Solid Phase–Enhanced Photothermal Lensing with Mesoporous Polymethacrylate Matrices for Optical-Sensing Chemical Analysis

Abstract

Procedures for the photothermal lens determination of metals and organic compounds, on the basis of solid-phase mesoporous optical-sensing materials (polymethacrylate [PMA]) matrices with immobilized reagents, were developed. These procedures combine (i) selective and efficient preconcentration of trace substances to be analyzed in specially designed and synthesized transparent mesoporous PMA plates; (ii) sensitive determination with the reliable and traceable photometric reactions previously developed for classical spectrophotometry; and (iii) the sensitivity enhancement of photothermal lens detection in polymers, which provides at least a ten-fold increase in sensitivity compared with solutions due to polymer thermo-optical properties (solid phase–enhanced thermal lensing). It is shown that the overall sensitivity of photothermal lens measurements in PMA matrices is two orders higher than photometric absorbance measurements for the same excitation source power, which is in good agreement with the expected theoretical sensitivity. Changes in the preparation of transparent PMA plates and analytical procedures for photothermal measurements compared with spectrophotometry are discussed. PMA matrices modified with various analytical reagents were applied to trace determination of Hg(II), Fe(II), Ag(I), Cu(II), and ascorbic acid, with subnanomolar to nanomolar limits of detection.

Keywords

Photothermal spectroscopy Thermal lens spectrometry Solid-phase spectrophotometry Optical-sensing materials Trace determination Sensitivity comparison

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References

Narayanaswamy

Wolfbeis

O.S.

. Optical Sensors. Industrial, Environmental and Diagnostic Applications. Berlin Heidelberg, Germany: Springer, 2004.

Gavrilenko

N.A.

Mokrousov

G.M.

Dzhiganskaya

O.V.

. “An Optical Sensor for the Determination of Ascorbic Acid”. J. Anal. Chem. (Russ). 2004. 59(9): 871–874.

Brykina

G.D.

Rybalka

V.V.

Dmitrienko

S.G.

Shpigun

O.A.

. “Sorption of Bilirubin and its Determination by Solid-State Spectrophotometry”. J. Anal. Chem. (Russ). 1994. 49(2): 162–167.

Saputro

Yoshimura

Matsuoka

Takehara

Narsito . “Improved Solid-Phase Spectrophotometry for the Microdetermrnation of Chromium(-VI) in Natural Water”. Anal. Sci. 2009. 25(12): 1445–1450. doi:10.2116/analsci.25.1445.

Amin

A.S.

. “Utilization of Solid-Phase Spectrophotometry for the Determination of Trace Amounts of Copper Using 5-(2-Benzothiazolylazo)-8-hydroxyquinoline”. Chem. Papers. 2009. 63(6): 625–634. doi:10.2478/s11696-009-0067-x.

Amin

A.S.

Gouda

A.A.

. “Utility of Solid-Phase Spectrophotometry for Determination of Dissolved Iron(II) and Iron(III) Using 2,3-Dichloro-6-(3-carboxy-2-hydroxy-1-naphthylazo)qurnoxalrne”. Talanta. 2008. 76(5): 1241–1245. doi:10.1016/j.talanta.2008.05,034.

Mokrousov

G.M.

Gavrilenko

N.A.

Izaak

T.I.

Garber

N.G.

. “Sensitive Polymethylacrylate-Based Element for a Moisture Sensor”. Russ. J. Appl. Chem. 2000. 73(9): 1643–1645.

Gavrilenko

M.A.

Gavrilenko

N.A.

Mokrousov

G.M.

. “Solid-Phase Extraction of Aliphatic Amines from the Aqueous Phase with a Methacrylate Polymer”. Russ. J. Appl. Chem. 2005. 78(9): 1408–1410. doi:10.1007/s11167-005-0527-1.

Taguchi

Sun

H.F.

Hata

Kasahara

. “Design of Simple and Sensitive Methods for Trace Analysis by Means of Concentration with a Membrane Filter”. Bunseki Kagaku. 2000. 49(12): 941–952.

10.

Hill

C.M.

Street

K.W.

Tanner

S.P.

Philipp

W.H.

. “Preparation of Ion Exchange Films for Solid-Phase Spectrophotometry and Solid-Phase Fluorometry”. Anal. Lett. 2000. 33(13): 2779–2792.

11.

Gavrilenko

N.A.

Mokrousov

G.M.

. Sensitive Indicator Material for Determining Substance Microquantities. Russian Patent WO/2006/025763. Filed March 09, 2006.

12.

Gavrilenko

M.A.

Gavrilenko

N.A.

. “Polymethacrylate Sorbent for the Solid-Phase Extraction of Amines”. Mendeleev Comm. 2006. 16(2): 117–119. doi:10.1070/MC2006v016n02ABEH002125.

13.

Anishchenko

E.V.

Eremina

N.S.

Gavrilenko

N.A.

Mokrousov

G.M.

. “Influence of the Silver Ions on the Physicochemical Properties of Methyl Methacrylate–Methacrylic Acid Copolymer Films”. Russ. J. Appl. Chem. 2006. 79(3): 453–456. doi:10.1134/sl070427206030244.

14.

Bialkowski

S.E.

. Photothermal Spectroscopy Methods for Chemical Analysis. New York: Wiley-Interscience, 1996.

15.

Mokrousov

G.M.

Gavrilenko

N.A.

Garber

N.G.

Gavrilenko

M.A.

. “Intermolecular Interactions in Poly(methyl methacrylate) Modified with Silver, Copper, or Neodymium Trifluoroacetates”. Russ. J. Phys. Chem. 2001. 75(6): 1023–1025.

16.

Mokrousov

G.M.

Gavrilenko

N.A.

Eremina

N.S.

Garber

N.G.

. “Effect of Metal Trifluoroacetates on the Thermal Decomposition of Poly(methyl methacrylate)”. Russ. J. Phys. Chem. 2001. 75(6): 1026–1028.

17.

Nedosekin

D.A.

Faubel

Proskurnin

M.A.

Pyell

. “Determination of Light-Absorbing Layers at Inner Capillary Surface by CW Excitation Crossed-Beam Thermal Lens Spectrometry”. Talanta. 2009. 78(3): 682–690. doi:10.1016/j.talanta.2008.12.020.

18.

Nedosekin

D.A.

Pirogov

A.V.

Faubel

Pyell

Proskurnin

M.A.

. “Investigation of Ionene Adsorption on Quartz Surfaces by Thermal Lens Spectrometry”. Talanta. 2006. 68(5): 1474–1481. doi:10.1016/j.talanta.2005.08.010.

19.

Smirnova

Proskurnin

M.A.

Bendrysheva

S.N.

Nedosekin

D.A.

Hibara

Kitamori

. “Thermooptical Detection in Microchips: From Macro- to Micro-scale with Enhanced Analytical Parameters”. Electrophoresis. 2008. 29(13): 2741–2753. doi:10.1002/elps.200700914.

20.

Proskurnin

M.A.

Chemysh

V.V.

Filichkina

V.A.

. “Some Metrological Aspects of the Optimization of Thermal Lens Procedures”. J. Anal. Chem. (Russ). 2004. 59(9): 818–827. doi:10.1023/B:JANC.0000040695.95051.be.

21.

Gavrilenko

N.A.

Saranchina

N.V.

. “Analytical Properties of 1-(2-Pyridylazo)-2-Naphthol Immobilized on a Polymethacrylate Matrix”. J. Anal. Chem. (Russ). 2009. 64(3): 226–230. doi:10.1134/S1061934809030034.

22.

Gavrilenko

N.A.

Saranchina

N.V.

. “Solid-Phase Spectrophotometric Determination of Silver Using Dithizone Immobilized in a Polymethacrylate Matrix”. J. Anal. Chem. (Russ). 2010. 65(2): 148–152. doi:10.1134/S1061934810020085.

23.

Gavrilenko

M.A.

Gavrilenko

N.A.

Mokrousov

G.M.

. “Preconcentration of Phenols on a Polymethacrylate Sorbent for Their Gas-Chromatographic Determination in Water”. J. Anal. Chem. 2006. 61(3): 216–218. doi:10.1134/S1061934806030038.

24.

Gavrilenko

M.A.

Mokrousov

G.M.

Dzhiganskaya

O.V.

. “An Optical Sensor for Determination of Ascorbic Acid”. J. Anal. Chem. 2004. 59(9): 871–874. doi:10.1023/B:JANC.0000040703.73042.61.

25.

Gavrilenko

N.A.

Saranchina

N.V.

Mokrousov

G.M.

. “A Sensitive Optical Element for Mercury(II)”. J. Anal. Chem. (Russ). 2007. 62(9): 832–836. doi:10.1134/sl061934807090043.

26.

Gavrilenko

N.A.

Mokhova

O.V.

. “Sorption-Spectrophotometric Determination of Iron(II, III) with the Use of Organic Reagents Immobilized in a Polymethacrylate Matrix”. J. Anal. Chem. (Russ). 2008. 63(11): 1038–1043. doi:10.1134/sl06193480811004x.

27.

Gavrilenko

N.A.

Sukhanov

A.V.

Mokhova

O.V.

. “Redox and Acid-Base Properties of 2,6-Dichlorophenolindophenol Immobilized on a Polymethacrylate Matrix”. J. Anal. Chem. (Russ). 2010. 65(1): 17–20. doi:10.1134/s1061934810010041.

28.

Mokrousov

G.M.

Gavrilenko

N.A.

Izaak

T.I.

. “Ionic Conductivity of Polymethyl Methacrylate–Metal Trifluoroacetate Composites”. Russ. J. Appl. Chem. 2000. 73(8): 1424–1426.

29.

Galkin

Ageeva

Nedosekin

Proskurnin

Olenin

Mokrousov

. “Thermal Lens Spectrometry for the Synthesis and Study of Nanocomposites on the Basis of Silver Salts Absorbed by a Polyacrylate Matrix”. Moscow University Chemistry Bulletin. 2010. 65(2): 91–97. doi:10.3103/s0027131410020070.

30.

Nedosekin

D.A.

Brusnichkin

A.V.

Luk'yanov

A.Y.

Eremin

S.A.

Proskurnin

M.A.

. “Heterogeneous Thermal Lens Immunoassay for Small Organic Compounds: Determination of 4-Aminophenol”. Appl. Spectrosc. 2010. 64(8): 942–948. doi:10.1366/000370210792081136.

31.

Proskurnin

M.A.

Kuznetsova

V.V.

. “Optimisation of the Optical Scheme of a Dual-Beam Thermal Lens Spectrometer Using Expert Estimation”. Anal. Chim. Acta. 2000. 418(1): 101–111. doi:10.1016/s0003-2670(00)00949-1.

32.

Pyatnitskii

I.V.

Sukhan

V.V.

. Analytical Chemistry of Silver. (Engl. Trans.). Moscow, USSR: Nauka, 1975.

33.

Snook

R.D.

Lowe

R.D.

. “Thermal Lens Spectrometry—A Review”. Analyst. 1995. 120(8): 2051–2068. doi:10.1039/an9952002051.

34.

Nedosekin

D.A.

Proskurnin

M.A.

Kononets

M.Y.

. “Model for Continuous-Wave Laser-Induced Thermal Lens Spectrometry of Optically Transparent Surface-Absorbing Solids”. Appl. Optics. 2005. 44(29): 6296–6306. doi:10.1364/ao.44.006296.

35.

Gaiduk

Yorulmaz

Ruijgrok

P.V.

Orrit

. “Room-Temperature Detection of a Single Molecule's Absorption by Photothermal Contrast”. Science. 2010. 330(6002): 353–356. doi:10.1126/science.H95475.

36.

Luk'yanov

A.Y.

Vladykin

G.B.

Novikov

M.A.

Yashin

Y.I.

. “Comparison of the Capability Limits of Some Optical Detectors for Liquid Chromatography”. J. Anal. Chem. (Russ). 1999. 54(7): 633–638.

37.

Chartier

Bialkowski

S.E.

. “Accurate Measurements of Organic Dye Solutions by Use of Pulsed Laser Photothermal Deflection Spectroscopy”. Anal Chem. 1995. 67(15): 2672–2684. doi:10.1021/ac00111a028.

38.

Pons

Nonell

Garcia-Moreno

Costela

Sastre

. “Time-Resolved Thermal Lens Study on the Heat Dissipation Effects in Solid Polymeric Matrices Used as Laser Dyes”. Appl. Phys. B Lasers Optics. 2002. 75(6–7): 687–694. doi:10.1007/s00340-002-1028-z.

39.

Einsiedel

Mittler-Neher

. “Polarization-Dependent Photothermal Beam Deflection for the Determination of the Order Parameter C₂ in a Laser-Oriented Polymer System”. Appl. Optics. 1996. 35(27): 5406–5411. doi:10.1364/AO.35.005406.

40.

Schilt

A.A.

. Analytical Application of 1,10-Phenanthroline and Related Compounds. Oxford, UK: Pergamon, 1969.

41.

Ewing

G.W.

. Instrumental Methods of Chemical Analysis. New York: McGraw-Hill, 1985. 5 ed.

42.

Tavallali

Shaabanpur

Vahdati

. “A Highly Selective Optode for Determination of Hg (II) by a Modified Immobilization of Indigo Carmine on a Triacetylcellulose Membrane”. Spectrochim. Acta Molecular Biomolecular Spectrosc. 2012. 89: 216–221. doi:10.1016/j.saa.2011.12.055.

43.

Safavi

Bagheri

. “Design and Characteristics of a Mercury(II) Optode Based on Immobilization of Dithizone on a Triacetylcellulose Membrane”. Sensor Actuator B Chem. 2004. 99(2, 3): 608–612. doi:10.1016/j.snb.2004.01.022.

44.

Sanchez-Pedreno

Ortuno

J.A.

Albero

M.I.

Garcia

M.S.

Valero

M.V.

. “Development of a New Bulk Optode Membrane for the Determination of Mercury(II)”. Anal. Chim. Acta. 2000. 414(1–2): 195–203. doi:10.1016/s0003-2670(00)00809-6.

45.

Cassella

R.J.

. “On-line Solid-Phase Extraction with Polyurethane Foam: Trace-Level Spectrophotometric Determination of Iron in Natural Waters and Biological Materials”. J. Environ. Monitor. 2002. 4(4): 522–527. doi:10.1039/b204700d.

46.

Zaporozhets

Gawer

Sukhan

. “Determination of Fe(II), Cu(II) and Ag(I) by Using Silica Gel Loaded with 1,10-Phenanthroline”. Talanta. 1998. 46(6): 1387–1394. doi:10.1016/s0039-9140(98)00007-1.

47.

Goodlet

Narayanaswamy

. “An Optical-Fiber Vitamin C Sensor–Based on Immobilized 2,6–Dichloroindophenol”. Meas. Sci. Technol. 1994. 5(6): 667–670. doi:10.1088/0957-0233/5/6/006.

48.

Safavi

Bagheri

. “Design of a Copper(II) Optode Based on Immobilization of Dithizone on a Triacetylcellulose Membrane”. Sensor Actuator B Chem. 2005. 107(1): 53–58. doi:10.1016/j.snb.2004.10.062.

49.

Rezaei

Hadadzadeh

Azimi

. “Fabrication of an Optical Sensor Based on the Immobilization of Qsal on the Plasticized PVC Membrane for the Determination of Copper(II)”. J. Anal. Chem. (Russ). 2012. 67(8): 687–693. doi:10.1134/s1061934812080060.

50.

Liu

Qin

. “Ion-Exchange Reaction of silver(I) and Copper(II) in Optical Sensors Based on Thiaglutaric Diamide”. Anal. Sci. 2008. 24(9): 1151–1156. doi:10.2116/analsci.24.1151.

51.

Mahendra

Gangaiya

Sotheeswaran

Narayanaswamy

. “Investigation of a Fiber Optic Copper Sensor–Based on Immobilised α-Benzoinoxime (Cupron)”. Sensor Actuator B Chem. 2003. 90(1–3): 118–123. doi:10.1016/s0925-4005(03)00044-3.

52.

Rastegarzadeh

Rezaei

. “A Silver Optical Sensor Based On 5(p-Dimethylaminobenzylidene)rhodanine Immobilized on a Triacetylcellulose Membrane”. J. Anal. Chem. (Russ). 2008. 63(9): 897–901. doi:10.1134/S1061934808090189.