UOA08-06: The first method of calibration-free pH measurement
Submitting Institution
University of OxfordUnit of Assessment
ChemistrySummary Impact Type
TechnologicalResearch Subject Area(s)
Chemical Sciences: Analytical Chemistry, Inorganic Chemistry, Physical Chemistry (incl. Structural)
Summary of the impact
Richard Compton's group at the University of Oxford has developed the
world's first calibration-free
pH meter, representing the first major advance in pH measurement for 80
years. In 2008, the
technology was licensed to Senova Systems Inc, who subsequently produced a
prototype hand-
held calibration-free pH meter. In September 2012 the device won the Frost
& Sullivan 2012 North
American New Product Innovation Award, and in March 2013 it won Best New
Product award at
Pittcon 2013, the world's largest annual conference and expo for
laboratory science. Following
successful field trials with end-users in diverse sectors, Senova is now
developing a commercial
product. Senova has already secured $ 9.7M to commercialise the
technology, with additional
ongoing venture capital investments. [text removed for publication].
Underpinning research
The electrochemical measurement of pH is a ubiquitous and routine tool
used in industries ranging
from pharmaceuticals to brewing. The standard apparatus for measuring pH
has not changed
significantly since it was developed by Beckman in the 1930s, and consists
of a glass electrode
connected to an electronic meter that measures and displays the pH
reading. The electrodes are
expensive and fragile, pH measurements are easily corrupted, and for
precise work the meter
needs calibration before every single measurement. Over the past eight
decades, vast amounts of
time (and therefore money) have been spent on pH meter calibration in both
academia and
industry. Incorrect calibration and other errors can also lead to huge
costs for companies in terms
of wasted supplies and products. These factors underline the pressing need
for a pH meter that
does not require calibration.
In 2001, Professor Richard Compton (Department of Chemistry, 1985 -
present) and his research
group at the University of Oxford sought to establish if it was possible
to derivatise carbon
nanotubes coated on an electrode surface in a way that made them
reproducibly and predictably
pH responsive. If his team could identify a molecule whose electrochemical
properties varied
consistently with pH, Compton believed it would be possible to create a
new breed of pH sensors.
Compton's team demonstrated that anthraquinone-derivatised carbon
(AQcarbon) nanotube
surfaces were in fact pH sensitive, accepting protons as pH conditions
changed and hence
exhibiting changing electrochemical properties. His team developed a
simple pH probe based upon
the covalent derivatisation of carbon particles with anthraquinone, and
found that its amperometric
response provided a Nernstian, linear response over the pH range 1 - 14
and over a temperature
range from 20 - 70°C [1, 2, 5].
The broad range of observed pH sensitivity using AQcarbon suggested that
an effective,
calibration-free pH sensor could be created. Compton and his team
developed electrodes which
were coated with carbon nanotubes functionalised with anthraquinone.
Alongside, they also
developed redox probes which were rigorously pH insensitive when similarly
deployed. Then, by
modifying electrodes with both pH sensitive and pH insensitive probes and
measuring the potential
difference between the two signals, it was possible to directly assess the
pH of the solution in
which the electrodes were immersed [3]. The research described in [1], [2]
and [3] was conducted
in collaboration with Schlumberger.
Compton and his team showed that the AQcarbon pH measurement technique
has distinct
advantages over existing glass electrodes. Firstly, the amperometric
signal shows a linear
relationship with the tiny currents used, which offers far higher
sensitivity than the logarithmic
voltage relationships exhibited by potentiometric glass electrodes.
Secondly, it is unaffected by
alkali errors which can corrupt the results provided by present
techniques. Thirdly (and most
importantly), because it is a potential difference that is measured, the
need for an ultra-stable
reference electrode is eliminated, in turn leading to calibration-free pH
measurement. Combined
with practical benefits — such as durability and speed — the newfound
theoretical insights provided
a promising springboard for the development of a new, revolutionary,
`disruptive' technology for pH
sensing. For these reasons, the concept was patented in 2005 by Richard
Compton and Isis
Innovation Ltd., the technology transfer arm of the University of Oxford
[4].
References to the research
Asterisked outputs denote best indicators of quality; University of
Oxford authors are underlined.
1. * Anthraquinone-derivatised carbon powder: reagentless voltammetric pH
electrodes. GG
Wildgoose, M Pandurangappa, NS Lawrence, L Jiang,
TGJ Jones and RG Compton. Talanta
60 (2003) 887-893. DOI: 10.1016/S0039-9140(03)00150-4
Reports the methodology for derivatising carbon surfaces with
anthraquinone moieties.
2. Derivatised carbon powder electrodes: reagentless pH sensors. HC
Leventis, I Streeter, GG
Wildgoose, NS Lawrence, L Jiang, TGJ Jones and RG
Compton. Talanta 63 (2004) 1039-1051.
DOI: 10.1016/j.talanta.2004.01.017
3. A sensitive reagentless pH probe with a ca 120 mV/pH unit response. I
Streeter, HC Leventis,
GG Wildgoose, M Pandurangappa, NS Lawrence, L
Jiang, TGJ Jones and RG Compton. J
Solid State Electrochem 8 (2004) 718-721. DOI: 10.1007/s10008-004-0536-7
4. * Patent WO 2005085825 A1. Electrochemical sensors. SP McCormack
and RG Compton,
Assignee: Isis Innovation Ltd, UK. https://www.google.com/patents/WO2005085825A1
The patent describes the principle of calibration-free measurement and
identifies chemical
systems for use in pH meters using such an approach.
5. *Investigating the reactive sites and the anomalously large changes in
surface pKa values of
chemically modified carbon nanotubes of different morphologies. AT
Masheter, P Abiman, GG
Wildgoose, E Wong, L Xiao, NV Rees, R
Taylor, GA Attard, R Baron, A Crossley, JH Jones
and RG Compton. J. Materials Chemistry 17 (2007) 2616-2626. DOI:
10.1039/b702492d
This paper reports the 2e, 2H+reduction of
anthraquinone-modified carbon nanotubes across
the full aqueous pH range up to 14.
Details of the impact
The calibration-free pH measurement system invented by the Compton group
is a truly innovative
technology which represents a landmark in the field of pH sensing. It has
led directly to the
commercial success of Senova Systems Inc, [text removed for publication].
In September 2008 Isis Innovation Ltd. exclusively licensed the patent
for calibration-free pH
sensing to San Francisco-based Senova Systems Inc [6]. The company was
founded in 2007 with
the sole aim of developing a commercial pH meter based on the Compton
research; Professor
Compton sits on Senova's advisory board. Based on the potential of the
technology and the high
value of the IP, Senova secured initial seed funding of $ 3M and raised a
further $ 6.7M in Series B
financing by January 2012 [7]. During the three years between licensing
and finalising funding, the
company developed a smart sensor platform capable of being produced on a
commercial scale. In
the first instance Senova designed a prototype hand-held pH sensor — the
pHit Scanner — which
offered a number of significant advantages over current standard glass
electrodes: it requires no
calibration, is temperature stable, does not suffer signal drift, can be
stored dry with no need for
electrolyte solution, can be sterilised, is physically robust and is
inexpensive to mass produce.
The scanner was previewed at Pittcon 2012, the world's largest annual
conference and expo for
laboratory science [8], and in September 2012 won the Frost & Sullivan
2012 North American New
Product Innovation Award [9]. In March 2013, the pHit Scanner was
recognized with the Pittcon
Editors' Gold Award for the best new product at Pittcon 2013 [10].
Feedback from an early adoption programme (EAP) evaluating the hand-held
meter has confirmed
the effectiveness of the technology and enabled Senova to embark on the
development of a larger-
scale meter aimed at the high-tech market, which will be more profitable
than the hand-held meter
[11]. [text removed for publication] [11]. Additional venture capital
funding (from Phoenix Venture
Partners and Harris & Harris Group Inc) for Senova is ongoing [12];
the continued investment
underlines the potential the technology has to revolutionise this field,
and the expectation that
Senova's products will be a commercial success.
As a result of the collaborative research between Oxford University and
Schlumberger described in
Section 2, Schlumberger filed a similar patent at roughly the same time as
[4]. This has led to a
mutually beneficial situation in which each party has rights on each
other's patent. [text removed for publication].
[text removed for publication][13].
Sources to corroborate the impact
-
http://senovasystems.com/press-release/oxford-university-licenses-ph-sensor-technology-senova-systems
August 2008 press release on the Senova website, confirming that the
calibration-free pH
meter is based on the Compton research and licensed to Senova.
-
http://senovasystems.com/press-release/senova-systems-closes-6-7m-series-financing
January 2012 press release on the Senova website, confirming details of
Series B investment
in Senova.
-
http://senovasystems.com/press-release/phit-ph-meter-introduction
January 2012 press release on the Senova website, confirming preview of
the pHit Scanner at
Pittcon 2012.
-
http://www.frost.com/prod/servlet/press-release.pag?docid=266584923
Frost & Sullivan webpage confirming the New Product Innovation Award
made to Senova for
its pHit Scanner.
-
http://www.pittconshowpreview-digital.com/pittconshowpreview/post201303?pg=1#pg1
Pittcon 2013 webpage corroborating the Editors' Gold Award made to Senova
Systems for its
pHit Scanner.
- Statement from the President and CEO of Senova (held on file),
corroborating details of field
trials and feedback from customers on the pHit Scanner.
-
http://senovasystems.com/about-us/investors
Senova webpage confirming Phoenix Venture Partners and Harris and Harris
Group Inc as
current venture capital investors in the company.
- [text removed for publication]