Sains Malaysiana 39(3)(2010): 423–433

 

A Surface Potential Study of Ion-Uptake by 5,11,17,23-Tetra-Tert-Butyl-

25,27-Diethoxycarbonyl Methyleneoxy-26,28,Dihydroxycalix[4]Arene and

5,17-(3-Nitrobenzylideneamino)-11,23-Di-Tert-Butyl-25,27- Diethoxycarbonyl

Methyleneoxy-26,28-Dihydroxycalix[4]Arene Langmuir Blodgett (LB) Monolayers

(Kajian Potensi Permukaan Bagi Angkutan-Ion oleh Satu Lapisan Langmuir Blodgett (LB) 5,11,17,23-tetra-tertbutil-25,27-dietoksikarbonil metileneoksi-26,28,dihidroksikaliks[4]aren dan 5,17-(3-nitrobeniylideneamino)

-11,23-di-tert-butil-25,27- dietoksikarbonil metileneoksi-26,28-dihidroksikaliks[4]aren)

 

 

F.L. Supian & T.H. Richardson*

Department of Physics & Astronomy, University of Sheffield

Hounsfield Road, Sheffield (UK) S3 7RH, United Kingdom

 

M. Deasy, F. Kelleher & J.P. Ward

Department of Science, Institute of Technology Tallaght (ITT Dublin), Dublin 24, Ireland

 

V. McKee

Department of Chemistry, Loughborough University

Loughborough, Leicestershire (UK) LE113TU, United Kingdom

 

Received: 17 July 2009 / Accepted: 1 October 2009

 

 

ABSTRACT

 

A study of surface pressure - area (Π-A) isotherms, surface potential (ΔV) and effective dipole moment () of two calix[4] arenes, 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28,dihydroxycalix[4]arene (calixarene I) and 5,17-(3-nitrobenzylideneamino)-11,23-di-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4] arene (calixarene II) LB films which have the same lower rim but different upper rim has been carried out. This work used a NIMA Surface Potential (S-POT) sensor attached to an LB trough. Space filling model or Corey, Pauling and Koltun (CPK) precision molecular models have been used to estimate the size and the flexibility of both calix[4]arenes, which has been confirmed by X-Ray analysis in one case. The Π-A-isotherms confirmed that both of the calix[4]arenes form a monolayer film and the orientations of the plane of the calix ring are parallel with the air-water interface. The value of limiting area, (Alim) increases as a result of adding Fe3+ salt in the water subphase. For I, the value increases from 1.28 nm2 to 1.44 nm2 while for II, it increases from 1.70 nm2 to 1.86 nm2. ΔV measurements were performed on a water subphase containing Fe3+ salt in the concentration range 0 – 1.25 10–1 mM. ΔV of the compressed monolayer films increased with increasing Fe3+ concentration indicating the presence of Fe3+ salt bound within the calix[4]arenes. Using the ΔV values, the effective dipole moment has been found using the Helmholtz equation.

 

Keywords: Π-A isotherm, calix[4]arenes, effective dipole moment; LB; surface potential

 

ABSTRAK

 

Tekanan permukaan–kawasan isoterma (Π-A), potensi permukaan (ΔV) dan momen dwikutub berkesan () bagi dua filem LB kaliks[4]arene, 5,11,17,23-tetra-tert-butil-25,27-dietoksikarbonil metileneoksi-26,28,dihdroksikaliks[4] aren (kaliksaren I) dan 5,17-(3-nitrobenzilideneamino)-11,23-di-tert-butil-25,27-dietoksikarbonil metileneoksi-26,28- dihidroksikaliks[4]aren (kaliksaren II) yang mempunyai struktur bawah yang sama tetapi struktur atas yang berbeza telah dikaji. Kajian menggunakan sensor potensi permukaan NIMA (S-POT) pada alat LB. Model ruang penuh atau model kepersisan molekul Corey, Pauling dan Koltun (CPK) telah digunakan untuk menganggar saiz dan kefleksibelan bagi kedua-dua kaliks[4]aren, dan dalam satu kes telah disahkan dengan analisis sinar-X. Isoterma Π-A mengesahkan bahawa kedua-dua kaliks[4]aren membentuk satu lapisan filem dan orientasi bagi cincin kaliks adalah selari dengan permukaan udara-air. Nilai bagi kawasan terhad (Alim) bertambah apabila ditambah Fe3+ di dalam air. Bagi I, nilai bertambah daripada 1.28 nm2 ke 1.44 nm2 manakala bagi II, ia bertambah daripada 1.70 nm2 ke 1.86 nm2. Pengukuran ΔV dilakukan pada sub-fasa air yang mengandungi garam Fe3+ pada julat ketumpatan 0 – 1.25 10–1 mM. Pertambahan ΔV filem satu lapisan mampat dengan pertambahan kepekatan Fe3+ menandakan kehadiran garam Fe3+ bergabung dengan kaliks[4]arene. Menggunakan nilai-nilai ΔV, momen dwikutub berkesan telah diperolehi dengan menggunakan persamaan Helmholtz.

 

Kata kunci: Isoterma Π-A; kaliks[4]aren; LB; momen dwikutub berkesan; potensi permukaan

 

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*Corresponding author; email: t.richardson@sheffield.ac.uk

 

 

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