Thiacalix[4]arene derivatives bearing imidazole units : a ditopic hard/soft receptor for Na⁺ and K⁺/Ag⁺ with an allosteric effect and a reusable extractant for dichromate anions

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Two novel receptors 5,11,17,23-tetra-tert-butyl-25,27-bis[(ethoxycarbonyl)methoxy]-26,28-bis-[1-methyl-(imidazole)meth-oxy] -2,8,14,20-tetra-thiacalix[4]arene (L1) and 5,11,17,23-tetra-tert-butyl-25,27-bis-[(benzyl)methoxy] -26,28-bis-[1-methyl-(imidazole)-methoxy]-2,8,14,20-tetrathiacalix[4] arene (L2) possessing imidazole moieties based on thiacalix[4]arene in the 1,3-alternate conformation have been synthesized and characterized. The crystal structures of L1 and L2 have been determined. The binding behaviour towards Li + , Na + , K + and Ag + ions has been examined by 1 H NMR titration experiments in (CDCl 3 /CD 3 CN; 10:1, v/v) solution. The exclusive formation of mononuclear complexes of L1 with metal cations is of particular interest revealing a negative allosteric effect in the thiacalix[4]arene family. Liquid-liquid extraction experiments indicate that synthesized L2 can be utilized as an efficient reusable extractant for dichromate anion by controlling the pH of the aqueous solution

Calixarene-Tethered Textile Fabric for the Efficient Removal of Hexavalent Chromium from Polluted Water

This study describes the tethering of dimethylamionomethyl bonded calixarene (DMAM-calixarene) onto cotton fabric surface functionalized with poly(glycidyl methacrylate) (PGMA) linker layer using initiated chemical vapor deposition (iCVD) technique and the efficient adsorption capability of DMAM-calixarene functional textiles for the toxic hexavalent chromium from polluted water. The characterization of DMAM-calixarene-tethered textile fabric was performed by FTIR and XPS spectroscopy. Cr(VI) solutions was passed over packed DMAM-calixarene-tethered textile fabric adsorbent and the highest adsorption was observed at pH 2 in dichromate anion form of COS. The regeneration and selectivity studies indicate that the DMAM-calixarene-tethered textile fabric has outstanding adsorbent features in used experimental conditions for hexavalent chromium. Moreover, it was observed that both H-bonding and electrostatic interactions were significant factors in the dichromate anion adsorption process. Thus, this study clearly revealed that any DMAM-calixarene-tethered textile fabric can be easily used as a selective hexavalent chromium capture filter in geographic regions lacking appropriate wastewater purification systems

Entnahmestrategien subgingivaler Plaqueproben für mikrobiologische Gensonden-Tests: 4 oder 6 Proben?

Für die systemische Antibiotikagabe in der Therapie spezieller Parodontitisformen ist nicht die subgingivale Flora einzelner Taschen, sondern ein repräsentatives Bild der subgingivalen Flora des jeweiligen Patienten relevant. Aus Kostengründen werden Proben aus mehreren Taschen zusammengefasst und als sogenannte „gepoolte“ Probe ausgewertet (Flemmig et al. 1998, Beikler et al. 2005). Die gepoolte Auswertungsstrategie bietet für den Nachweis von A. actinomycetemcomitans, T. forsythia, P. gingivalis und T. denticola eine zumindest gleichwertige Nachweissicherheit wie Einzelauswertungen der Proben (Schacher et al. 2007). Die Probenentnahme aus der tiefsten Tasche eines jeden Quadranten (MT4) erwies sich als relativ verlässliche Methode, um Parodontalpathogene - bei Patienten die bisher keine Parodontitistherapie hatten -, nachzuweisen (Mombelli et al. 1991, 1994, Haffajee & Socransky 1992). Neuere Untersuchungen anderer Arbeitsgruppen konnten zeigen, dass die Entnahme von subgingivalen Plaqueproben an den 6 tiefsten Stellen (MT6), die höchste Prävalenz ergeben (Beikler et al. 2006). Allerdings erhöht die Entnahme von 6 statt 4 Proben den Aufwand. Bislang gab es nur Studien, die einen Vergleich zwischen 4 und 6 Stellen nur anhand von PCR-basierter Analyse, untersuchten (Himmer et al. 2009). Ziel dieser Studie war der Vergleich von Zahl und Nachweishäufigkeit von Parodontalpathogenen, bei Patienten mit aggressiver (AgP) oder generalisierter schwerer chronischer Parodontitis (ChP), mittels gepoolten subgingivalen Plaqueproben aus den tiefsten Taschen pro Quadrant und pro Sextant, mithilfe eines 16S rRNA-Gensonden-Tests. Insgesamt wurden bei 50 Patienten (30 weiblich) mit einer unbehandelten aggressiven (n=16) oder generalisierten schweren chronischen Parodontitis (n= 34) klinische Befunde erhoben und vor antiinfektiöser Therapie von jeweils den tiefsten Taschen jedes Quadranten (MT4) bzw. jedes Sextanten (MT6) subgingivale Plaqueproben für mikrobiologische Analysen gewonnen. Dazu wurden an 4 Stellen jeweils 2 sterile Papierspitzen gleichzeitig in den parodontalen Taschen platziert. Jeweils 1 Papierspitze aus jeder Tasche wurde mit den 3 Proben aus den anderen Taschen gepoolt (MT4). Die jeweils verbleibenden 4 Papierspitzen wurden mit 2 weiteren Papierspitzen aus den tiefsten Taschen der 2 verbliebenen Sextanten gepoolt (MT6). MT4 und MT6 wurden zum Nachweis von Aggregatibacter actinomycetemcomitans (AA), Porphyromonas gingivalis (PG), Tannerella forsythia (TF) und Treponema denticola (TD) mit einem 16S rRNS-Gensonden-Test verschickt. Für die statistische Analyse wurden die Bakterienzahlen logtransformiert. Mit MT6 wurde A. actinomycetemcomitans statistisch signifikant häufiger (46%) und in höheren Mengen (2,53±2,79) nachgewiesen als mit MT4 (32%/1,67±2,48) (P=0,035/P=0,002). Die Nachweishäufigkeiten und Durchschnittszahlen für PG, TF und TD waren generell hoch (>95%/>6,0), d.h. sie wurden insgesamt häufiger und in höheren Zahlen nachgewiesen als AA. Somit ergaben sich für die Keime PG, TF und TD keine statistisch signifikanten Unterschiede zwischen MT4 und MT6 hinsichtlich der Nachweishäufigkeit. Nur TF wird durch die Entnahmestrategie MT6 in statistisch signifikant höheren Zahlen nachgewiesen als mit MT4. Innerhalb der Grenzen der vorliegenden Studie können folgende Schlüsse gezogen werden: 1) Beim Gebrauch eines 16S rRNS Gensonden-Tests, ist die Nachweishäufigkeit und Zahl von A. actinomycetemcomitans bei der Entnahmestrategie MT6 gegenüber MT4 erhöht. Die Probenentnahme der tiefsten Tasche je Sextant (MT6) erscheint günstiger als die je Quadrant (MT4). 2) Die Nachweishäufigkeiten von P. gingivalis, T. forsythia und T. denticola lagen bei allen Patienten, die in dieser Studie untersucht wurden, bei mehr als 95%. Auch wurden diese Keime in höheren Mengen nachgewiesen, d.h. die logarithmierten Bakterienzahlen lagen bei 6.0. Diese Studie wurde von der Firma IAI Pado, Zuchwil, Schweiz unterstützt.A microbiological analysis representative for the subgingival micro flora of the whole oral cavity is relevant for adjunctive systemic antibiotic therapy of certain forms of periodontitis. Therefore due to economic reasons also the analysis of pooled plaque sampled from several sites is recommended (Beikler et al. 2005). Sampling of the deepest pocket of each quadrant has been demonstrated to detect quite reliably the subgingival presence of periodontal pathogens in untreated patients (Mombelli et al. 1991, 1994, Haffajee & Socransky 1992). The pooled plaque sampling strategy provides quite the same detection reliability (for A. actinomycetemcomitans, T. forsythia, P. gingivalis and T. denticola) as separately analyzed plaque samples (Schacher et al. 2007). After sampling 1 to 6 sites per patient increasing probability to detect the targeted bacteria with increasing number of sampled sites was reported (Beikler et al. 2006). However, sampling 6 sites instead of 4 sites increases the effort. Up to now the comparison of pooled samples from 4 to 6 sites has only been investigated for PCR-based microbiological analysis (Himmer et al. 2009). The aim of this study was to compare numbers and detection frequencies of periodontal pathogens in aggressive (AgP) or severe chronic periodontitis (ChP) by using pooled plaque samples from the deepest pockets per quadrant and per sextant using 16S rRNA gene probes. In 50 patients with AgP (n=16) or ChP (n=34), subgingival plaque was sampled from the deepest pockets per quadrant (MT4) and per sextant (MT6). Plaque was sampled using two sterile paper points simultaneously. One paper point from each pocket was pooled with 3 paper points of the other pockets (MT4). The remaining 4 paper points were pooled with 2 paper points from the deepest pockets from the two remaining sextants (MT6). Analysis was performed by 16S rRNA gene probes for Aggregatibacter actinomycetemcomitans, Tannerella forsythia, Porphyromonas gingivalis, and Treponema denticola. Detection frequency and counts for A. actinomycetemcomitans were statistically significantly higher with MT6 (46%/2.53±2.79) than MT4 (32%/1.67±2.48) (P=0.035/P=0.002). Detection and mean counts were high for P. gingivalis, T. forsythia, and T. denticola (>95 %/>6.0). This pathogens were detected in almost all patients (P. gingivalis: 98-100%, T. forsythia: 100%, T. denticola: 98%). These detection frequencies are in accordance with observations previously made by others in patients with untreated aggressive and generalized severe chronic periodontitis study (Krigar et al. 2007, Schacher et al. 2007). Thus, in untreated aggressive and generalized severe chronic periodontitis detection of P. gingivalis, T. forsythia, and T. denticola is no essential information because it may be expected in more than 95% of this kind of patients any way. Within the limitations of the present study the following conclusions may be drawn: 1) Using 16S rRNA gene probes sampling the deepest sites per sextant (MT6) provides a higher detection frequency and bacterial counts for A. actinomycetemcomitans than sampling the deepest sites per quadrant (MT4). 2) P. gingivalis, T. forsythia, and T. denticola were detected in more than 95% of all patients and with mean log-transformed numbers more than 6.0 in untreated aggressive and generalized severe chronic periodontitis. This study was supported by IAI Pado, Zuchwil, Switzerland

A Model-Theoretic Logical Inferentialist Account of Three-Valued Strong Kleene Logics

Proponents of model-theoretic logical inferentialism defend the view that the meaning of logical vocabulary, such as the truth functions associated with conjunction or negation, is determined by their inferential use. This position provides a naturalist and empiricist account of the meaning of logical vocabulary, since inferences consist of concrete speech acts that can be observed, such as assertions and denials. As a consequence, model-theoretic inferentialism gives an account of a problem widely discussed in philosophy of language as well as cognitive science for the meaning of logical vocabulary, that is, it provides an account of meaning based on the use of language. In this dissertation, we provide a model-theoretic logical inferentialist account to three-valued Strong Kleene Logics. In particular, we will show various solutions to the categoricity problem regarding these logics in order to show that we can determine the intended models of these logics from their inferences, we will give a model-theoretic logical inferentialist account to Quine [94]'s challenge ``Do proponents of different logics talk past each other, i.e., does the meaning of logical operators change when logics change?", and last we will give an account of Prior [93]'s challenge of tonk to inferentialism.In Chapter 1, we introduce model-thereotic logical inferentialism, and we introduce the technical machinery to determine the inferential semantics from a logic. In Chapter 2, we show how we can determine the intended semantics of Classical Logic and a class of Strong Kleene logics. In other words, we provide a number of well-motivated solutions to the categoricity problem, also known as Carnap's problem, regarding these logics. In Chapter 3, we provide a model-theoretic logical inferentialist account Quine [94]'s question: Do proponents of different logics talk past each other, i.e., does the meaning of logical operators change when logics change? We argue that model-theoretic inferentialists can provide an alternative account to this problem in comparison to the traditional model-theoretic or proof-theoretic accounts, since model-theoretic inferentialists use the inferential semantics of a logic. Chapter 4, we discuss the problem of tonk from a model-theoretic logical inferentialist point of view. We first introduce different tonk-like logical operators in our metainferential system, and define notions of metainferential existence and metainferential uniqueness. Then, we argue that the solution discussed by Fjellstad [39] is favored by model-theoretic logical inferentialist, given that the non-determinate interpretation of tonk discussed in Teijeiro [126] does not yield a completeness result when tonk-like connectives are introduced to our metainferential systems. Then, we argue that the substructural solution to tonk cannot be generalized to all logical operators

Mechanical Properties Identification of Viscoelastic/Hyperelastic Materials Using Haptic Device Based Experimental Setup

Mechanical behavior simulation of viscoelastic materials is a difficult task. In order to obtain accurate simulations, material model should be well chosen and hyperelastic characteristics of the viscoelastic materials should also be incorporated in the model. Once the material model is selected the coefficients can be identified with the help of mechanical tests/experiments. The main goal of this study is to optimize material model's coefficients by using the designed indenter test setup results and inverse finite element modeling. Indenter test setup was designed by using a haptic device, force sensor and data acquisition card to test the mechanical properties of the viscoelastic/hyperelastic materials. Inverse finite element modeling method is used in order to model the materials according to their material characteristics. The model obtained from the analysis was optimized by using the data obtained from indenter tests. The conformity of the chosen model and the tested materials is shown by inverse finite element modeling and the material model coefficients are proved to be identified correctly

Developmental Examination of Effect of Learned Helplessness on Feelinf-of-Knowing Judgment

In this research, it was aimed to exhibit whether learned helplessness influences feeling-of-knowing scores and accuracy of feeling-of-knowing judgments or not. It was also intended to specify whether a developmental difference between feeling-of-knowing scores and accuracy of feeling-of-knowing judgments exists. The research was conducted on age groups of adolescent (16-18 age), early adult (21-24 age) and medium adult (40-45 age). 90 subjects participated in the study. While to create feeling of helplessness Maze of Line Test was used, to measure feeling of knowing an episodic task composed of stages of learning, recall, making decision and recognition was used. One-way Analysis of Variance results showed that exposure to helplessness training did not affect feeling-of-knowing scores and accuracy of feeling-of-knowing judgments. Furthermore, it was found that any significant difference among adolescent, early adult and medium adult age groups did not exist with respect to feeling-of-knowing scores and accuracy of feeling-of-knowing judgments