Subscriber access provided by UNIV OF NEBRASKA - LINCOLN

Article
An Au nanocomposite based chemiresistive
ammonia sensor for health monitoring
Sadanand Pandey, and Karuna Kar Nanda
ACS Sens., Just Accepted Manuscript DOI: 10.1021/acssensors.5b00013 Publication Date (Web): 15 Oct 2015
Downloaded from http://pubs.acs.org on October 17, 2015

Just Accepted

Just Accepted manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides Just Accepted as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. Just Accepted manuscripts
appear in full in PDF format accompanied by an HTML abstract. Just Accepted manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI). Just Accepted is an optional service offered
to authors. Therefore, the Just Accepted Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the Just
Accepted Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these Just Accepted manuscripts.

ACS Sensors is published by the American Chemical Society. 1155 Sixteenth Street
N.W., Washington, DC 20036
Published by American Chemical Society. Copyright American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.
Page 1 of 26 ACS Sensors

1
2
3
4 An Au nanocomposite based chemiresistive ammonia sensor
5
6 for health monitoring
7
8
9 Sadanand Pandey1,2* and Karuna K. Nanda1
10
11 1
12 Materials Research Centre, Indian Institute of Science, Bangalore 560012, India.
13 2
Department of Applied Chemistry, University of Johannesburg, 37 Nind Street,
14
15 Doornfontein, Johannesburg 2028, South Africa
16
17
18
19
20
21
22
23
24 ABSTRACT
25
26
27
We have developed a fast and highly sensitive chemiresistive sensor based on the nanocomposite
28
29 of polysaccharide (guar gum) and gold nanoparticles for the room temperature detection of
30
31 ammonia in the range of 0.1 parts-per-quadrillion (ppq) to 75000 parts-per-million (ppm). Sensor
32
33
34 response, selectivity and stability studies reveal excellent sensing of the nanocomposite. The
35
36 room temperature operation under ambient and the wide range sensing indicates that the
37
38 composites can be explored for environmental as well as biomedical applications. We have first
39
40
41 time quantified the ammonia level released from the urine and blood serum of human beings
42
43 using the resisitive sensor. The urine ammonia level was found to be ~24000 ppm and is higher
44
45
for patients with renal problems. This demonstrated the utility of the sensor for health
46
47
48 monitoring.
49
50
51
52
53
KEYWORDS: Nanocomposites, Ammonia sensor, Gold nanoparticle, Blood urea nitrogen,
54
55 Urine, chemiresistive sensor
56
57
58
59
60 1
ACS Paragon Plus Environment
 ACS Sensors Page 2 of 26

1
2
3
Ammonia is one of the most harmful environmental pollutants. Not only chemical processing
4
5 plants, but also our body releases ammonia that is high for patients with congestive heart failure,
6
7 heart attack, kidney failure/disorder, gastrointestinal bleeding, urinary tract obstruction, etc.1-3 In
8
9 this regard, early and accurate ammonia detection is essential. Chemiresistive sensors based on
10
11
three-terminal transistors and two-terminal resistive sensors for ammonia detection have
12 attracted significant attention.4-6 The sensing is based on the conductance change of the sensor
13
14 when exposed to ammonia vapour. Though there are several reports on chemiresistive sensing,
15 2,7-24
16 we summarize few important results in Table. 1. It may be noted that the sensors can be
17
18 useful for ammonia detection either in parts-per-trillion (ppt) range 17-19 or few thousands of part-
19 per million (ppm) range.22-25 The sensing from ppt to ppm level by a single sensor is very rare. In
20
21 the literature, several reports are found for ammonia sensing using Ag, Al, Pt, Ni, etc. however,
22
23 to the best of our knowledge, we obtain only one report based on NanoPANI-Au composite
24
25 material as chemiresistive ammonia sensor.26 So, "not much investigation is found on Au which
26
27
is a known a good catalyst" or "Need to improve the sensing performance". Hence, it can be a
28 motivation for this work.
29
30 Breath ammonia level is of the order of few ppm and can be investigated
31
32 spectroscopically.2 Body fluids such as blood and urine is expected to have very high ammonia
33
34 level. Therefore, detection of ammonia at few thousands of ppm is of paramount importance for
35 health monitoring and to the best of our knowledge, no quantification analysis of ammonia level
36
37 in urine is available. Here, we report for the first time a rapid and highly sensitive chemiresistive
38
39 sensor for the room temperature detection of ammonia levels in a wide range from 0.1 parts-per-
40
41 quadrillion (ppq) to 75000 ppm or higher. The sensor is based on the nanocomposite
42
43
(abbreviated as GG/Au nanocomposite) of polysaccharide (guar gum, GG) and gold (Au)
44 nanoparticles. Sensor response, temporal response, reversibility, selectivity and stability studies
45
46 reveal excellent ammonia sensing of the nanocomposite. Moreover, for the first time, we
47
48 quantify the ammonia level in urine. The ammonia level is found to be few thousand ppm and is
49
50 higher for patients with renal problems. This demonstrates that the chemiresistive sensor can be
51 used for the health monitoring. In addition, the sensor can also be used in environmental
52
53 monitoring, chemical processing plants, and gas detection for counter-terrorism because of the
54
55 remarkable low as well as high detection limit along with the simplicity of the operation.
56
57 *[Appropriate place for Table.1]
58
59
60 2
ACS Paragon Plus Environment
Page 3 of 26 ACS Sensors

1
2
3
EXPERIMENTAL SECTION
4
5 Chemicals and Biofluid
6
7 Chloroauric acid (HAuCl4) was obtained from Aldrich and GG from Merck, India.
8
9 Aqueous solutions were prepared using De-ionized (DI) water from a Milli-Q Plus system
10
11
(Millipore Co.). The urine and blood serum samples were collected from male and female
12 patients of different age groups through our Institute (IISc, Bangalore) health centre and stored at
13
14 -80 C until used. The clinical tested values were obtained by using Roche Cobas C111.
15
16 Synthesis and characterization of GG/Au nanocomposites
17
18 The synthesis procedure and the characterization of Au nanoparticles in GG have been
19 reported in Ref. 25. For the synthesis of Au nanoparticles in GG, a 1% w/v of GG is added with
20
21 aqueous solution of HAuCl4 (10 mM). The pH of the solution at the beginning of the experiment
22
23 was kept at 8 and the reaction temperature was 80 oC. In order to make the double loading,
24
25 aqueous solution of HAuCl4 (20 mM) are used, keeping all the conditions same.
26
27
Fabrication and characterization of the sensor device
28 Nanocomposite films based on Au nanoparticles and GG were formed on cover slip (1cm
29
30 x 1cm) by drop casting method followed by dring in air. Electrodes were prepared using silver
31
32 paste and are connected to source-measurement-unit which are used for measuring the electrical
33
34 properties of the sensing film. A Keithley meter was used to serve as both DC voltage source and
35 current meter. The measurements were performed in a very simple home-made testing chamber
36
37 (approximate volume of ~800 cm3) as shown in Figure 1c. The distance between aqueous
38
39 ammonia solution and sensor film is kept 1 cm. In the sensing experiment, the ammonia vapours
40
41 of different concentration (Supplemetary information, method of preparation of samples) evolves
42
43
spontaneously from aqueous solution were introduced into the testing chamber manually at the
44 humidity of ~48% and temperature of 20-250C. The detected concentration of the ammonia
45
46 vapours inside the testing chamber was evaluated by the change in current at constant voltage of
47
48 20 V. The response time (tres) and recovery time (trec), defined as the time required to reach 90%
49
50 of the final equilibrium value, was also evaluated. The sensor response, defined as the relative
51
variation in conductance due to the introduction of analyte G/Go, G= G Go, where Go is the
52
53 27
conductance in dried air and G is that in the dried air mixed with ammonia vapor . The
54
55 variation of current with time (temporal response) has been monitored for the sensing study. All
56
57 the results were obtained from the same sensor device in the static state and the dry air
58
59
60 3
ACS Paragon Plus Environment
 ACS Sensors Page 4 of 26

1
2
3
background. Finally, the sensing properties of the GG/Au nanocomposites are tested against
4
5 increasing ammonia concentration in the range of 0.1 ppq100000 ppm by monitoring the
6
7 changes in current through DC current-voltage (I-V) measurement using Keithley 237. The
8
9 method for the detection of urea level in human urine is same as the detection of ammonia vapor
10
11
evolved from aqueous ammonia solution, experimentally. The level of urea in human urine as
12 well as UUN can be quantified by using the calibration curve for ammonia and the equations 1
13
14 and 2. The topographical image of the sensing film was taken in an optical profilometer Zeta 20
15
16 instrument. Structural configuration analysis was performed using a PerkinElmer PE 1600
17
18 FTIR spectrophotometer (USA) in the range of 4000800 cm-1. Presence of Au nanoparticles
19 within the polymer network of GG/Au nanocomposites was confirmed by using JEOL JEM-
20
21 2100F and field emission electron transmission microscope (TEM).
22
23 Preparation of ammonia stock solution for sensing study
24
25 Concentrated ammonia (~25%) solution with an assay of 99.9% was purchased from
26
27
Merck (Germany). The different ammonia concentration was prepared by diluting in DI water.
28 However for the selectivity study of the sensor, ammonia concentration of 100000 ppm was used
29
30 and compared with analytical reagent (AR) graded various volatile organic compounds (VOCs)
31
32 without any dilution. The concentration measurement is based on the current against
33
34 concentration plot. This calibration plot was used as the reference for determination of amount of
35 urea in urine samples.
36
37
38
39 RESULTS AND DISCUSSION
40
41 Our sensor is based on the nanocomposite film of GG/Au and the configuration used is shown in
42
43
Figure 2a. The digital photograph and scanning electron microscopy image of the film with
44 electrical leads is shown in (Figure 1a,b). Au nanoparticles are found to be spherical in shapes
45
46 with the average particle size of 6.5 nm obtained using transmission electron microscopy
47
48 analysis. The sensing films are prepared by using drop-casted techniques are in the range of 0.25
49
50 to 0.35 mm thick.
51 Conductivity of a GG thin film and that of the composite films was found to be 8.45x10-9
52
53 and 2.56x10-6 -1cm-1, respectively. This clearly indicates that the conductivity of the films is
54
55 enhanced by the loading of Au nanoparticles in GG. This can be due to the formation of electron
56
57 conducting channel by the presence of Au nanoparticles in the film. The ammonia sensing
58
59
60 4
ACS Paragon Plus Environment
Page 5 of 26 ACS Sensors

1
2
3
experiments are carried out using a static testing chamber as shown in Figure 1c. In this context,
4
5 it is worthy to note that the static system is better suited for environmental as well as health
6
7 monitoring. Figure 1d shows the room temperature I-V characteristics of a sensing film at
8
9 different ammonia concentrations (1 ppq, 1 ppt, 1 ppb and 1 ppm). Here, the ammonia is
10
11
generated from aqueous ammonia as NH4OH
NH3+H2O and the current increases with
12 increase in ammonia concentration which has been exploited for ammonia sensing.
13
14 *[Appropriate place for Figure.1]
15
16 Temporal response for different ammonia concentrations is shown in Figure 2b ranging from 0.1
17
18 ppq to 100 ppm. The response at higher range of concentrations (10000-100000 ppm) is shown
19 in the inset. The change in current with increase in the ammonia concentration follows a linear
20
21 behaviour as shown in Figure 2c. It increases with the increase in ammonia concentration as
22
23 shown in Figure 2c. Figure 2d shows the response/recovery time which increases with increasing
24
25 the ammonia concentration. The response G/Go of the film at different ammonia concentration
26
27 are shown in Figure 2e. It can be noted that the sensor response increases linearly with the
28 increase in ammonia concentration and saturates beyond 30000 ppm. The sensor response
29
30 G/Go for 0.1 ppq is found to be ~26 which is extremely high and sensitive. This means that the
31
32 low detection limit of the sensor is at the level of ppq. Response, current and sensitivity are
33
34 included separately from 0.1ppq to 10ppq in (Fig.S1a,b,c) for better clarification.The highest
35
36 detection limit is 75000 ppm when the loading of Au nanoparticles in the film is doubled (Figure
37 3a,b).
38
39
40 *[Appropriate place for Figure.2]
41
42 Lastly, the stability of the sensor towards ammonia sensing has been studied over a
43
period of 6 months (Figure 3c). It is observed that the sensor response G/Go of the sensor at 1
44
45 ppm concentration of ammonia decreases by 6% in 6 months and then remains stable revealing a
46
47 remarkable stability of the sensor. Overall, the sensor response is excellent and very fast. It may
48
49 be noted that the sensor recovers automatically in the ambient at room temperature without any
50
51 external stimulus like UV irradiation or Joule heating.
52 As the concentrated ammonia is diluted with water to obtain different concentration, we
53
54 have investigated the response of the sensor with DI water. It is worthy to mention here that
55
56 water vapour alone is hardly contributing to the sensing of ammonia (Figure S2a) and hence,
57
58 different water vapour content in the analyte sample has negligible effect on the sensor response.
59
60 5
ACS Paragon Plus Environment
 ACS Sensors Page 6 of 26

1
2
3
We have also studied the ammonia sensing under the variation of humidity from 22 to
4
5 72% at room temperature condition by keeping the other parameters constant (100 ppm ammonia
6
7 concentration, distance of the film and the analyte, temperature). It follows that there is an
8
9 increase in the sensor response G/Go with relative humidity. The change in the sensor response
10
11 G/Go is only about 7.1% in the range of 22 to 72 %RH. Thus, the sensor can work efficiently
12
within the range 22 to 72%RH (figure.3d).
13
14 *[Appropriate place for Figure.3]
15
16 Sensing mechanism
17
18 In order to investigate the mechanism associated with ammonia sensing, temporal response of
19
20
the analyte in different environments (ambient, nitrogen and oxygen) has been performed (Figure
21 4a). Nitrogen and oxygen environments are created by purging the chamber with using pure and
22
23 dry gases. It is found that the sensor does not respond in nitrogen environment and the
24
25 performance of the sensor is similar both in ambient and oxygen environments. This suggests
26
27 that the measured current is the outcome of the interaction of ammonia with the sensor in
28 presence of oxygen rather the influence of physisorbed water to the film. It is observed that
29
30 neither GG nor Au film exclusively is responsible for the ammonia sensing. However in the
31
32 composite, it is suspected that oxygen chemisorption is facilitated at the interface of GG and Au
33
34 NPs. It plausibly be due to the breaking of the H-bonding of OH groups in GG in the presence
35
36
of Au NPs. Hence, oxygen adsorption takes place by H-bonding with OH groups. The oxygen
37 adsorption in the film facilitates the ammonia sensing by the change in the conductivity of the
38
39 sensor. The oxygen adsorption in the film decreases its electrical conductivity by withdrawing
40
41 electron from the film (Figure 4b). However, upon exposure to ammonia vapor, electrical
42
43 conductivity increases by reverting back electron to the film as ammonia removes adsorbed
44 oxygen from the surface (Figure 4c) [24]. It is reported in the literature28-30 that ammonia reacts
45
46 with adsorbed oxygen giving nitrous oxide (or nitrogen) and water at room temperature: 2NH3 +
47
48 5O-
2NO + 3H2O + 5e-. Importantly, almost no response is observed in nitrogen
49
50 environment. This mechanism is similar to sensing in metal oxide semiconductors where the
51
ammonia reacts with adsorbed oxygen causing the successful detection. Overall, the presence of
52
53 oxygen is essential for ammonia sensing and is available from the ambient. Moreover, a film
54
55 composed of GG alone or Au film (Figure not provided) is found futile in ammonia sensing
56
57 under identical experimental condition suggesting the combined effect of GG and Au.
58
59
60 6
ACS Paragon Plus Environment
Page 7 of 26 ACS Sensors

1
2
3
It can be noted from Table 1 that the performance of GG/Au sensor in terms of
4
5 24
sensitivity and is far superior as compared to our previously reported GG/Ag sensor . In this
6
7 context, we would like to note that the average size of Au nanoparticles (~6.5 nm) is smaller as
8
9 compared to Ag nanoparticles (~8.5 nm) and the density (4.7x1011 #/cm2) of Au nanoparticles in
10
11
the GG/Au film is also very high. This is believed to be the reason for the superior performance
12 of GG/Au film.
13
14
15 *[ Appropriate place for Figure.4]
16
17 In order to further explore the mechanism, ammonia of 100 ppm was exposed to the
18
19
GG/Au film and FTIR spectroscopy studies before and after exposure were carried out. Spectrum
20 of unexposed GG/Au film as shown in Figure 5a, mainly reveals water absorption bands with O
21
22 H stretching vibrations at 30003500 cm-1. Bands corresponding to aliphatic C-H stretching and
23
24 C=O stretching carboxylate group of typical saccharides appears at 2917 and 1641 cm1,
25
26 respectively. The polysaccharide displays other peaks at 1010 and 869 cm-1, due to the bending
27 vibration of the O-H and C-H bond, respectively. Interestingly, the spectrum remains identical
28
29 after the ammonia exposure (Figure 5a, Table S1).
30
31 We have also performed the TEM characterization of sensing film before and after
32
33 ammonia exposure. No change in shape, morphology or crystallinity is observed (Fig. 5b). The
34
topographical images taken in an optical profilometer before and after the ammonia exposure
35
36 show identical features as shown in Figure 5c,d with nearly identical root-mean-square
37
38 roughness (~0.07 m) of the film. Over all, GG/Au film retains its structure/morphology even
39
40 after the ammonia exposure suggesting that the sensor film can be used several times.
41
42 *[Appropriate place for Figure.5]
43
44 Selectivity is one of the important criteria for a useful sensor. In this regard, various
45
46 volatile organic compounds (VOCs) such as cyclohexane, n-butyl acetate, o-xylene, acetone,
47
48 acetonitrile, diethylether, ethanol, iso-propyl alcohol, methanol, tetrahydrofuran, and organic
49
50 sulphides (hydrogen sulphide, mercaptoacetic acid ) have been studied as analytes. It can be
51 noted from (Figure. 6a,b) that all the other analytes except sulphides show almost negligible
52
53 response (Fig.S2b). As ammonia is known to be a strong reducing agent over all these VOCs, we
54
55 believe that ammonia efficiently donates electron to the adsorbed oxygen and enhances the
56
57
58
59
60 7
ACS Paragon Plus Environment
 ACS Sensors Page 8 of 26

1
2
3
sensor response. However, the interference of sulphides cannot be ignored in ammonia detection
4
5 though the response to sulfides is low as compared ammonia.
6
7 *[Appropriate place for Figure.6]
8
9
10
11 Urea determination in human urine
12 Urine is found to be sterile until it reaches the urethra, where epithelial cells lining the
13
14 urethra are colonized by facultative anaerobic Gram negative rods and cocci.31 In the process of
15
16 elimination from the body, urine can acquire strong odours due to bacterial action by the release
17
18 of ammonia from the urea. In order to estimate urea concentration in urine, samples from 42
19 males and females patients were collected and used for the sensing experiments and then
20
21 corresponding temporal responses are obtained for these samples under identical conditions. The
22
23 concentration of ammonia for these samples is found out from the calibration curve for known
24
25 concentrations of ammonia. The urea concentration is evaluated using the following relation
26
27
where urea is completely converted into ammonia. The relationship between the concentrations
28 of urea and ammonia is given by
29
30 2x [A] (mg/dL) = [U] (mg/dL) (1)
31
32 where [U]= urea concentration and [A] = ammonia concentration. As the molecular weight of
33
34 urea is 60 and that of urea nitrogen is 28, the conversion factors between urine urea nitrogen
35 (UUN) and urea are given by
36
37 Urea [mg/dL] = UUN [mg/dL] * 60/28 (2)
38
39 The same conversion is valid for blood urea nitrogen (BUN) in case of human serum.
40
41 The temporal responses of urine samples from three volunteers are shown in Figure S2c.
42
43
Each sample is examined at least three times and the average result is presented here. The
44 average amount of ammonia is detected to be 2400 mg/dL (24000 ppm) which indicates the urea
45
46 present in human urine is ~1200 mg/dL (12000 ppm) which is in agreement with reported
47
48 value.31 The accuracy is found to be better than 97% over the entire range. Overall, the
49
50 chemiresistive sensor based urea quantification method reported here has high accuracy over a
51 wide concentration range. As a whole, the presence of ascorbic acid and glucose which are
52
53 present in human urine sample does not interfere in the detection of urea or UUN. It shows good
54
55 selectivity of the sensor towards urea quantification from urine sample. The reliability of the
56
57 ammonia quantification from urine has further been evaluated by measuring the current for
58
59
60 8
ACS Paragon Plus Environment
Page 9 of 26 ACS Sensors

1
2
3
24000 ppm of ammonia and comparing with the urine sample (Figure S2d). Almost similar
4
5 current is obtained for both the analytes as can be seen from Figure S2d. This demonstrates that
6
7 the quantification of ammonia/urea is possible through a chemiresistive sensor.
8
9 We have also examined the UUN and urea in urine samples of different age groups as
10
11
shown in Figure S3a,b. It is observed that the average urea level and UUN are found to be in the
12 range of 474-733 and 221-342 mg/dL, respectively for the age group 0-20 and 21-50 years. On
13
14 the other hand, the average value of urea and UUN are 1312 and 628 mg/dL, respectively for 51-
15
16 90 years of age group. Our observation is that the urea and UUN in the urine is very high for 51-
17
18 90 years of age group and is believed to be due to some abnormality, diseases or reduce
19 efficiency of the kidney. In order to establish the quantification of urea by using chemiresistive
20
21 sensor, we compare the value of urea in urine samples obtained using our sensor (measured
22
23 values) with the clinical tested values as shown in Figure S3c. It is interesting to note a linear
24
25 relation between them with a slope of ~1.0 and a correlation coefficient (R2=0.99) indicating the
26
27
high accuracy and preciseness of our sensor.
28
29
30 Urea in blood serum
31
32 There are several methods such as conductometry, amperometry, potentiometry, fiber-optic
33
34 sensor, colorimetric, photometric, mass spectrometry etc. for urea determination.32-35 Roche
35 Cobas C111 is based on the principle of photometric determination and is widely used. Clinical
36
37 values of BUN were obtained by using this instrument and compared with values obtained using
38
39 our chemiresistive sensors. It may be noted that samples were diluted several times for
40
41 measuring BUN/UUN.
42
43
In order to estimate urea concentration of blood serum, samples from 33 male and female
44 patients were collected and then corresponding temporal responses are obtained for these
45
46 samples under identical conditions. The average amount of ammonia detection is 616 mg/dL
47
48 (6160 ppm). This indicates that the urea present in blood serum is approximately 30 mg/dL (300
49
50 ppm) which is in agreement with reported values32. A typical temporal response for three
51 volunteers serum samples are illustrated in Figure S4a-c (Supplementary Information).
52
53 Different serum samples obtained from 6-72 years old different patients have been
54
55 analysed for urea and BUN by using our sensor and the histogram is shown in Figure 7a,b. It was
56
57 observed that normal average range of urea and BUN are between 27-48 and 13-22 mg/dL,
58
59
60 9
ACS Paragon Plus Environment
 ACS Sensors Page 10 of 26

1
2
3
respectively irrespective of the ages. The higher urea levels above this range are due to diabetic
4
5 or kidney disorder.
6
7 *[Appropriate place for Figure.7]
8
9 In order to compare the significance of our method for urea/BUN detection, we compare
10
11
our measured values with the clinical tested values for twenty serum samples (Figure 7c,d).
12 Interestingly, a linear relation is obtained and R2 of 0.90, a slope of 0.821 and an intercept of
13
14 0.026 are obtained when the data are fitted into a straight line. Similarly, R2 of 0.90, a slope of
15
16 0.821 and an intercept of 0.0123 are obtained from BUN data (Figure 7d). As the intercept is
17
18 close to zero for both the cases, the sensor value can be retrieved by multiplying the clinical
19 value with the respective slopes.
20
21 It is worthy to mention here that the method proposed here does not require any
22
23 additional reagents such as urease to facilitate the measurement or any external reference. In
24
25 addition, there is no pre-requisite sample preparation step for the analysis which takes not more
26
27
than 3 minutes per sample on an average. Furthermore, the sensor proposed here can be used for
28 several investigations. Overall, the method is convenient and environment friendly for laboratory
29
30 measurements and can not only be used for biomedical applications but also for environmental
31
32 monitoring as well chemical reaction studies. 24
33
34
35 Reproducibility of sensor
36
37 The reproducibility of the sensor has been tested for aqueous ammonia, serum as well as urine
38
39 samples. The relative standard deviation (RSD) of the sensor response with different ammonia
40
41 concentrations (fig.2c,e) and the comparison of the measured value of urea and BUN
42
43
concentrations with the clinical tested values (fig.7c,d) are found to be less than 3% for three
44 successive measurements. The maximum RSD of sensor response with double loading of Au
45
46 nanoparticles (fig.3a,b) is ~2.2%. This study confirms excellent reproducibility of the ammonia
47
48 sensor for detecting ammonia vapour from aqueous ammonia/serum/urine samples.
49
50
51 CONCLUSIONS
52
53 We have developed a highly sensitive chemiresistive sensor based on GG/Au
54
55 nanocomposite for environmental and biomedical diagnosis. The sensing is based on the
56
57 conductance change of the sensor when exposed to ammonia vapour. The sensor shows an
58
59
60 10
ACS Paragon Plus Environment
Page 11 of 26 ACS Sensors

1
2
3
excellent low as well high detection limit of 0.1 ppq and 30000 ppm, respectively at room
4
5 temperature at a very fast response/recovery time of few seconds to few minutes. The high
6
7 detection limit can be enahnced to 75000 ppm by simply increasing the loading of Au
8
9 nanoparticles. We have explored the real life application of our sensor for the detection of the
10
11
ammonia vapour released from the biofluid (urine/serum) which is first of its kind and shown
12 that the chemirestive sensor can suitably be calibrated for the diagnosis of various diseases. We
13
14 have also shown that the urea concentration in human urine and blood serum can easily be
15
16 quantified. The same technique can in principle be applicable to measure ammonia/urea in other
17
18 biological fluids, such as plasma, sweat, saliva, cerebrospinal liquids, etc. One of the biggest
19 advantages of the sensor is the room temperature operation under ambient in the wide range and
20
21 do not required any external stimulus for response or recovery of a sensor. The response,
22
23 stability, spontaneity, selectivity and reproducibility make this sensor excellent as compared to
24
25 the sensors reported in the literature. The films are stable over 6 months and can be used many
26
27
times without affecting the sensing efficiency. Hence, the application of these films is promising
28 as simple, robust, cost-effective for ultra trace to extremely higher detection of ammonia in
29
30 clinical samples.
31
32
33
34 ASSOCIATED CONTENT
35 Supporting Information Available: Preparation of NH3 solution of different concentration,
36
37 Additional figures of response time curve of the film in presence of water, ammonia; selectivity
38
39 study of the sensor; temporal response for volunteers` urine and serum samples. Additional
40
41 information as noted in text. This material is available free of charge via the Internet at
42
43
http://pubs.acs.org.
44
45
46 AUTHOR INFORMATION
47
48 Corresponding Author: sadanand.au@gmail.com; spandey@uj.ac.za (Dr. Sadanand Pandey)
49
50 Ph.; +27-11-5596644
51 Notes: The authors declare no competing financial interest.
52
53
54
55
56
57
58
59
60 11
ACS Paragon Plus Environment
 ACS Sensors Page 12 of 26

1
2
3
ACKNOWLEDGEMENTS
4
5 The authors SP is thankful to University Grant Commission (UGC), India and National research
6
7 foundation (NRF), South Africa for its generous financial support. The authors also acknowledge
8
9 financial assistance of Robert Bosch Center for Cyber Physical Systems, and Indian institute of
10
11
science for Lab facilities, Dr. Gopal Goswami for help and support. I would like to give thanks to
12 Mr. Hari for sulphide sensing study. Dr. Nagabhusan (CMO) for permitting and Mr. Rajesh
13
14 (Pathologist) for helping us to analyze the body fluid of different patients in IISc health centre,
15
16 We also thank R.V metropolis diagnostic & health care centre Pvt. Ltd, Bangalore (India) for
17
18 examining the urine samples.
19
20
21 REFERENCES
22
23 (1) Modi, A.; Koratkar, N.; Lass, E.; Wie, B.; Ajayan, P.M. Miniaturized gas ionization
24
25 sensors using carbon nanotubes. Nature 2003, 424, 171174.
26
27
(2) Kong, J. et al. Nanotube molecular wires as chemical sensors. Science 2000, 287, 622-624.
28 (3) Narasimhan, L.R.; Goodman, W.; Patel, N. Correlation of breath ammonia with blood urea
29
30 nitrogen and creatinine during hemodialysis. Proc. Natl. Acad. Sci. 2011, 98, 4617-4621.
31
32 (4) King, B.H.; Gramada, A.; Link, J.R.; Sailor, M.J. Internally referenced ammonia sensor
33
34 based on an electrochemically prepared porous SiO2 photonic crystal. Adv. Mater. 2007,
35 19, 40444048.
36
37 (5) Ding, M.; Tang, Y.; Gou, P.; Reber, M.J.; Star, A. Chemical sensing with polyaniline
38
39 coated single-walled carbon nanotubes. Adv. Mater. 2011, 23, 536-540.
40
41 (6) Tricoli, A.; Righettoni, M.; Telekki, A. Semiconductor gas sensors: dry synthesis and
42
43
application. Angew. Chem. 2010, 49, 7632-7659.
44 (7) Li, L. et al. High performance field-effect ammonia sensors based on a structured ultrathin
45
46 organic semiconductor film. Adv. Mater. 2013, 25, 34193425.
47
48 (8) Du, N. et al. Porous indium oxide nanotubes: layer-by-layer assembly on carbon-nanotube
49
50 templates and application for room-temperature NH3 gas sensors. Adv. Mater. 2007, 19,
51 16411645.
52
53 (9) Lee, K.; Gatensby, R.; McEvoy, N.; Hallam, T.; Duesberg, G.S. High-performance sensors
54
55 based on molybdenum disulfide thin films. Adv. Mater. 2013, 25, 66996702 .
56
57
58
59
60 12
ACS Paragon Plus Environment
Page 13 of 26 ACS Sensors

1
2
3
(10) Llobet, E. et al. Fabrication of highly sensitive tungsten oxide ammonia sensors.
4
5 Electrochem. Soc. 2000, 147, 776-779.
6
7 (11) Chen, T.-Y. et al. Ammonia sensing properties of a Pt/AlGaN/GaN Schottky diode. IEEE
8
9 Trans. Electron Devices 2011, 58, 1541-1547.
10
11
(12) Chabukswar, V.V.; Pethkar, S.; Athawale, A.A. Acrylic acid doped polyaniline as an
12 ammonia sensor. Sens. Actuators 2011, B 77, 657-663.
13
14 (13) Ghosh, R.; Midya, A.; Santra, S.; Ray, S.K.; Guha, P.K. Chemically reduced graphene
15
16 oxide for ammonia detection at room temperature. Appl. Mater. Interfaces 2013, 5,
17
18 75997603.
19 (14) Xing, W.; Hu, J.; Kung, S.-C.; Donavan, K.C.; Yan, W.; Wu, R.; Penner, R.M. A
20
21 chemically-responsive nanojunction within a silver nanowire. Nano Lett. 2012, 12,
22
23 17291735.
24
25 (15) Yavari, F.; Castillo, E.; Gullapalli, H.; Ajayan, P.M.; Koratkar, N. High sensitivity
26
27
detection of NO2 and NH3 in air using chemical vapor deposition grown graphene. Appl.
28 Phys. Lett. 2012, 100, 203120.
29
30 (16) Zan, H.W.; Dai, M.Z.; Hsu, T.Y.; Lin, H.C.; Meng, H.F.; Yang, Y.S. Ammonia gas
31
32 sensor based on pentacene organic field-effect transistor. IEEE Sensor Journal 2012, 12,
33
34 504-601.
35 (17) Chen, G. et al. Enhanced gas sensing in pristine carbon nanotubes under continuous
36
37 ultraviolet light illumination. Sci. Rep. 2012, 2, 343.
38
39 (18) Dai, M-J. et al. Highly sensitive ammonia sensor with organic vertical nanojunctions for
40
41 noninvasive detection of hepatic injury. Anal.Chem. 2013, 85, 31103117.
42
43
(19) Field, C.R.; In, H.J.; Begue, N.J.; Pehrsson, P.E. Vapor detection performance of vertically
44 aligned, ordered arrays of silicon nanowires with a porous electrode. Anal. Chem. 2011, 83,
45
46 47244728.
47
48 (20) Gong, J.; Li, Y.H.; Hu, Z.S.; Zhou, Z.Z.; Deng, Y.L. Ultrasensitive NH3 gas sensor from
49
50 polyaniline nanograin enchased TiO2 fibers. J. Phys. Chem C 2010, 114, 99709974.
51 (21) Chen, S.; Sun, G. High sensitivity ammonia sensor using a hierarchical
52
53 polyaniline/poly(ethylene-co-glycidyl methacrylate) nanofibrous composite membrane.
54
55 Appl. Mater. Interfaces 2013, 5, 64736477.
56
57
58
59
60 13
ACS Paragon Plus Environment
 ACS Sensors Page 14 of 26

1
2
3
(22) Krutovertsev, S.A.; Sorokin, S.I.; Zorin, A.V.; Letuchy, Ya. A.; Antonova, Yu. O. Polymer
4
5 film-based sensors for ammonia detection. Sens. Actuators B 1992, 7, 492494.
6
7 (23) Penza, M.; Milella, E.; Musion, F.; Alba, M.B.; Cassano, G.; Quirini, A. AC and DC
8
9 measurements on Langmuir-Blodgett polypyrrole films for selective NH3 gas detection.
10
11
Mater. Sci. Eng. C 1998, 5, 255258.
12 (24) Pandey, S.; Goswami, G.K.; Nanda, K.K. Nanocomposite based flexible ultrasensitive
13
14 resistive gas sensor for chemical reactions studies. Sci. Rep. 2013, 3, 2082.
15
16 (25) Pandey, S.; Goswami, G.K.; Nanda, K.K. Green synthesis of polysaccharide/gold
17
18 nanoparticle nanocomposite: An efficient ammonia sensor. Carbohydr Polym. 2013, 94,
19
229-234.
20
21 (26) Venditti, I.; Fratoddi, I.; Russo, V.; Bearzotti. A. A nanostructured composite based on
22
23 polyaniline and gold nanoparticles: synthesis and gas sensing properties. Nanotechnology
24
25 2013, 155503.
26
27
(27) Wang Z.H. Nanobelts, nanowires and nanodiskeltes of semiconducting oxides-From
28 materials to nanodevices. Adv. Mater. 2003, 15, 432-436.
29
30 (28) Ebbing, D.; Gammon, S.D. General Chemistry, 10th ed.; Brooks Cole publisher: US, 2012,
31
32 ISBN-13: 978-1285051376
33
34 (29) Duo, W.; Dam-Johnsen, K.; Ostergaard, K. Kinetics of the gas-phase reaction between
35 nitric oxide, ammonia and oxygen. Can. J. Chem. Eng. 1992, 70, 1014-1020.
36
37 (30) Tulliani, J.-M.; Cavalieri, A.; Mussob, S.; Sardellad, E.; Geobaldo, F. Room temperature
38
39 ammonia sensors based on zinc oxide and functionalized graphite and multi-walled carbon
40
41 nanotubes. Sens. Actuat. B 2011, 152, 144.
42
43
(31) Stevens, L.A.; Lafayette, R.A.; Perrone, R.D.; Levey, A.S. Laboratory evaluation
44
45
of kidney function, in Diseases of the Kidney and Urinary Tract, R. W. Schrier,
46 Ed., pp. 299336, Lippincott Williams & Wilkins, Philadelphia, Pa, USA, 8th ed.;
47
48 2007. Geigy Scientific Tables, 8th Rev. Ed.; Basle, Switzerland: Ciba-Geigy, 19811992.
49
50 (32) Walker, H.K.; Hall, W.D.; Hurst, J.W. Clinical Methods: The History, Physical, and
51
52 Laboratory Examinations. 3rd ed.; Boston: Butterworths; 1990, (chapter.193 BUN and
53
54 creatinine, Adrian O Hosten).
55
56
(33) Beckman. Beckman Synchron LX Systems Chemistry Information Manual. Beckman
57 Coulter, Inc., Brea, California. 2001.
58
59
60 14
ACS Paragon Plus Environment
Page 15 of 26 ACS Sensors

1
2
3 13
(34) Tanigawa, T. et al. Simple and rapid quantitative assay of C-labelled urea in human
4
5 serum using liquid chromatography-atmospheric pressure chemical ionization mass
6
7 spectrometry. J. Chromatogr. B: Biomed. Appl. 1996, 683, 135142.
8
9 (35) Kessler, A.; Siekmann, L. Measurement of urea in human serum by isotope dilution mass
10
11
spectrometry: a reference procedure. Clin. Chem. 1999, 45, 15231529.
12
13
14 List of figures and table caption
15
16
17
18 Figure 1. Characterisation of sensing film (a) Digital photograph and (b) SEM image of the film.
19 (c) The schematic of the testing chamber. (d) I-V characteristic of a sensor made of the GG/Au
20
21 nanocomposite film with different concentrations of ammonia vapors.
22
23
24
25 Figure 2 Ammonia sensing of GG/Au nanocomposite film. (a) Schematic of the configuration
26
27
used for ammonia sensing. (b) Temporal response curve of our GG/Au sensor in 0.1 ppq to 100
28 ppm range. Temporal response at higher ppm concentrations (10000, 20000, 30000, 50000,
29
30 100000 ppm) is shown in the inset marked as 1 to 5, respectively. The response to different
31
32 concentrations is studied differently though the film is the same and presented together with the
33
34 baseline adjusted for simplicity. (c) Log-log plot of current versus different ammonia
35 concentration. Dashed line is its linear fit. (d) Semi-log plot of response and recovery time of
36
37 different ammonia concentration. The solid line is guide to eye. (e) Log-log plot of sensor
38
39 response with different ammonia concentration. The solid line is the linear fit. Error bars
40
41 obscured by data points.
42
43
44 Figure 3. Effect of different parameters on sensing performance (a) Current and (b) sensor
45
46 response with double loading of Au nanocrystals; (c) Stability plot of the sensor for a period of 6
47
48 months.(d) sensor response G/Go of ammonia under different natural humidity (%RH). Vertical
49
50 error bars represent the standard deviation from the mean.
51
52 Figure 4 Ammonia sensing at different environment. (a) The temporal ammonia response of 1
53
54 ppm in different environments (ambient, nitrogen and oxygen). (b) oxygen adsorption occurs on
55
56 sensor surface and (c) introduction of ammonia removes adsorbed oxygen.
57
58
59
60 15
ACS Paragon Plus Environment
 ACS Sensors Page 16 of 26

1
2
3
Figure 5 Characterization of sensor- before and after ammonia exposure (a) FTIR spectra of
4
5 sensing film (a1) before and (a2) after ammonia sensing experiment; (b) TEM image of sensing
6
7 film; (c) Image of optical profilometer of the sensor film taken before and ; (d) after ammonia
8
9 sensing experiment.
10
11
12 Figure 6 Selectivity of sensing film. (a) selectivity response of the sensor towards different
13
14 analytes in their pure form; (b)The sensor towards different sulphide analytes at 50 ppm.
15
16
17
18
Figure 7 Measurement of BUN and urea in blood serum. (a) Urea and (b) BUN obtained from
19 the serum samples of 6-72 years old patients by using our sensor. A* represents for a diabetic
20
21 patient with renal disorder and B* represents for another diabetic patient with renal disorder and
22
23 peptic ulcer. Comparison of the measured value of (c) urea and (d) BUN concentrations with the
24
25 clinical tested values. Error bars obscured by data points.
26
27
28 Table 1: Summarize results of chemiresistive ammonia sensors.
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 16
ACS Paragon Plus Environment
Page 17 of 26 ACS Sensors

1
2
3
4
5
6
7
8
a b
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 d 15
1 ppq
24
25
c Current (A)
1 ppt
1ppb
26 10 1ppm
27
28
29 5
30
31
32 0
33 0 10 20
34 Voltage (V)
35
36
37
38
39
40 Figure.1
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 17
ACS Paragon Plus Environment
 ACS Sensors Page 18 of 26

1
2
3
4
5
6
7
8
9
10
a Ag
11 Sensor
12
13
film
14
15 Glass
16
17 50 c
b baseline 120
100
18 0.1 ppq 100
3 4 5

19 40 1 ppq 2

Current (A)
Current (A)

80
1
20 100 ppq
Current (A)

60

21 1 ppt
30
40
10
22 100 ppt 20

23 1 ppb 0
0 900 1800 2700 3600

20 100 ppb Time (s)

24
1 ppm 1
25 100 ppm
26 10
27
28 0 0.1
29 0 400 800 1200 1600 1E-12 1E-8 1E-4 1 10000
30 Time (s) Ammonia concentration (ppm)
31
32
33 300
d e
34 10000
35 250
36
200
Time (s)

37 Response 1000
G/Go

38 150
39 Recovery
40 100
41 100
42 50
43
44 0 10
45 1E-12 1E-8 1E-4 1 10000 1E-12 1E-8 1E-4 1 10000
46 Ammonia concentration (ppm) Ammonia concentration (ppm)
47
48
49
50 Figure.2
51
52
53
54
55
56
57
58
59
60 18
ACS Paragon Plus Environment
Page 19 of 26 ACS Sensors

1
2
3
4
5
6
7
8
9 a 200 b 9600
10
11
12
13 180
Current(A)

14 8400

G/Go
15
16 160
17
18 7200
19 140
20
21
22 120 6000
23
24 20000 40000 60000 80000 100000 20000 40000 60000 80000 100000
25 Ammonia concentration (ppm) Ammonia concentration (ppm)
26
27
28
29 c 103 d 4300
30
% Relative G/Go

31 101
32 4200
33 99
34
G/Go

35 97 4100
36
37
95
38 4000
39
40 93
41 3900
42 91
0 50 100 150 200
43 20 30 40 50 60 70 80
44 time (days) %RH
45
46
47
48
49
50
51
52
53 Figure.3
54
55
56
57
58
59
60 19
ACS Paragon Plus Environment
 ACS Sensors Page 20 of 26

1
2
3
4
5
6 90
7 a 2 2
8 1 flow on
9
2 flow off
10
Current (A)

11 60 ammonia
12 nitrogen
13 oxygen
14 2
15 30
16 1 1 2 1 1
1
17
18
19
20 0
21 0 400 800 1200 1600
22
23
time (s)
24
25
26
27
28 b - -
29
30
O2 - O2 O - O2 - O2
2
31
32
33 NH3+O2
34
NH3
35
36
c
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51 Figure.4
52
53
54
55
56
57
58
59
60 20
ACS Paragon Plus Environment
Page 21 of 26 ACS Sensors

1
2
3
4
5
6
7
8
a 100
9
10
a1
a2
b
95
11
12 90 -1
13 1638 cm
-1 2916 cm
-1
14 3330 cm
85
15
%T

16 -1
80 1009 cm
17
18
19 75
20
21 70
-1
22 868 cm
23 65
24 800 1600 2400 3200 4000
25
26
Wavenumber (cm-1)
27
28
29 c d
30
31
32
33
34
35
36
37
38
39
40
41
42
43 10 m 10 m
44
45
46
47
48
49
50
51 Figure 5.
52
53
54
55
56
57
58
59
60 21
ACS Paragon Plus Environment
 ACS Sensors Page 22 of 26

1
2
3
4
5
6

o
a
in

fd
lie
G

/o
1
0
2
3

m
A

rp
o
a
ie
tcd M
H
g
n
su
y
0 A
n
a
1 l3yte
2 s

7
8 a 11500 b 4000

Hydrogen sulfide
Ammonia
9 Ammonia
10 11000

Mercaptoacetic acid
11 10500
12 10000 3000
13

o-xylene
14 9500

G/Go
9000
Iso propyl alcohol

15
G/Go

2000
Tetrahydrofuran
N-butyl acetate
16
Cyclohexane
Diethylether

17
Acetonitrile

18 4
Methanol
Ethanol
Acetone

19 1000
20
2
21
0
22 0
23 -2 1 2 3
24
25
Analytes Analytes
26
27
28
29
30
31
32
33
34
35
36 Figure 6.
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 22
ACS Paragon Plus Environment
Page 23 of 26 ACS Sensors

1
2
3
4
5
6
7 40
a 80
B* b
8
70 B*
9
10 60
A* 30 A*
Urea (mg/dL)

BUN (mg/dL)
11
50
12
13 40 20
14
30
15
16 20 10
17
10
18
19 0 0
20 0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
21 Age (years) Age (years)
22
23 c 60
d 30
Urea (mg/dL) BUN (mg/dL)
24
Measured value (mg/dL)
50 y = 0.821x + 0.0123
Measured value (mg/dL)

25 y = 0.821x + 0.0264
26
40 R = 0.90 R = 0.90
27 20
28
30
29
30
20 10
31
32
10
33
34
0
35 0 10 20 30 40 50 60 70 0
36 0 10 20 30
Clinical tested value (mg/dl)
37 Clinical tested value (mg/dl)
38
39
40
41
42
43
Figure.7
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 23
ACS Paragon Plus Environment
 ACS Sensors Page 24 of 26

1
2
3
4
5 Table 1
6
7 Active Sensitivity tres (s) trec (s) T Selectivity Lowest Highest
8 materials (%) (C) detection detection
9
limit limit
10
11 (ppm)
12 Carbon ~100 at 60- RT
13 nanotubes[2] 1% NH3 120
14 DTBDT-C6 98.6 5-45 4-35 Good N/A 10
15 microstripe[7] at 50 ppm
16
17 In2O3 3500 20 20 RT N/A ~5 ppm N/A
18 nanotubes[8] at 25 ppm
19 MoS2 thin 0.06 at 20 300 ppb
20 film[9] ppm
21
22 WO3 thin 5 at 15 60 300 Good N/A N/A
23 film[10] 1000 ppm
24
25 ~10 at 10 Poor 10 ppb
26 ppm
27
28 Pt/AlGaN/GaN ~2.8 15 60 300 Good 35 ppm 1000
29 Schottky-type
30 sensor[11] (100 )
31 Acrylic acid 0.98 at 60s 360s RT N/A 1 ppm 600
32 doped 600 ppm
33
34
polyaniline [12]
35 Reduce 5.5 at - - RT Poor 200 ppm 2800
36 graphene 200 ppm
37 oxide[13]
38 Ag nanowires 138 - - RT N/A 0.7% 7%
39
40
based 7% NH3
41 nanojuction[14]
42 Graphene[15] ~100 at 3600 3600 N/A 0.5 ppm N/A
43 1000 ppm
44
45
46
Pentacene 23 at 500 100- N/A 3 0.5
47 based OTFT[16] 3 ppm 200
48
49 Carbon N/A UV RT N/A ~1 ppt* 500
50 nanotube (0.0000278) irradia
51
52
network[17] tion
53 VNJ-P3HT (0.02) ~100 Flushing RT Good 5 ppb 3
54 diode [18] air
55 PTE Si 0.35 at ~480 Flushing 40 N/A 500 ppb 10
56 nanowires 1 ppm air
57
58
(porous top
59
60 24
ACS Paragon Plus Environment
Page 25 of 26 ACS Sensors

1
2
3
4
electrode silicon
5 NW)[19]
6 TiO2 fiber 0.004 at 50 ~60 Flushing RT N/A 50 ppq 2x10-4
7 coated PANI[20] ppq air
8 PANI/PE-co- ~2500% ~75 RT N/A 0.1 25
9
10
GMA (25)
11 nanofibrous
12 composite[21]
13 Polyaniline 1585 at <15 <30 1 ppm 10000
14 films doped 10000 ppm
15
with Ni[22]
16
17 Polypyrrole[23] ~2 at Poor N/A 10000
18 8000 ppm recovery
19 GG/Ag ~18 at 25 ~200 ~200 RT Excellent 500 ppt 10000
20 nanocomposite[2 ppm
21 4]
22
23 *GG/Au ~2600 at 25 200 180 RT Excellent 0.1 ppq 30000
24 nanocomposite ppm
25 (Present work)
26
27
N/A: Not discussed,
28
29 * Represents theoretical detection limit is ppq,
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 25
ACS Paragon Plus Environment
 ACS Sensors Page 26 of 26

1
2
3
4
5
6
7
8 For TOC Only
9
10
11
12
13
14
15
16 SENSOR

17
18 40 30

19 A*: Diabetic/ renal disorder

Measured value (mg/dl)

30 B*: Diabetic/renal disorder/peptic ulcer B*
BUN (mg/dl)

20
A*
20 20

10

21 10

22
0 0 10 20 30
0 10 20 30 40 50 60 70
Clinical tested value (mg/dl)
Age (years)

23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 26
ACS Paragon Plus Environment