Anaiyttca Chtmlca Acta, 235 (1990) 445-449 445

Elsevter Sctence Pubhshers B V , Amsterdam

Short Communication

Multi-wavelength thermal lens spectrophotometer

MINREN XU and CHIEU D TRAN *

Department of Chemrstry, Marquette Vntuersrty, Mdwaukee, WI 53233 (V S A )

(Recerved 1st February 1990)

ABSTRACT

A novel four-wavelength pump-probe conftguratron thermal lens spectrophotometer that 1s capable of stmulta-
neously measunng thermal lens signals at four dtfferent wavelengths has been developed. The four excrtatton beams
were denved from the same argon ion laser, whrch operated m a multt-hne mode The sample was sequenttally exctted
by these four beams and the correspondmg thermal lens srgnals were momtored by a He-Ne laser. Compared with
other exrstmg thermal lens apparatus, tms four-color spectrophotometer has advantages that include Its abthty to
provide rdentiftcatton of the analyte (as the ratios of the stgnals at four dtfferent excttatton wavelengths) and to analyze
stmultaneously four-component samples without the need for any pnor sample preparation With thts apparatus and
wtth the use of 6-mW excrtatton beams modulated at 102 Hz, the detection hmrt for four-component samples 1s
estimated to be about M+ M.- whrch is stmtlar to the detectron fmut obtamed~ for a one-component sample using a
single-wavelength system.

Keywords Thermal lens

Thermal lens techniques have been demon- In view of the above, efforts have been focused
strated to be sensitive methods for low-absorbance on the development of a novel instrument that has
measurements. Absorptivities as low as lo-’ have a higher selectivity than the conventional thermal
been measured by using these techniques [l-6]. lens instruments. This approach is based on the
Unfortunately, although a large number of appli- fact that the most powerful means of increasing
cations of thermal lens techniques to chemical the selectivity is to measure absorption at more
analysis have been reported during the past few than one wavelength simultaneously, because the
years, the methods are still relative under-utilized ratios of the absorptions at these wavelengths will
compared with other spectrochemical methods. permit the identification of a substance m a mx-
This is surprising as the techniques offer substan- ture, thereby introducing selectivity into the tech-
tial advantages over conventional spectroscopic nique. The development of a novel dual-wave-
methods with respect to non-contacting, in situ length thermal lens spectrophotometer which is
capability, precision, sensitivity, expanded dy- capable of simultaneously measuring the thermal
namic range and minimal sample requirements. lens signals as two different wavelengths has re-
The limited use of the thermal lens techniques is cently been successful [7-lo]. The dual-wave-
probably due to a combination of factors, but length capability enables this spectrometer to be
mainly the lack of selectivity. Most published used for the identification of samples, the detec-
thermal lens techniques have employed only one tion of two-component mixtures and the de-
excitation wavelength, which severely hinders their terminatton of the pHs of solutions at very low
application to the identification of unknown sam- indicator concentrations [7-lo].
ples and to the analysis of mixtures of compounds It was evident from these preliminary studies
[l-6]. that the use of multi-wavelength excitation tech-

0003-2670/90/$03 50 0 1990 - Elsevter Scrence Publishers BV

 M XUANDCD I-RAN

BS

BS

BS

DF

FIN. 1 Schematic diagram of the four-color thermal lens spectrophotometer BS = beam splitter, L = lens, DF = dlchrolc flter;
S = sample, F = filter, PH = pm-hole, PD = photodiode

niques introduces much needed selectivity mto the ment of the excitation and monitoring beams.
system [7-lo]. This selectivity is expected to de- These difficulties have recently been overcome
pend on the number of excitation wavelengths; and it was possible to develop the first thermal
the greater the number of excitation wavelengths lens spectrophotometer which is capable of simul-
employed, the higher is the selectivity. In addition, taneously measuring thermal lens signals at four
the number of components in a mixture which can different wavelengths. The mstrumentatlon and
be determmed equals the number of excitation application of this apparatus to the analysis of
wavelengths used [7-lo]. As real samples gener- four-component samples 1s reported in this com-
ally have many components, it 1s desirable for the munication.
thermal lens spectrophotometer to have multi-
component capabllity so that its utilization can be Experimental
extended to the area of general trace analysis. Figure 1 shows a schematic diagram of the
The instrumentation, i.e., optical arrangement, four-wavelength thermal lens apparatus. A Coher-
alignment and modulation, for the multl-wave- ent Innova 70-4 argon ion laser operated in the
length thermal lens spectrophotometer is more multi-line mode was used as an excitation source.
complex than that for dual-wavelength apparatus, The multi-line output was separated into individ-
because in addition to the ease of alignment, the ual wavelengths by an Amici Prism (Ealing Elec-
spatial arrangement of the two excitation beams in tro-Optics, Holliston, MA). Wavelengths of 514.5,
the dual-wavelength apparatus facilitates the use 488.0, 476.5 and 457.9 nm were selected as the
of only a single chopper to modulate sequentially four excitation wavelengths for this work. Four
the two beams at the same frequency. Addition of Uniblitz electronic shutters (Vincent Associates,
extra excitation wavelengths into the system Model LS6-Z) were used to modulate sequentially
creates several requirements, which include a novel the four beams at the same frequency. This modu-
optical arrangement, an electronic device to con- lation was accomplished by driving each shutter at
trol the timing and frequency of the choppers or the same frequency but at a different time interval
electronic shutters and the precise colinear align- with the reference signal from the previous one
MULTI-WAVELENGTH THERMAL LENS SPECTROPHOTOMETER 441

and to use its reference signal to drive the next of a vortex mixer and a sonicatton bath. Prior to
one. A mirror and three cubic beam splitters (BS) any measurement, solutions were filtered through
were used to align the four modulated excitation a Spartan nylon filter of 0.45~pm pore size. The
beams to propagate coincidentally. The four exci- thermal lens signal of the four-component mixture
tation beams were reflected into the sample (S) by and the slopes and intercepts of the 16 calibration
means of a beam splitter having 99.8/0.2 R/T graphs for each component at each excitation
(reflection/transmission). The intensities of the wavelength were used to calculate the concentra-
four excitation beams were monitored by measur- tion of each component in the mtxture. Detailed
ing the intensities of the four colinear and sequen- information for the calculation can be found in [9]
tial beams transmitted from this beam splitter and [lo], which describe the calculation method
with a PIN photodiode (PD2, United Detector for two-component mixtures.
Technology, PIN 10 DP) whose output was
amplified and fed to a personal computer (AT & Results and dmxwon
T Model 6300). The four (reflected) excitation A dichroic filter is generally used to facilitate
beams were focused onto the sample by an the colinear alignment of the pump and probe
achromatic lens of focal length 80 mm. The probe beam. It can be used either to reflect the pump
beam was provided by a Spectra-Physics Model beam(s) and transrmt the probe beam or to trans-
105-l He-Ne laser. The pump beams and the mit the pump beam(s) and reflect the probe beam.
probe beam were aligned to overlap colinearly at The first type has been widely used for conven-
the sample by a dichroic mirror (DC) whtch re- tional apparatus, winch is mostly based on a single
flects the 632.8-nm probe beam but transmits all excitation wavelength. It was found, however, that
other wavelengths. The heat generated by the sam- thts type of filter is not suitable for the present
ple absorption of the pump beams changed the multi-wavelength spectrometer, owing to the un-
intensity of the probe beam. The intensity fluctua- wanted deviations m the reflected beams winch
tion of the probe beam was measured with a PIN arise from the inability of the filter to provide the
photodiode (PDl, United Detector Technology same reflected angle for the incoming beams whose
PIN 10 DP) placed 2.5 m from the sample and wavelength difference was as large as 56 nm. This
behind an interference filter (F) and a 4-mm pin- difficulty is eliminated in the second type of filter
hole (PH). A lens of focal length 50 mm was used because it transmits the excitation beams and
to focus the probe beam, and its relative distance therefore does not produce any deviation due to
from the sample was adjusted to give maximum the difference in wavelength of the excitation
thermal lens signals. The output of the PDl was beams. Accordingly, this kmd of filter was used
amplified and fed into the PC for data acqutsttion for the present system.
and analysis through a 12-bit DAS 16 interface The intensity profiles of the excitation beams
board. Absorption spectra were taken on a and the probe beam are shown in Fig. 2. The
Perkin-Elmer 320 spectrophotometer. sample was excited sequentially by the four drffer-
1,2-Diaminoanthraquinone (DAA) (Aldrich), ent wavelengths, i.e., 514.5, 488.0, 476.5 and 457.9
l-amino-8chloroanthraquinone (ACA) (K & K nm, whose intensities as measured by the PD2 are
Laboratories), l,lO-phenanthrolme-tron(I1) per- shown in Fig. 2A. As shown, the four beams did
chlorate (PFeP) (GFS Chemicals) were used as not have the same intensity, but this differences
received. Iron(bipyrtdyl complexes (FeBP) did not create any problem as the thermal lens
were a gift from the Royal Instttution (London). srgnal is known to be directly proporttonal to the
Standard solutions for calibration graphs were excitation laser power [l-lo] so that it can be
prepared by injecting the required amount of stock normalized by taking the ratio of the signal (as
soluttons (5 X lop4 M in methanol) of DAA, measured by the probe beam intensity) to the
FeBP, ACA or PFeP into methanol. Four-compo- corresponding excitation beam intensity as re-
nent mixtures were prepared by mixing ap- corded by the PD2. Between two consecuttve exct-
propriate amounts of each component by means tations, there was always a dark period m which
448 M XUANDCD I-RAN

5145
4765
4579 beam in Fig. 2B by the corresponding excitation
4800 - -
-
beam intensities m Fig. 2A.
(A) One of the advantages provided by this ap-
paratus is its ability to provide additional infor-
- - mation on the identification of the analyte. This
selectivity is achieved by calculating the ratios of
the thermal lens signals at these four excitation
wavelengths. For the example shown in Fig. 2, the
ratios of the normalized thermal lens signals at
514.5, 488.0, 476.5 and 457.9 nm to that at 514.5
(B) nm were found to be 1, 0.844, 0.758 and 0.561,
respectively. These values are in relatively good
agreement with the values of 1, 0.853, 0.753 and
0.559 which were determined using a conventional
absorption spectrophotometer. The thermal lens
Rg. 2. (A) Excitation beam mtenslty and (B) probe beam
signals and ratio values of three other compounds,
mtenslty as as function of time. (A) Excltatlon beam mtenslty
for the 514.5-, 488.0-, 476.5- and 457 9-nm beams, (B) probe
viz., ACA, PFeP and FeBP, were also determined
beam mtenslty measured using the four excltahon beams shown and the values are given m Table 1. Table 1 also
m A on a sample of 5.0 X 10m8 M DAA m methanol. lists the ratio values obtained usmg the conven-
tional absorption technique. In all instances the
the sample was not excited by any beams. This values obtained using the two methods agree very
dark period enabled the sample to return to its well. This agreement demonstrates that the multi-
original thermal state before being excited again. wavelength thermal lens spectrophotometer is ca-
The heat generated as a consequence of the ab- pable of simultaneously determining the absorp-
sorption of the excitation beams by the sample tion of compounds at different wavelengths.
(5 X lop8 M DAA in methanol) was monitored by As mentioned earlier, the use of four-color exci-
the probe beam, whose beam center intensity pro- tation also facilitates the simultaneous analysis of
file is shown in Fig. 2B. As depicted, the intensity four-component samples. To demonstrate this ca-
of the probe beam decreased as the shutter opened pability, four different sets of four-component
to allow irradiation of the sample by the pump samples contaimng various concentrations of
beam, because the heat that was produced by the DAA, ACA, PFeP and FeBP were prepared. From
absorption of the pump beam by the sample acted their thermal lens signals and calibration graphs,
as a diverged thermal lens to defocus the probe the concentrations of each component in the rmx-
beam and, hence, decreased the beam center in- tures were calculated and are given in Table 2.
tensity. The normalized thermal lens signal was Very good agreement between the calculated and
calculated by dividing the peak height of the probe added values was found for samples containing

TABLE 1

Ratios of absorbances at 514.5, 488.0, 476 5 and 457.9 nm to that at 514 5 nm determmed by conventional and thermal lens
techmques

Corn- Conventlonal techmque Thermal lens techmque

pound
As14 s/A514 5 &is o/As14 5 A416 5/A514 5 A451 9/A514 5 A514 5/A514 5 A488 o/A514 5 A4l6 51-4514 5 -4457 s/A514 5

DAA 1.00 kOO1 0.84 kO.01 0.76 f 001 0.56 kOO1 1.000 f 0 002 0.853 f 0.001 0.753 f 0.003 0.559 f 0.004
ACA 1 00 f 0.01 1.526 f 0.008 1.607 f 0.006 1.590 f 0.009 l.ooO + 0.003 1530 f 0 004 1597 f 0 005 1 593 f 0.004
PFeP 1000 f 0.009 0.98 f 0.01 0 96 f 0.01 0.90 f 0.01 1.000 kO.003 0.968 f 0.009 0.97 fO.O1 0905 f 0.002
FeBP 1.00 f 0.01 0.898 f 0.008 0 855 f 0.006 0.58 + 0 01 1000 f 0.002 0.892 f 0.005 0.850 + 0 005 0 580 f 0.002
MULTI-WAVELENGTH THERMAL LENS SPECTROPHOTOMETER 449

TABLE 2 was accomplished by derivmg the four excitation

Simultaneous determmatlon of DAA, ACA, PFeP and FeBP wavelengths from the ion laser, whtch operated m
by m&l-wavelength thermal lens spectrometry a multi-line mode. The sample was sequentially
Compound Added (lo-’ M) Found (lo-’ M) excited by these four excitation wavelengths. Im-
tial alignment of the four excitation beams to
DAA 0.125 0 122
ACA 0 250 0 248 achieve the colinear overlap might prove to be
PFeP 0100 0 102 difficult but, once aligned, the four beams remam
FeBP 0500 0511 the same because they are derived from the same
DAA 0 650 0 649 ion laser. The selectivity of the present four-color
ACA 2 250 2 252 instrument is, however, much higher than that of
PFeP 0900 0 899 other available thermal lens systems as this spec-
FeBP 2500 2 345 trophotometer provides, for the first time, a sensi-
DAA 1250 1256 tive means to analyze simultaneously samples that
ACA 1 250 1 239 have up to four different components without any
PFeP 0500 0.508 prior sample preparation. To demonstrate the
FeBP 5000 4 910
principle, in the present system, only four out of
DAA 2500 2 486 nine output wavelengths from the argon ton laser
ACA 5000 4 971 were used. Additional wavelengths can be derived
PFeP 2000 2.021
10 015
from the same laser or from a mixed argon-kryp-
FeBP 10.000
ton laser, which has almost wlnte light output.
Experiments are in progress to explore this posst-
bility and to apply the apparatus to the analysis of
DAA, ACA, PFeP and FeBP at concentrations
real multi-component samples.
rangmg from 1 x lo-* to 1 x lop6 M.
The limits of detection (LOD) for the above
compounds were calculated from the calibration
graphs by determming the amount of the sample REFERENCES
that yielded a signal at the least absorbing wave-
length (i.e., 457.9 nm for DAA, PFeP and FeBP 1 D.S Khger (Ed ), Ultrasensltlve Laser Spectroscopy,
and 514.5 nm for ACA) twice the standard devia- Acadermc, New York, 1983
tion of the blank. For 6-mW excitation laser power 2 M D Morns and K Peck, Anal Chem , 58 (1986) 811A
3 J.M Harris and NJ DOVIC~, Anal Chem, 52 (1980)
modulated at 1.02 Hz, the LOD values were 5.0 X
695A.
10B9, 6.0~ 10e9, 2.0~ 10e9 and 3.4~ 10M9 M 4 N Teramae and J D Wmefordner, Appl Spectrosc, 41
for DAA, ACA, PFeP and FeBP, respectively. (1987) 164.
These values are comparable to those obtained on 5 C D Tran, Anal Chem., 60 (1980) 182
single- and dual-wavelength thermal lens appara- 6 C D Tran and T A Van Fleet, Anal Chem , 60 (1988)
2478
tus [l-10].
7 M Frank0 and CA Tran, Anal Chem , 60 (1988) 1925
A novel four-color excitation thermal lens spec- 8 C D Tran and M Franko, J Phys E, 22 (1989) 586
trophotometer was developed with the use of an 9 M Frank0 and C.D. Tran, Appl Spectrosc , 43 (1989) 661
argon ion laser as the only excitation source. This 10 C D Tran and M Xu, Appl Spectrosc , 43 (1989) 1056