An efficient and a green route to synthesize phthalide-fused indoline, 3-[(5-chloro-1,3,3-trimethylindolin-2-ylidene)methyl]
isobenzofuran-1(3H)-one (3) has been developed by the coupling reaction of 5-chloro-2-methylene-1,3,3-trimethylindoline,
1 and 2-formylbenzoic acid, 2 under solvent-free domestic microwave irradiation. The compound was produced in 85%
yield. Compound 3 was characterized by analytical and spectral methods and its structure was confirmed by chemical
crystallography. Compound 3 was successfully crystallized in triclinic system with space group Pī. The molecular structure
consists of fused 1 and 2 groups connected by the enamine carbon. Binding study of 3 towards different types of metal
cations was done by colorimetric detection and UV-vis titrations. Compound 3 exhibited good selectivity and sensitivity
for Sn2+ compared to other metal cations tested. The stoichiometric binding ratio of 3 toward Sn2+ is found to be 1:1
and the binding constant (Ka) is 1.07×104 M–1 on the basis of Job’s plot and Benesi-Hildebrand analysis.
The two new symmetrical bis-thiourea compounds, 2,2’-[{(terephthaloylbis(azanediyl)bis (carbonothioyl)bis(azanediyl)}
bis(4-methylpentanoicacid)] 1A and 2,2’-[{(isophthaloylbis (azanediyl)bis(carbonothioyl)bis(azanediyl)}bis(4-
methylpentanoic acid)] 1B have been synthesized by reacting terephthaloyl/isophthaloyl chloride and L-leucine in high
yields. Newly synthesized bis-thiourea derivatives were characterized using FTIR, 1D NMR, 2D NMR, MS spectrometry and
Elemental analysis. Their binding properties with various cations were also carried out using UV-vis titration experiments.
Both isomers exhibited effective binding against Ag+, Cu2+, Ni2+, Hg2+, Pb2+, Fe2+, and Fe3+ in the presence of other cations,
such as Na+, Co2+, Cd2+, Zn2+, Mn2+, Mg2+, Ca2+, Sn2+, and Al3+. Stoichiometries of the host-guest complexation for both
isomers were found to be 1:4 by plotting molar-ratio curves. Pearson Product moment correlation coefficient was in the
range of 0.83-0.99 and nonlinear regression equation was used to calculate dissociation constant (Kd
). Both compounds
displayed weak antibacterial activities against gram-positive and gram negative bacteria. Cytotoxicity testing on CCD841
Normal human colon epithelial cell line showed that both compounds are non-toxic, with an IC50 value of 1.50 mg/mL.
A copper ion sensor based on a new bis-thiourea compound N1,N3-bis[[3,5-bis(trifluoromethyl)phenyl]carbamothioyl]isophthalamide (or TPC) as neutral carrier was investigated. The immobilization of the TPC into poly(n-butyl acrylate) (pBA) membrane via drop casting and the sensor was characterized by potentiometry. The sensor fabricated from TPC only showed a good Nernstian response towards copper ion with a sensitivity slope of 28.81±0.53mV/decade in the range of 1.0 × 10-6 - 1.0 × 10-4 M. The limit of detection of this sensor was found to be 6.11 × 10-7 M and with short sensor response time (60 - 80 s). This sensor also demonstrated reversibility and reproducibility with 3.69% and 1.84% (Relative Standard Deviation, RSD), respectively. Based on the separate solution method (SSM), the logarithm selectivity coefficients were better than -2.00 for monovalent, divalent and trivalent cations and this confirmed that the sensor exhibited good selectivity towards copper ion. The sensor could attain optimum function without the need in the inclusion of either lipophilic anions as a membrane additive nor plasticizer as a membrane softener. Thus, these are the main advantages. The addition of lipophilic anions into the pBA membrane could cause the sensitivity and selectivity of the copper ion sensor based on ionophore TPC to deteriorate.