Spectrophotometric Study of the Complexation of Some Lanthanide (III) Ions with a Series of 18-Crowns-6 in DMSO Solution Using Murexide as a Metallochromic Indicator

The complexation of La(III), Ce(III), Pr(III) and Er(III) with 18-crown-6(18C6), dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6 (DCY18C6) anddibenzopyridino-18-crown-6 (DBPY18C6) has been studied in dimethylsulfoxide(DMSO) by means of a competitive spectrophotometric method using murexide asa metal ion indicator. The formation constants of the 1 : 1 complexeswere found tovary in the order La(III) > Ce(III) > Pr(III) > Er(III). It was foundthat the structure influences the formation and stability of the resultingcomplexes. The effects ofvarious parameters on complexation are discussed. The order of the stabilityconstants of each lanthanide ion with these macrocycles are18C6 > DC18C6 > DB18C6 > DBPY18C6.     

Application of a dispersive micro‐solid‐phase extraction method for pre‐concentration and ultra‐trace determination of cadmium ions in water and biological samples

A method for the trace determination of cadmium ions in water, human urine and human blood serum samples using ultrasonic‐assisted dispersive micro‐solid‐phase extraction (UA‐D‐μSPE) was developed. Silica‐coated magnetic nanoparticles were coated with polythiophene, and the resulting sorbent was characterized using thermogravimetry, differential thermal analysis, scanning electron microscopy, Fourier transform infrared spectrometry and X‐ray diffraction. Following UA‐D‐μSPE, cadmium ions were quantified using graphite furnace atomic absorption spectrometry. A Box–Behnken design was used for optimization of important sorption and desorption parameters in UA‐D‐μSPE: in the sorption step, pH of solution, sorption amount and sonication time for sorption; in the desorption step, concentration of eluent, volume of eluent and sonication time. The optimum conditions for the method were: pH of solution, 7.5; sonication time for sorption, 3 min; sorption amount, 35 mg; type and concentration of eluent, HCl and 1.1 mol l^?1; volume of eluent, 360 μl; sonication time for desorption, 110 s. Under the optimized conditions the limit of detection and relative standard deviation for the detection of cadmium ions by UA‐D‐μSPE were found to be 0.8 ng l^?1 and <6%, respectively.     

A generalization of the Erdös-Ko-Rado theorem

In this note, we investigate some properties of local Kneser graphs defined in [János Körner, Concetta Pilotto, Gábor Simonyi, Local chromatic number and sperner capacity, J. Combin. Theory Ser. B 95 (1) (2005) 101-117]. In this regard, as a generalization of the Erdös-Ko-Rado theorem, we characterize the maximum independent sets of local Kneser graphs. Next, we provide an upper bound for their chromatic number.     

A three-dimensional model of vocal fold abduction/adduction

A three-dimensional biomechanical model of tissue deformation was developed to simulate dynamic vocal fold abduction and adduction. The model was made of 1721 nearly incompressible finite elements. The cricoarytenoid joint was modeled as a rocking-sliding motion, similar to two concentric cylinders. The vocal ligament and the thyroarytenoid muscle's fiber characteristics were implemented as a fiber-gel composite made of an isotropic ground substance imbedded with fibers. These fibers had contractile and/or passive nonlinear stress-strain characteristics. The verification of the model was made by comparing the range and speed of motion to published vocal fold kinematic data. The model simulated abduction to a maximum glottal angle of about 31 degrees. Using the posterior-cricoarytenoid muscle, the model produced an angular abduction speed of 405 degrees per second. The system mechanics seemed to favor abduction over adduction in both peak speed and response time, even when all intrinsic muscle properties were kept identical. The model also verified the notion that the vocalis and muscularis portions of the thyroarytenoid muscle play significantly different roles in posturing, with the muscularis portion having the larger effect on arytenoid movement. Other insights into the mechanisms of abduction/adduction were given.     

Fragmentation energetics of the phenol(+)···Ar(3) cation cluster

The various dissociation thresholds of phenol(+)···Ar(3) complexes for the consecutive loss of all three Ar ligands were measured in a molecular beam using resonant photoionization efficiency and mass analyzed threshold ionization spectroscopy via excitation of the first excited singlet state (S(1)). The adiabatic ionization energy is derived as 68077 ± 15 cm(-1). The analysis of the dissociation thresholds demonstrate that all three Ar ligands in the neutral phenol···Ar(3) tetramer are attached to the aromatic ring via π-bonding, denoted phenol···Ar(3)(3π). The value of the dissociation threshold for the loss of one Ar ligand from phenol(+)···Ar(3)(3π), ～190 cm(-1), is significantly lower than the binding energy measured for the π-bonded Ar ligand in the phenol(+)···Ar(π) dimer, D(0) = 535 ± 3 cm(-1). This difference is rationalized by an ionization-induced π → H isomerization process occurring prior to dissociation, that is, one Ar atom in phenol(+)···Ar(3)(3π) moves to the OH binding site, leading to a structure with one H-bonded and 2 π-bonded ligands, denoted phenol(+)···Ar(3)(H/2π). The dissociation thresholds for the loss of two and three Ar atoms are also reported as 860 and 1730 cm(-1). From these values, the binding energy of the H-bound Ar atom can be estimated as 870 cm(-1).