[32]π Fused Core‐Modified Heptaphyrin with Möbius Aromaticity

A new fused core‐modified 32π heptaphyrin with Möbius aromatic character is reported. The ¹H NMR data indicated a weak Möbius aromaticity at 298 K; however, at 213–183 K, the molecule predominates [4n]π Möbius conformation with strong diatropic ring current, which was further confirmed by X‐ray analysis. The protonation experiment led to preservation of the Möbius aromaticity at 298 K. Nevertheless, the experimental results were further supported by theoretical studies. Overall, this study represents the first example of Möbius aromatic fused core‐modified expanded porphyrin.     

Attachment of 4-methoxy benzyl units to a tripodal fluoroionophore shows reversal of output functionality with Cu(II) input

Syntheses of three tris-(2-aminoethyl)amine, tren based tripodal fluoroionophores (L₂, L₃, and L₅), are reported. These fluoroionophores are designed based on the fluorophore–spacer–receptor format (choice of fluorophore in all three cases is anthryl unit). In L₂, three anthracene moieties are attached to the three arms of tren via –CH₂-spacer whereas L₃ and L₅ have p-nitro benzyl and p-methoxy benzyl substitutions, respectively, on L₂, which are in close proximity to the photoinduced electron transfer (PET) center. All three fluoroionophores show appreciably lower fluorescence compared to anthracene due to effective PET process in these systems but the quantum yield varies depending upon the nature of substitution at the PET center. In the cases of L₂ and L₅ different amounts of fluorescence recovery are observed in the presence of different cation inputs whereas L₃ is almost inactive toward cation sensing. Detailed fluorescence emission studies on L₂ and L₅ in the presence of different cation inputs showed that L₅ having N4 donor sets bearing three p-methoxy benzyl units attached to the three nitrogen centers involving photoinduced electron transfer process is a viable candidate for enhancement of fluorescence with Cu(II) input. In the absence of p-methoxy benzyl units at the nitrogen centers' resulting system, L₂ shows quenching of fluorescence with the Cu(II) under same experimental conditions.     

Syntheses, characterization and solid state thermal studies of N-propyl-1,2-diaminoethane (L) and N-isopropyl-1,2-diaminoethane (L′) complexes of nickel(II) nitrite: X-ray single crystal structure of trans-[NiL2(NO2)2]

Linkage isomers trans-bis(N-propyl-1,2-diaminoethane)dinitronickel(II) (brown, 1), trans-bis(N-isopropyl-1,2-diaminoethane)dinitritonickel(II) (blue-violet, 2a) and trans-bis(N-isopropyl-1,2-diaminoethane)dinitronickel(II) (brown, 2b) have been synthesized from solution and X-ray single crystal structure analysis of complex (1) has been performed. Simultaneous TG-DTA analyses reveal that complex (1) exhibits two successive phase transitions before to undergo decomposition (initial temperature of decomposition, Ti = 215 °C). The first one is reversible (82–98 °C; ΔH = 1.75 kJ mol⁻¹ for heating and 93–77 °C; ΔH = −1.65 kJ mol⁻¹ for cooling) and the second one is irreversible endothermic (135–150 °C kJ mol⁻¹; ΔH = 1.80 kJ mol⁻¹) phase transition. No visual color changes are observed in any of the two transitions. The causes related to the first phase transition remain unexplored. However, on the basis of IR spectral studies the second phase transition is supposed to be due to conformational changes of the diamine chelate rings. On the other hand, complexes (2a) and (2b) undergo decomposition without showing any phase transition [Ti = 185 and 195 °C for (2a) and (2b), respectively].     

Theoretical and experimental analysis of iron-exchanged X-zeolite catalyst for SI engine emission control

The fuel economy potential of lean-burn gasoline engines can be utilized without any adverse effect on the environment, only if a suitable catalytic system for converting NO_x in an oxidizing atmosphere is available. Selective catalytic reduction of NO_x over metal-exchanged zeolite can be one of the solutions for reducing NO_x in automobile exhaust containing excess oxygen. Iron-exchanged X-zeolite catalyst (Fe–X) has been developed and tested in the exhaust of an actual SI engine over a wide range of air–fuel ratio, space velocity (SV) and catalyst temperature. Maximum conversion efficiencies of 55.8% and 57.4% were recorded for NO_x and CO, respectively. The catalyst also maintains its high performance through a wide range of temperatures. A mathematical model has been developed as well for predicting the performance of the catalytic converter containing Fe–X catalyst and the numerical solutions are presented. The predicted results agree well with the experimental results and are within the experimental uncertainty limits. The absolute average deviations are found to be within 6% and 5% of the predicted conversion efficiencies for NO_x and CO, respectively.     

Role of positional isomers on receptor-anion binding and evidence for resonance energy transfer

New urea-based sensors show a strong affinity for F⁻, CH₃COO⁻, and H₂PO₄⁻ with an appreciable color change in the presence of excess F⁻. The position of the nitro group in the urea derivative influences the relative affinity toward anionic analytes. Spectral and ab initio studies showed the difference in the deprotonation sites for the ortho- and meta/para-isomers in these cases. Photophysical studies confirmed the resonance energy transfer in the case of the ortho-isomer. The ortho-isomer can act as a dual emission probe for F⁻.     

Determination of carbidic carbon in steels

An attempt has been made to develop a simple analytical technique that can readily be used in an industrial laboratory to isolate and quantify the precipitated carbides in steel samples. Attempt has also been made to correlate this value with the thermodynamically predicted values. There is good agreement between the predicted and experimental results. More work is in progress to develop this technique for the preparation of Certifed Reference Materials with dissolved and precipitated carbon in steels.     

Inhibition of phosphatase activity by positively-charged cyclodextrins

[formula: see text] Aminocyclodextrins are known to bind phosphate esters such as phosphotyrosine and p-nitrophenyl phosphate. This paper describes the inhibition of phosphate ester hydrolysis, as catalyzed by lambda-protein phosphatase and acid phosphatase, that is caused by such binding interactions. ROESY studies provide structural information about the cyclodextrin-aryl phosphate complexes. In addition, these experiments are used to generate approximations of the rates of dissociation of the noncovalent complexes.     

A Study on Hall Voltage and Electrical Resistivity of Doped Conducting Polyaniline

We report the electrical resistivity of HCl doped polyaniline in the temperature range 77 T 300 K. A maximum is obtained in the conductivity versus concentration of HCl curve at 3(N) HCl. The resistivity of the sample has been observed to show a decreasing trend with increase in temperature. The resistivity obeys the Mott variable range hopping theory. The Mott characteristic temperature (T _Mott) is very low in this sample compared to other studies. The Hall voltages have been found to be negative. The Hall coefficient, carrier concentration, and density of states have been determined from Hall measurement. From the conductivity versus temperature plot, different physical quantities such as localisation length and molecular vibrational frequency have been determined.