Fluorescence switchable sensor enabled by a calix[4]arene-Cu(II) complex system for selective determination of itraconazole in human serum and aqueous solution.

A switchable fluorescence sensor based on a calix (Monapathi et al., 2021) [4]arene:Cu2+ complex (FLCX/Cu) has been developed for the detection of itraconazole (ITZ) with high sensitivity and specificity. For the development of the sensor, the selective complexation of a fluorescent calix (Monapathi et al., 2021) [4]arene derivative (FL-CX) with the Cu2+ ion causing fluorescence quenching was utilized. In addition, the sensor properties of the FLCX/Cu prepared were investigated. For this purpose, various substances (selected anions, cations, and drugs) with which ITZ can be found together were studied in an aqueous solution. Limit of detection (LOD) and limit of quantification (LOQ) values were determined in the range of 1.00-60.0 µg/L as 3.34 µg/L and 11.1 µg/L for ITZ, respectively. Moreover, the real sample analyses were performed in human serum and tablet form. Furthermore, the effect of some possible serum contents on sensor performance was also studied. All these studies confirmed the development of a simple, precise, accurate, reproducible, highly sensitive, and very stable fluorescence sensor.

Nano-scale selective and sensitive optical sensor for metronidazole based on fluorescence quenching: 1H-Phenanthro[9,10-d]imidazolyl-calix[4]arene fluorescent probe.

It is crucial to determine and control the metronidazole (MET) ingredient in food and pharmaceuticals for human health and food safety. Even though many sensors have been previously reported to detect MET, there is still a need for a highly selective and sensitive, easy, fast, cost-effective sensor in this area. Herein, we report a fluorescent calix[4]arene derivative (PIMC) for highly selective and sensitive and facile and rapid MET detection based on fluorescence (FL) quenching. The highest FL quenching occurs when PIMC is exposed to MET solution at 400 nm (λex = 340). Owing to the quenching efficacy of MET linearly up to 5.5 × 104 nM was obtained a detection limit of 2.44 nM. Besides, interferences of other pharmaceuticals and ions on probe performance were investigated. The FL probe was successful in MET detection without the assistance of any separation techniques in a pharmaceutical sample (tablet) with an acceptable recovery of 101.3%. The applicability of the current probe as a paper-based sensor to MET detection has been successfully tested. As a result, the proposed probe presents a fast and suitable strategy to sensitive and selective detect MET and proves a good potential for practical applications, especially pharmaceutical preparations.

Capture and Release Recyclable Dimethylaminomethyl-Calixarene Functional Cloths for Point-of-Use Removal of Highly Toxic Chromium Water Pollutants.

Chromium(VI) contamination of drinking water arises from industrial activity wherever there is a lack of environmental legislation enforcement regarding the removal of such pollutants. Although it is possible to remove such harmful metal ions from drinking water through large-scale facilities, there currently exists no safe and simple way to filter chromium(VI) oxoanions at the point of use (which is potentially safer and necessary in remote locations or humanitarian scenarios). High-surface-area cloth substrates have been functionalized with calixarene molecules for the selective capture of aqueous chromium(VI) oxoanions in the presence of structurally similar anions. This is accomplished by pulsed plasmachemical deposition of a linker layer and subsequent functionalization with dimethylaminomethyl-calixarene (5,11,17,23-tetrakis[(dimethylamino)methyl]-25,26,27,28-tetrahydroxycalix[4]arene). Chromium(VI) oxoanions are captured by simply passing polluted water through the functionalized cloth, while other ions not harmful/beneficial to human health remain in the water. These cloth filters are simple to use, highly selective, and easily recyclable-thus making them attractive for point-of-use application in geographic regions lacking appropriate wastewater treatment plants or flawed environmental monitoring systems. Chromium(VI) pollutants have been successfully removed from real-world contaminated industrial wastewater streams using the dimethylaminomethyl-calixarene functionalized cloths.

Rapid and real-time detection of arginine enantiomers by QCM sensor having a Calix[4]arene receptor bearing asymmetric centers.

This paper describes the sensing studies of a chiral calix[4]arene receptor (5) having (R)-2-phenylglycinol moiety for arginine enantiomers (D-/L-arginine) by using Quartz Crystal Microbalance (QCM) technique. The initial experiments have revealed that the chiral calix[4]arene 5 coated QCM (CCC-QCM) sensor showed good sensing for arginine enantiomers, such that it has exhibited higher sensing towards D-arginine than that of L-arginine. It has been determined that the sensitivity, limit of detection values of CCC-QCM sensor for the D-/L-arginine solutions as 0.024/0.023 Hz/µM and 0.38/1.29 µM, respectively. On the other hand, the racemic mixture studies were optimized using the response surface methodology with central composite design. Consequently, it has been demonstrated that the QCM sensor modification with a calix[4]arene receptor bearing asymmetric centers provided rapid, real-time, sensitive and effective sensing of arginine enantiomers.

A phenyl glycinol appended calix[4]arene film for chiral detection of ascorbic acid on gold surface.

This paper describes the synthesis of new chiral calix [4]arene derivative having (R)-2-phenylglycinol moiety (compound 6), and its chiral recognition studies for ascorbic acid (AA) enantiomers by using Quartz Crystal Microbalance (QCM). Initial experiments indicated that the outstanding selective chiral recognition (α) was observed as 2.61 for l-enantiomer of AA. The sensitivity (S) and the limit of detection (LOD) values for L-AA were calculated as 0.0226 Hz/µM and 0.63 µM, respectively. Furthermore, the sorption behavior and mechanism of AA onto compound 6 film were evaluated and the sorption data exhibited a good correlation with the Freundlich isotherm models. The maximum uptake of L-AA by the sensor was found as 5895.76 mg/g. In conclusion, chiral recognition of AA enantiomers as real-time, sensitive, selective and effective was performed by a calixarene derivative coated QCM sensor.

Selective chiral recognition of alanine enantiomers by chiral calix[4]arene coated quartz crystal microbalance sensors.

We describe the synthesis of new chiral calix[4]arene derivatives having (R)-1-phenylethylamine, (S)-1-phenylethylamine, (R)-2-phenylglycinol, and (S)-2-phenylglycinol moieties, and chiral recognition studies for enantiomers of some selected α-amino acid derivatives such as alanine, phenylalanine, serine, and tryptophan using a quartz crystal microbalance (QCM). Initial experiments indicated that the highest selective chiral recognition factor was 1.42 for alanine enantiomers. The sensitivity, limit of detection, and time constant for L-alanine were calculated as 0.028 Hz/µM, 60.9 µM, and 36.2 s, respectively. The results indicated that real-time, sensitive, selective, and effective chiral recognition of alanine enantiomers was achieved with a QCM sensor coated with a chiral calix[4]arene derivative having (R)-2-phenylglycinol moieties.

Atrial electromechanical delay in patients undergoing heart transplantation.

BACKGROUND: We aimed to assess atrial electromechanical delay (AEMD) in patients who had undergone heart transplantation. METHODS: A total of 32 patients who underwent biatrial anastomosis heart transplantation (24 men, 8 women; mean age: 42±11 years) and 30 healthy volunteers (20 men, 10 women; mean age: 36±13 years) were included in the study. Atrial electromechanical coupling (PA), intra-AEMD, and inter-AEMD were measured. RESULTS: PA lateral (68±7 vs. 51±11 ms, p<0.01), PA septal (50±5 vs. 42±8 ms, p< 0.01) and PA tricuspid (39±6 vs. 36±9 ms, p<0.01), inter-AEMD (PA lateral-PA tricuspid) (27±7 vs. 10±4 ms, p<0.01), left intra-AEMD (PA lateral-PA septal) (18±7 vs. 10±4 ms, p<0.01), right intra-AEMD (PA septal-PA tricuspid) (13±5 vs. 5±3 ms, p<0.01) values were higher in patients who underwent heart transplantation than in a control population. CONCLUSION: Inter-AEMD and intra-AEMD were prolonged in patients who underwent heart transplantation as compared to a control population. This may explain the increased atrial fibrillation and other atrial arrhythmia incidences associated with the biatrial anastomosis heart transplantation technique and may contribute to the treatment of atrial fibrillation in this special patient group.

Evaluation of Tp-e Interval, Tp-e/QT Ratio, and Tp-e/QTc Ratio in Patients with Asymptomatic Arrhythmogenic Right Ventricular Cardiomyopathy.

BACKGROUND: Arrhythmogenic right ventricular dysplasia (ARVD) is characterized by progressive replacement of ventricular myocytes with variable amounts of fibrous and adipose tissue. Several studies have suggested that the interval from the peak to the end of the electrocardiographic T wave (Tp-e) may correspond to the transmural dispersion of repolarization and that increased Tp-e interval and Tp-e/QT ratio are associated with malignant ventricular arrhythmias. The aim of this study was to evaluate repolarization dispersion measured from the 12-lead surface electrocardiogram (including Tp-e interval, Tp-e/QT, and Tp-e/QTc ratio) in asymptomatic ARVD patients METHODS: We selected 27 patients with asymptomatic ARVD and 27 age- and gender-match young, healthy volunteers. RESULTS: Tp-e interval, Tp-e/QT and Tp-e/QTc ratio were also significantly higher in ARVD group compared to the control group (all P < 0.001). There were negative correlation between S global and Tp-e, Tp-e/QT, Tp-e/QTc ration (r = -0.57, P = 0.02; r = -0.85, P = 0.02; r = -0.63, P < 0.01; respectively). There were also negative correlation between Sm global and Tp-e, Tp-e/QT, Tp-e/QTc ration (r = -0.61, P < 0.01; r = -0.67, P < 0.01; r = -0.68, P < 0.01; respectively). Moreover, Em global were negative correlation between Tp-e, Tp-e/QT, and Tp-e/QTc (r = - 0.64, P < 0.001, r = - 0.75, P < 0.01; r = -0,69, P < 0.01; respectively) CONCLUSION: In conclusion, we have presented strong evidence suggesting that Tp-e interval, Tp-e/QT ratio, and Tp-e/QTc ratio were increased in asymptomatic ARVD patients.

Calix[4]arene coated QCM sensors for detection of VOC emissions: Methylene chloride sensing studies.

This paper describes the sensing studies of QCM sensors with coated some calixarene derivatives bearing different functional groups for some selected Volatile Organic Compounds (VOCs) such as acetone, acetonitrile, carbon tetrachloride, chloroform, methylene chloride (MC), N,N-dimethylformamide, 1,4-dioxane, ethanol, ethyl acetate, xylene, methanol, n-hexane and toluene. The initial experiments have revealed that whole the calix[4]arene modified QCM sensors exhibited strongest sensing ability to MC emissions. Thus, the detailed studies were performed for only MC emissions after the determination of relatively more effective calix-coated QCM sensors for MC emissions in aqueous media. The results demonstrated that QCM sensor coated with calix-7 bearing both amino and imidazole groups was most useful sensor for MC emissions with 54.1ppm of detection limit. Moreover, it was understood that cyclic structures, H-bonding capabilities and also good preorganization properties of calixarene derivatives played an important role in VOC sensing processes.

The Effect of Chronic Anabolic-Androgenic Steroid Use on Tp-E Interval, Tp-E/Qt Ratio, and Tp-E/Qtc Ratio in Male Bodybuilders.

BACKGROUND: The chronic consumption of androgenic anabolic steroids has shown to cause atrial arrhythmias. Several studies have suggested that the interval from the peak to the end of the electrocardiographic T wave (Tp-e) may correspond to the transmural dispersion of repolarization and that increased Tp-e interval and Tp-e/QT ratio are associated with malignant ventricular arrhythmias. The aim of this study was to evaluate repolarization dispersion measured from the 12-lead surface electrocardiogram (including Tp-e interval, Tp-e/QT ratio, and Tp-e/cQT ratio) in bodybuilders who are using anabolic androgenic steroids (AAS). METHODS: We selected a population of 33 competitive bodybuilders, including 15 actively using AAS for ≥ 2 years (users) and 18 who had never used AAS (nonusers), all men. RESULTS: QT, cQT, QTd, cQTd, JT, and cJT were significantly increased in AAS users bodybulders compared to the nonusers (all P < 0.001). Tp-e interval, Tp-e/QT ratio, and Tp-e/cQT ratio were also significantly higher in AAS user group compared to the nonuser group (all P < 0.001). QRS duration was not different between the groups. There were negative correlation between E(m) and Tp-e, Tp-e/QT ratio, Tp-e/cQT ration (r = -0.657, P < 0.01; r = -0.607, P = 0.02; r = -0.583, P = 0.02; respectively).There were also negative correlation between S(m) and Tp-e, Tp-e/QT ratio, Tp-e/cQT ration (r = -0.681, P < 0.01; r = -0.549, P = 0.03; r = -0.544, P = 0.023; respectively). CONCLUSION: In conclusion, we have presented a strong evidence suggesting that Tp-e interval, Tp-e/QT ratio, and Tp-e/QTc ratio were increased in AAS users, which suggest that there might be a link between AAS use and ventricular arrthymias and sudden death.

Association between restless leg syndrom and slow coronary flow.

OBJECTIVE: Restless legs syndrome (RLS) is a common sleep disorder in which patients feel unpleasent leg sensations and urge to move the legs during rest, especially at night, and symptoms are improved by leg movement. Prior studies analyzing the associations between cardiovascular disease and restless legs syndrome has shown controversial results. The goal of the study was to estimate the relationship between restless legs syndrome and slow coronary flow (SCF). METHODS: The present study was cross-sectional and observational and consists of 176 individuals who underwent coronary angiography and had angiographically normal coronary arteries of varying coronary flow rates. The study included 86 patients with isolated SCF and 90 control participants with normal coronary flow (NCF). RLS was assessed the day after the coronry flow was evaluated, using a self-administered questionnaire based on the International Restless Legs Study Group criteria. The following question was asked: "Do you have unpleasant leg sensations (like crawling, paraesthesia, or pain) combined with motor restlessness and an urge to move?" The possible responses were as follows: no, less than once/month, 2-4 times/month, 5-14 times/month, and 15 or more times per month. Those who answered that they had these feelings were asked the following two more questions: 1) "Do these symptoms occur only at rest and does moving improve them?" and 2) "Are these symptoms worsen in the evening/at night compared with the morning?" RLS is considered to be probable if the participant has answered "yes" for all three of the above questions, and has a frequency of ≥5 times/month. Student's t-test, Mann-Whitney U test, multiple logistic regression analysis were used for statistical analysis. RESULTS: The prevalence of restless legs syndrome was 48 (27%) and increased significantly with age. Patients with SCF have more likely had RLS than the control group (p<0.001). The age-adjusted prevalence odds of SCF were 3.11 times higher (95% CI: 1.54-6.29; P<0.001) among patients with RLS symptoms. Significant associations between RLS and SCF did not materially change after further adjustment for other potential covariates, such as sex, BMI, BMI squared, smoking. CONCLUSION: Our study concluded that there is a strong link between SCF and RLS.

Removal of lindane from an aqueous solution by using aminopropyl silica gel-immobilized calix[6]arene.

An aminopropyl silica gel-immobilized calix[6]arene (C[6]APS) has been used for the removal of lindane from an aqueous solution in batch sorption technique. The C[6]APS was synthesized with p-tert-butylcalix[6]arene hexacarboxylate derivative and aminopropyl silica gel in the presence of N,N'-diisopropyl carbodiimide coupling reagent. The sorption study was carried out as functions of solution pH, contact time, initial lindane concentration, C[6]APS dosage and ionic strength of solution. The matrix effect of natural water samples on the sorption efficiency of C[6]APS was also investigated. Maximum lindane removal was obtained at a wide pH range of 2-8 and sorption equilibrium was achieved in 2h. The isotherm analysis indicated that the sorption data can be represented by both Langmuir and Freundlich isotherm models. Increasing ionic strength of the solutions increased the sorption efficiency and matrix of natural water samples had no effect on the sorption of lindane. By using multilinear regression model, regression equation was also developed to explain the effects of the experimental variables.

Synthesis of a chitosan-linked calix[4]arene chelating polymer and its sorption ability toward heavy metals and dichromate anions.

This communication describes preparation, characterization, and the evaluation of sorption properties of a calix[4]arene-based chitosan polymer (C[4]BCP). C[4]BCP was used to sorption studies of some heavy metal cations (Co(2+), Ni(2+), Cu(2+), Cd(2+)(,) Hg(2+) and Pb(2+)) and dichromate anions (Cr(2)O(7)(2-)/HCr(2)O(7)(-)) as sorbent material. Also the supporting material (chitosan) was used for comparison in these experiments. The results for heavy metal cations showed that C[4]BCP was excellent sorbent and the effect of chitosan was low. In the sorption studies of dichromate anions, C[4]BCP was highly effective sorbent at pH 1.5.

Sorption characteristics of Cu(II) ions onto silica gel-immobilized calix[4]arene polymer in aqueous solutions: batch and column studies.

In the present study, Cu(II) removal from aqueous solutions by sorption was investigated. Aminopropyl silica gel-immobilized calix[4]arene polymer (APSIC[4]P) was used in sorption as sorbent. During the experimental part of this study, the effect of parameters, such as pH, initial Cu(II) concentration, temperature on Cu(II) removal was observed. In addition, sorption isotherm studies and column studies were made. Maximum Cu(II) removal was obtained at pH 6 and 25 degrees C. In the isotherm studies, Langmuir and Freundlich isotherm models were applied and it was determined that the experimental data confirmed to Langmuir isotherm model. Batch sorption capacity (q0) was calculated as 5.08 mg/g. The capacity value for column study was obtained by graphical integration as 1.14 mg/g. The Thomas and the Yoon-Nelson models were applied to experimental data to predict the breakthrough curves and to determine the characteristics parameters of the column useful for process design.

Preparation, characterization of cellulose-grafted with calix[4]arene polymers for the adsorption of heavy metals and dichromate anions.

In this paper, the adsorbents were prepared from cellulose-grafted with calix[4]arene polymers (CGC[4]P-1 and CGC[4]P-2) and their sorption properties studied. The polymers were characterized by Fourier transform infrared spectroscopy, elemental analysis, thermal gravimetric analysis and scanning electron microscopy. They were then used to evaluate the sorption properties of some heavy metal cations (Co(2+), Ni(2+), Cu(2+), Cd(2+), Hg(2+) and Pb(2+)) and dichromate anions (Cr(2)O(7)(2-)/HCr(2)O(7)(-)). Results showed that CGC[4]P-2 was a good sorbent for heavy metal cations while CGC[4]P-1 was ineffective. In the studies of dichromate anion sorption, it was observed that CGC[4]P-2 was a more highly effective sorbent at pH 1.5 than was CGC[4]P-1.