Smart Living domain. Core elements of this approach adapt the Privacy by Design concept to the domain of smart living and extend it to enable artificial intelligence integration. To improve security, we created a minimum framework based on an existing information security management system to offer a holistic perspective on that topic. This, we think, is necessary, primarily if legacy Internet of Things devices should be supported

Robot-based service platforms are currently establishing themselves as new and affordable variants for supporting care in elderly, retirement and nursing homes. Many are open multifunctional platforms, which can potentially be integrated into such environments, if the necessary infrastructure is available. Furthermore, many services can be realized on these platforms, which can be used to foster distant interactions between inhabitants and care-providers, while simultaneously keeping up the quality of life of the inhabitants. Open mobile robotic platforms allow the extension with adequate new sensors. To detect infectious diseases of residents and healthcare-professionals, optical sensors can be used for the assessment of vital data such as heartrate and heartrate variability, respiratory rate, SpO2 or temperature. Additionally, you can consider demographic data (age, gender, constitution) of the observed person for the optical assessment, i.e. obtained by facial image analysis. As these mobile platforms are also equipped for telepresence, in case of detecting an infected person, these systems support video conferencing with their built-in cameras and microphones. Finally, the interaction with the electronic care record is necessary to upload all acquired vital data and further relevant information. All the named technologies have been under investigation in the past years and are currently moving from laboratory settings to real-world scenarios. Nevertheless, the smooth integration of all components into one system architecture in combination with (AI-based) data analysis are still open issues.

All aspects of daily life increasingly include digitization. So-called „smart home“ technologies, as well as „wearables“, are gaining attention from more and more dwellers. Therefore, sensor-based, individualized, AI-based services for improved post-intervention monitoring and therapy accompaniment will become feasible and possible if these systems offer a related context-awareness. This paper provides an approach on how to sense and interpret specific contexts with the help of wearables, smartwatches, smart home sensors, and emotion detection software.

In the upcoming years, the internet of things (IoT) will enrich daily life. The combination of artificial intelligence (AI) and highly interoperable systems will bring contextsensitive multi-domain services to reality. This paper describes a concept for an AI-based smart living platform with open- HAB, a smart home middleware, andWeb of Things (WoT) as key components of our approach. The platform concept considers different stakeholders, i.e. the housing industry, service providers, and tenants. These activities are part of the Fore- Sight project, an AI-driven, context-sensitive smart living platform.

C24H66Li6Si6, triclinic, P1̄ (no. 2), a = 12.2492(9) Å, b = 12.4617(9) Å, c = 14.3841(11) Å, α = 74.189(6), β = 74.543(7), γ = 85.970(6), V = 2036.2(3) Å3, Z = 2, Rgt(F) = 0.0465, wRref(F2) = 0.0802, T = 173(2) K.

Structural investigations of molecular crystal solvates can provide important information for the targeted crystallization of particular inclusion compounds. Here, the crystal structure of the first ether solvate of hexaphenyldistannane [(Ph3Sn)2 • 2 THF] is reported. Structural features in terms of host-guest interactions and in the context of the previously reported polymorphs and solvates of (Ph3Sn)2 are discussed.

In the last decades, biological databases became the major knowledge resource for researchers in the field of molecular biology. The distribution of information among these databases is one of the major problems. An overview about the subject area of data access and representation of protein and protein-protein interaction data within public biological databases is described. For a comprehensive and consistent way of searching and analysing integrated protein and protein-protein interaction data, the InSilico Proteomics (ISP) project has been initiated. Its three main objectives are (1) to provide an integrated knowledge pool for data investigation and global network analysis functions for a better understanding of a cell’s interactome, (2) employment of public data for plausibility analysis and validation of in-house experimental data and (3) testing the applicability of Microsoft’s .NET architecture for bioinformatics applications. Data integrated into the ISP database can be queried through the Web portal PRIMOS (PRotein Interaction and MOlecule Search) which is freely available at http://biomis.fh-hagenberg.at/isp/primos.

Abstract Background The Gram-negative bacterium Chlamydia pneumoniae (Cpn) is the leading intracellular human pathogen responsible for respiratory infections such as pneumonia and bronchitis. Basic and applied research in pathogen biology, especially the elaboration of new mechanism-based anti-pathogen strategies, target discovery and drug development, rely heavily on the availability of the entire set of pathogen open reading frames, the ORFeome. The ORFeome of Cpn will enable genome- and proteome-wide systematic analysis of Cpn, which will improve our understanding of the molecular networks and mechanisms underlying and governing its pathogenesis. Results Here we report the construction of a comprehensive gene collection covering 98.5% of the 1052 predicted and verified ORFs of Cpn (Chlamydia pneumoniae strain CWL029) in Gateway® ‘entry’ vectors. Based on genomic DNA isolated from the vascular chlamydial strain CV-6, we constructed an ORFeome library that contains 869 unique Gateway® entry clones (83% coverage) and an additional 168 PCR-verified ‘pooled’ entry clones, reaching an overall coverage of ~98.5% of the predicted CWL029 ORFs. The high quality of the ORFeome library was verified by PCR-gel electrophoresis and DNA sequencing, and its functionality was demonstrated by expressing panels of recombinant proteins in Escherichia coli and by genome-wide protein interaction analysis for a test set of three Cpn virulence factors in a yeast 2-hybrid system. The ORFeome is available in different configurations of resource stocks, PCR-products, purified plasmid DNA, and living cultures of E. coli harboring the desired entry clone or pooled entry clones. All resources are available in 96-well microtiterplates. Conclusion This first ORFeome library for Cpn provides an essential new tool for this important pathogen. The high coverage of entry clones will enable a systems biology approach for Cpn or host–pathogen analysis. The high yield of recombinant proteins and the promising interactors for Cpn virulence factors described here demonstrate the possibilities for proteome-wide studies.

Abstract Background Cytokines such as interleukin 6 (IL-6) have been implicated in dual functions in neuropsychiatric disorders. Little is known about the genetic predisposition to neurodegenerative and neuroproliferative properties of cytokine genes. In this study the potential dual role of several IL-6 polymorphisms in brain morphology is investigated. Methodology In a large sample of healthy individuals (N = 303), associations between genetic variants of IL-6 (rs1800795; rs1800796, rs2069833, rs2069840) and brain volume (gray matter volume) were analyzed using voxel-based morphometry (VBM). Selection of single nucleotide polymorphisms (SNPs) followed a tagging SNP approach (e.g., Stampa algorigthm), yielding a capture 97.08% of the variation in the IL-6 gene using four tagging SNPs. Principal findings/results In a whole-brain analysis, the polymorphism rs1800795 (−174 C/G) showed a strong main effect of genotype (43 CC vs. 150 CG vs. 100 GG; x = 24, y = −10, z = −15; F(2,286) = 8.54, puncorrected = 0.0002; pAlphaSim-corrected = 0.002; cluster size k = 577) within the right hippocampus head. Homozygous carriers of the G-allele had significantly larger hippocampus gray matter volumes compared to heterozygous subjects. None of the other investigated SNPs showed a significant association with grey matter volume in whole-brain analyses. Conclusions/significance These findings suggest a possible neuroprotective role of the G-allele of the SNP rs1800795 on hippocampal volumes. Studies on the role of this SNP in psychiatric populations and especially in those with an affected hippocampus (e.g., by maltreatment, stress) are warranted.

Abstract Background The current analyses focus on the need for services from the perspective of individuals considering preventive measures. A new approach imported from social and health psychology is used for assessing subjective need. This indicator is used for predicting actual health behaviour under field conditions and simultaneously other relevant background variables are taken into account. Methods A mail survey was conducted prior to the start of a coaching program for teachers. A sample of n = 949 respondents were queried about mental distress and their intention to participate in the program. This intention to participate and actual attendance were taken as outcome variables in logistic regression analyses adjusted for relevant background variables. Results Intention and participation in the coaching program three months later were associated with an unadjusted OR of 90.1 (95% CI: 39.2 - 207.0) for male teachers. For female teachers the crude effect was OR = 80.0 (95% CI: 45.7 - 140.1). The positive predictive value (PPV) was 96.4% among males and 94.5% among females. Adjusting for covariates results in higher values. Among female, but not among male teachers, the participation depended on psychological distress as assessed by the General Health Questionnaire (GHQ). Conclusions There is strong evidence for using subjective need as an additional component in assessing the need for services and for predicting actual health behaviour. But it needs to be confined to intended behaviour which is under behavioural control.

Abstract Background In the present biomechanical study, the torsional stability of different interference screws, made of bovine bone, was tested. Interference screws derived from bovine bone are a possible biological alternative to conventional metallic or bioabsorbable polymer interference screws. Methods In the first part of the study we compared the torsional stability of self-made 8 mm Interference screws (BC) and a commercial 8 mm interference screw (Tutofix®). Furthermore, we compared the torsional strength of BC screws with different diameters. For screwing in, a hexagon head and an octagon head were tested. Maximum breaking torques in polymethyl methacrylate resin were recorded by means of an electronic torque screw driver. In the second part of the study the tibial part of a bone-patellar tendon-bone graft was fixed in porcine test specimens using an 8 mm BC screw and the maximum insertion torques were recorded. Each interference screw type was tested 5 times. Results There was no statistically significant difference between the different 8 mm interference screws (p = 0.121). Pairwise comparisons did not reveal statistically significant differences, either. It was demonstrated for the BC screws, that a larger screw diameter significantly leads to higher torsional stability (p = 9.779 × 10-5). Pairwise comparisons showed a significantly lower torsional stability for the 7 mm BC screw than for the 8 mm BC screw (p = 0.0079) and the 9 mm BC screw (p = 0.0079). Statistically significant differences between the 8 mm and the 9 mm BC screw could not be found (p = 0.15). During screwing into the tibial graft channel of the porcine specimens, insertion torques between 0.5 Nm and 3.2 Nm were recorded. In one case the hexagon head of a BC screw broke off during the last turn. Conclusions The BC screws show comparable torsional stability to Tutofix® interference screws. As expected the torsional strength of the screws increases significantly with the diameter. The safety and in vivo performance of products derived from xenogeneic bone should be the focus of further investigations.

Abstract Background Protein-protein interaction (PPI) data sets generated by high-throughput experiments are contaminated by large numbers of erroneous PPIs. Therefore, computational methods for PPI validation are necessary to improve the quality of such data sets. Against the background of the theory that most extant PPIs arose as a consequence of gene duplication, the sensitive search for homologous PPIs, i.e. for PPIs descending from a common ancestral PPI, should be a successful strategy for PPI validation. Results To validate an experimentally observed PPI, we combine FASTA and PSI-BLAST to perform a sensitive sequence-based search for pairs of interacting homologous proteins within a large, integrated PPI database. A novel scoring scheme that incorporates both quality and quantity of all observed matches allows us (1) to consider also tentative paralogs and orthologs in this analysis and (2) to combine search results from more than one homology detection method. ROC curves illustrate the high efficacy of this approach and its improvement over other homology-based validation methods. Conclusion New PPIs are primarily derived from preexisting PPIs and not invented de novo. Thus, the hallmark of true PPIs is the existence of homologous PPIs. The sensitive search for homologous PPIs within a large body of known PPIs is an efficient strategy to separate biologically relevant PPIs from the many spurious PPIs reported by high-throughput experiments.

Abstract Background The bacterium Staphylococcus aureus causes significant morbidity and mortality in humans, primarily due to the emergence of strains that are resistant to antibiotics – notably methicillin-resistant S. aureus (MRSA) isolates. Development of effective strategies for the control and treatment of MRSA infections may best be achieved through 'omics' approaches, which first requires cloning the entire set of S. aureus' protein-encoding open reading frames (ORFs), or ORFeome. Results The complete genome sequence of S. aureus strain Mu50 has 2697 predicted protein-coding ORFs. Based on the sequence of this strain we designed PCR primers to construct from an S. aureus (non-MRSA) clinical isolate an ORFeome library that contains 2562 unique Gateway® entry clones (95% coverage), each corresponding to a defined ORF. The high quality of the ORFeome library was verified by DNA sequencing and PCR amplification, and its functionality was demonstrated by expressing recombinant proteins and observing protein interactions in a yeast 2-hybrid homodimerization screen. Conclusion This first ORFeome library for S. aureus provides an essential new tool for investigating the systems biology of this important pathogen.

Abstract Background Information on the effectiveness of elementary school level, tobacco-use prevention programs is generally limited. This study assessed the impact of a structured, one-time intervention that was designed to modify attitudes and knowledge about tobacco. Participants were fifth-grade students from schools in western New York State. Methods Twenty-eight schools, which were in relatively close geographic proximity, were randomized into three groups; Group 1 was used to assess whether attitudes/knowledge were changed in the hypothesized direction by the intervention, and if those changes were retained four months later. Groups 2 and 3, were used as comparison groups to assess possible test-retest bias and historical effects. Groups 1 and 3 were pooled to assess whether attitudes/knowledge were changed by the intervention as measured by an immediate post-test. The non-parametric analytical techniques of Wilcoxon-Matched Pairs/Sign Ranks and the Mann-Whitney-Wilcoxon Rank Sums Tests were used to compare proportions of correct responses at each of the schools. Results Pooled analyses showed that short-term retention on most items was achieved. It was also found that retention on two knowledge items 'recognition that smokers have yellow teeth and fingers' and 'smoking one pack of cigarettes a day costs several hundred dollars per year' was maintained for four months. Conclusions The findings suggest that inexpensive, one-time interventions for tobacco-use prevention can be of value. Changes in attitudes and knowledge conducive to the goal of tobacco-use prevention can be achieved for short-term retention and some relevant knowledge items can be retained for several months.

For more than five decades, P-stereogenic aminophosphine chalcogenides and boranes have attracted scientific attention and are still in the focus of ongoing research. In the last years, novel transition metal-based synthesis methods have been discovered, in addition to the long-known use of chiral auxiliaries. Enantiomerically pure compounds with N-P + -X - (X=O, S, BH 3 ) motifs served as valuable reactive building blocks to provide new classes of organophosphorus derivatives, thereby preserving the stereochemical information at the phosphorus atom. Over the years, intriguing applications in organocatalysis and transition metal catalysis have been reported for some representatives. Asymmetric reductions of C=C, C=N, and C=O double bonds were feasible with selected P-stereogenic aminophosphine oxides in the presence of hydrogen transfer reagents. P-stereogenic aminophosphine boranes could be easily deprotected and used as ligands for various transition metals to enable catalytic asymmetric hydrogenations of olefins and imines. This review traces the emergence of a synthetically and catalytically powerful functional compound class with phosphorus-centered chirality in its main lines, starting from classical approaches to modern synthesis methods to current applications., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Stereochemically pure phosphines with phosphorus-heteroatom bonds and P-centered chirality are a promising class of functional building blocks for the design of chiral ligands and organocatalysts. A route to enantiomerically pure primary aminophosphine sulfides was opened through stereospecific reductive C-N bond cleavage of phosphorus(V) precursors by lithium in liquid ammonia. The chemoselectivity of the reaction as a function of reaction time, substrate pattern, and chiral auxiliary was investigated. In the presence of exclusively aliphatic groups bound to the phosphorus atom, all competing reductive side reactions are totally prevented. The absolute configurations of all P-stereogenic compounds were determined by single-crystal X-ray diffraction analysis. Their use as synthetic building blocks was demonstrated. The lithium salt of (R)-BINOL-dithiophosphoric acid proved to be a useful stereochemical probe to determine the enantiomeric purity. Insights into the coordination mode of the lithium-based chiral complex formed in solution was provided by NMR spectroscopy and DFT calculations., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Understanding the interplay of structural and electronic parameters in the stabilization of Lewis acidic silicon centers is crucial for stereochemical questions and applications in bond activation and catalytic transformations. Phosphine chalcogenide functionalized (Ch = O, S, and Se) hydrosilanes having tert -butyl and 2,4,6-trimethoxyphenyl (TMP) substituents on the silicon atom were synthesized, and the ring-closing reactions to afford the heterocyclic four-membered CPChSi cations were investigated. Synthetic access was only achieved for the sulfur- and selenium-based cations. A thorough study by means of single-crystal X-ray structure determination, NMR spectroscopic data, and density functional theory (DFT) calculations provided insight into important electronic and structural parameters affecting the stability of the intramolecularly stabilized cations. Detailed structural considerations were made on the contributions to the ring strain (angular strain and steric repulsion). Thermochemical investigations showed that the substituents on the silicon and phosphorus atoms play an important role for the stability of the cationic heterocycles. In the absence of large steric repulsions through bulky substituents (methyl groups on silicon and tert -butyl groups on phosphorus), an intrinsic stability sequence of the intramolecular Ch-Si coordination depending on the chalcogen atom in the direction Se ≤ S < O can be observed. However, the order is reversed (O < S < Se) in the case of strong repulsions between sterically demanding substituents ( tert -butyl groups on both silicon and phosphorus atoms). Natural bond orbital (NBO) analysis supported the explanations for the observed deshielding trends in 31 P NMR spectroscopy and revealed that the O-Si bond is more ionic in nature compared to the S-Si and Se-Si bonds, with the latter exhibiting higher covalent character due to a more efficient charge transfer through a σ-type n Ch → p Si interaction.

A new class of siloxane-based cations with hidden silylium-type reactivity is provided, which, in combination with an arylborate counteranion, initiates a highly selective para -C(sp 2 )-F defunctionalization of a perfluorinated aryl group. The hydrodefluorinated aryl borane is obtained as a crystalline solid via continuous sublimation during the reaction. The heterocyclic six-membered cation could be obtained single-crystalline after dehydrogenative anion exchange. DFT calculations give insight into the bonding within the siloxane-based cation and the mechanism of the ion pair reaction.

The controlled design of functional oligosiloxanes is an important topic in current research. A consecutive Si-O-Si bond cleavage/formation using siloxanes that are substituted with 1,2-diaminobenzene derivatives acting as molecular scissors is presented. The method allows to cut at certain positions of a siloxane scaffold forming a cyclic diaminosilane or -siloxane intermediate and then to introduce new functional siloxy units. The procedure could be extended to a direct one-step cleavage of chlorooligosiloxanes. Both siloxane formation and cleavage proceed with good to excellent yields, high regioselectivity, and great variability of the siloxy units. Control of the selectivity is achieved by the choice of the amino substituent. Insight into the mechanism was provided by low temperature NMR studies and the isolation of a lithiated intermediate., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

We report a highly selective substitution of silicon-bound methoxy groups by primary lithium amides. This unusual reactivity is possible because of the formation of particularly stable lithium methoxide, which compensates for the decreased Si-N bond enthalpy compared to Si-O bonds. In contrast to substitution reactions on halosilanes, highly selective monosubstitutions under mild conditions are possible, even in the presence of further reactive methoxy groups. A combination of experiments and density functional theory calculations was carried out in order to get an extensive understanding of the reaction. The calculations reveal a possible reaction mechanism with considerably low activation barriers and the entry of the nucleophile to be the rate-determining step. The low activation energies allow for the substitutions to be carried out at low temperatures, therefore preventing side reactions from occurring. The presented investigations expand the view of fundamental transformation processes on silicon and give access to a wide variety of functionalized silicon-based building blocks for various fields of chemistry.

Phosphonium ions are widely used in preparative organic synthesis and catalysis. The provision of new types of cations that contain both functional and chiral information is a major synthetic challenge and can open up new horizons in asymmetric cation-directed and Lewis acid catalysis. We discovered an efficient methodology towards new Si-chiral four-membered CPSSi* heterocyclic cations. Three synthetic approaches are presented. The stereochemical sequence of anchimerically assisted cation formation with B(C 6 F 5 ) 3 and subsequent hydride addition was fully elucidated and proceeds with excellent preservation of the chiral information at the stereogenic silicon atom. Also the mechanism of dihydrogen release from a protonated hydrosilane was studied in detail by the help of Si-centered chirality as stereochemical probe. Chemoselectivity switch (dihydrogen release vs. protodesilylation) can easily be achieved through slight modifications of the solvent. A matched/mismatched case was identified and the intermolecularity of this reaction supported by spectroscopic, kinetic, deuterium-labeling experiments, and quantum chemical calculations., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Structural knowledge on ubiquitous lithium salts in solution and in the crystalline state is of paramount importance for our understanding of many chemical reactions and of the electrolyte behaviour in lithium ion batteries. A bulky bidentate Si-based ligand (6) was used to create simplified model systems suitable for correlating structures of LiCl and LiPF 6 complexes in the solid-state and in solution by combining various experimental, spectroscopic, and computational methods. Solution studies were performed using 1 H DOSY, multinuclear variable temperature NMR spectroscopy, and quantum chemical calculations. [Ph 2 Si(2-CH 2 Py) 2 ·LiCl] 2 (3) dissociates into a monomeric species (9) in THF. For [Ph 2 Si(2-CH 2 Py) 2 ·LiPF 6 ] 2 (11), low temperature NMR studies revealed an unprecedented chiral coordination mode (12) in non-coordinating solvents.

Background: The aim of this study was to evaluate whether calcium (CaL) solution would enhance the capacity of sodium fluoride (NaF) solution in reducing the permeability of hypersensitive dentin., Material and Methods: Thirty-two Wistar rats ingested for 45 days acidic isotonic drink (Gatorade, pH 2.7) ad libitum to induce dental erosion. Then, molar teeth received a cold stimulus to confirm the presence and score the intensity of dentin hypersensitivity based on body contraction and noise. Animals were allocated to four groups (n=8), according to the solution(s) applied in the oral cavity: NaF (12 mmol/L, 1 min); CaL (150 mmol/L, 1 min); CaL followed by NaF (CaF+NaF, 1 min each); distilled water (DW, 1 min, as negative control). The animals were euthanized and the mandibles dissected into hemimandibles, which were sealed with sticky wax, except for the occlusal surface of the molar teeth. The samples were immersed in 10% copper sulphate solution and in 1% dithioxamide alcoholic solution (25 min each). The samples were sectioned longitudinally and imaged under optical microscope. Then, dentin permeability was measured as the area of copper ion penetration, using ImageJ software. Photomicrographs were obtained by scanning electron microscopy., Results: 68.7% of animals had body contraction associated or not with noise. One-way ANOVA followed by Tukey´s test indicated that groups treated with NaF solution, whether or not preceded by CaL solution, presented lower permeability than the remaining groups [CaL+NaF: 3405.7 μm2 (±1796.4); NaF: 4111.7 μm2 (±2450.6); CaL: 42254.6 μm2 (±30399.2); DW: 37064.6 μm2 (±21994.4)]. Photomicrographs showed that CaL+NaF group presented an increased proportion of occluded dentin tubules in comparison to the NaF-only group., Conclusions: Although qualitatively there seems to be a benefit in using CaL pre-rinse, this solution did not quantitatively enhance the capacity of NaF in reducing permeability of hypersensitive dentin. Key words: Dentin hypersensitivity, Fluoride, Calcium lactate, Animal model., Competing Interests: Conflict of interest statement:The authors declare no conflict of interest.

A novel enantioselective approach to the synthesis of a compound collection inspired by natural pyrrolizidine alkaloids was developed, employing an enantioselectively catalyzed 1,3-dipolar cycloaddition as the key step. The cycloadducts were obtained with excellent enantio- and diastereoselectivity. Biological evaluation of the resulting compound collection revealed that the compound class has multiple bioactivities, including activity against Plasmodium falciparum 3D7 and inhibition of Hedgehog signaling.

Complexity-generating chemical transformations that afford novel molecular scaffolds enriched in sp 3 character are highly desired. Here, we present a highly stereoselective scaffold diversity synthesis approach that utilizes cascade double-annulation reactions of diverse pairs of zwitterionic and non-zwitterionic partners with 3-formylchromones to generate highly complex tetracyclic benzopyrones. Each pair of annulation partners adds to the common chroman-4-one scaffold to build two new rings, supporting up to four contiguous chiral centers that include an all-carbon quaternary center. Differently ring-fused benzopyrones display different biological activities, thus demonstrating their immense potential in medicinal chemistry and chemical biology research.

Selective cleavage of a silicon-carbon bond in tetraorganosilanes is still a great challenge. A new type of Si-C(sp 3 ) bond cleavage in bench-stable (aminomethyl)silanes with common organolithium reagents as nucleophiles has now been identified. Suitable leaving groups are benzyl, allyl, and phenylthiomethyl groups. A β-donor function and polar solvents are essential for the reaction. Simple switching between α-deprotonation and substitution is possible through slight modifications of the reaction conditions. The stereochemical course of the reaction was elucidated by using a silicon-chiral benzylsilane. The new transformation proceeds stereospecifically with inversion of configuration and can be used for the targeted synthesis of enantiomerically pure tetraorganosilanes, which are otherwise difficult to access. Quantum chemical calculations provided insight into the mechanism of the new substitution., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Azines (2,3-diazabuta-1,3-dienes) are a widely used class of compounds with conjugated C=N double bonds. Herein, we present a direct synthesis of azines from alcohols and hydrazine hydrate. The reaction, catalyzed by a ruthenium pincer complex, evolves dihydrogen and can be run in a base-free version. The dehydrogenative coupling of benzylic and aliphatic alcohols led to good conversions and yields. Spectroscopic evidence for a hydrazine-coordinated dearomatized ruthenium pincer complex was obtained. Isolation of a supramolecular crystalline compound provided evidence for the important role of hydrogen bonding networks under the reaction conditions.

Iridoids comprise a large group of monoterpenoid natural products displaying a diverse array of biological activities ranging from neurotrophic to anti-inflammatory and anti-tumorigenic properties. Therefore, the development of concise synthesis routes to compound collections inspired by the structural features of these natural products is of particular relevance for chemical biology and medicinal chemistry. Herein we describe a samarium diiodide-mediated synthesis of a small, focused iridoid-inspired compound collection. Characterization of these iridoid analogues in biological assays revealed novel small-molecule inhibitors of autophagy.

A natural product-inspired synthesis of a compound collection embodying the tetrahydroindolo[2,3-a]quinolizine scaffold was established with a five step synthesis route. An imino-Diels-Alder reaction between Danishefsky's diene and the iminoesters derived from tryptamines was used as a key reaction. Reductive amination of the ketone function and amide synthesis with the carboxylic acid derived from the ethyl ester, were used to decorate the core scaffold. Thus a compound library of 530 tetrahydroindolo[2,3-a]quinolizines was generated and submitted to European lead factory consortium for various biological screenings., (Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Biology-oriented synthesis employs the structural information encoded in complex natural products to guide the synthesis of compound collections enriched in bioactivity. The trans-hydrindane dehydro-δ-lactone motif defines the characteristic scaffold of the steroid-like withanolides, a plant-derived natural product class with a diverse pattern of bioactivity. A withanolide-inspired compound collection was synthesized by making use of three key intermediates that contain this characteristic framework derivatized with different reactive functional groups. Biological evaluation of the compound collection in cell-based assays that monitored biological signal-transduction processes revealed a novel class of Hedgehog signaling inhibitors that target the protein Smoothened., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Eight new triterpenoids, prototiamins A-G (1-6, 9) and seco-tiaminic acid A (10), were isolated along with four known compounds from the bark of Entandrophragma congoënse. Their structures were elucidated by means of HRMS and different NMR techniques and chemical transformations. Assignments of relative and absolute configurations for the new compounds were achieved using NOESY experiments and by chemical modification including the advanced Mosher's method. Additionally, the structure and relative configuration of compound 3 were confirmed by single-crystal X-ray diffraction analysis. Compounds 1, 3, and 5 displayed significant in vitro antiplasmodial activity against the erythrocytic stages of chloroquine-sensitive Plasmodium falciparum strain NF54. Prototiamin C (3) was the most potent of the compounds isolated, with an IC50 value of 0.44 μM. All compounds tested showed low cytotoxicity for the L6 rat skeletal myoblast cell line.

Intramolecular isomerization in pentacoordinate compounds can play an essential role for the adjustment of defined stereochemical information. Here, we present a conclusive mechanism of a stereocontrolled reaction on chiral dimethoxysilanes that opens new aspects in understanding the origin of creating silicon-centered chirality during a nucleophilic substitution process. By combining experimental, structural, and quantum chemical methods, we were able to disclose an interconversion process, based on consecutive Berry-type motions, as the most plausible mechanism for describing the stereochemical outcome in suchlike substitution reactions.

A transition metal-free, oxidative, regioselective cross-coupling between non-functionalized azoles and chromones at C2-position was developed. A broad reaction scope and further transformation of products were demonstrated. The biological evaluation of products revealed a novel class of hedgehog signaling pathway inhibitors.

The stem bark of Polyalthia oliveri was screened for its chemical constituents using liquid chromatography high resolution mass spectrometry resulting in the isolation of three indolosesquiterpene alkaloids named 8α-polyveolinone (1), N-acetyl-8α-polyveolinone (2) and N-acetyl-polyveoline (3), together with three known compounds, dehydro-O-methylisopiline (4), N-methylurabaine (5) and polycarpol (6). The structures of the compounds were elucidated by means of high resolution mass spectrometry and different NMR techniques and chemical transformations. Their absolute configurations were assigned by ab-initio calculation of CD and ORD data (for 2 and 3) and X-ray diffraction analysis (for 2). Compounds 2 and 3 exhibited moderate antiplasmodial activity against erythrocytic stages of chloroquine-sensitive Plasmodium falciparum NF54 strain and low cytotoxicity on rat skeletal myoblast (L6) cell line., (Copyright © 2014 Elsevier Ltd. All rights reserved.)