Citterio, Daniel



Faculty of Science and Technology, Department of Applied Chemistry (Yagami)



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Career 【 Display / hide

  • 2002.11

    Swiss Federal Institute of Technology Zurich (ETHZ), Switzerland, Centre for Chemical Sensors, Senior Research Scientist

  • 2005.02

    Ciba Specialty Chemicals Inc., Basel (Switzerland), Scientific Information Department, Patent Attorney

  • 2006.03

    Keio University Faculty of Science and Technology, Graduate School of Science and Technology, Special Research Associate Professor

  • 2007.04

    Keio University Faculty of Science and Technology, Department of Applied Chemistry, Associate Professor (non-tenured)

  • 2009.04

    Keio University Faculty of Science and Technology, Department of Applied Chemistry, Associate Professor

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Research Areas 【 Display / hide

  • Analytical chemistry

Research Keywords 【 Display / hide

  • biosensors

  • chemical sensors

  • functional dyes

  • functional materials


Books 【 Display / hide

  • Applications of Microfluidic Systems in Biology and Medicine

    Yamada Kentaro, Citterio Daniel, Springer, Singapore, 2019.04

    Scope: Paper-Based Microfluidics for Point-of-Care Medical Diagnostics / 353-382

  • Materials for Chemical Sensing

    Citterio Daniel, Springer, 2017

    Scope: (Bio)Chemical Sensors Based on Paper / 29-74

  • Design of Polymeric Platforms for Selective Biorecognition

    Citterio Daniel, Springer, 2015

    Scope: Inkjet Printing of Biomolecules for Biorecognition / 197-235

Papers 【 Display / hide

  • Biothiol-activatable bioluminescent coelenterazine derivative for molecular imaging in vitro and in vivo

    Nomura N., Nishihara R., Nakajima T., Kim S., Iwasawa N., Hiruta Y., Nishiyama S., Sato M., Citterio D., Suzuki K.

    Analytical Chemistry (Analytical Chemistry)  91 ( 15 ) 9546 - 9553 2019.08

    ISSN  00032700

     View Summary

    © 2019 American Chemical Society. There is a high demand for sensitive biothiol probes targeting cysteine, glutathione, and homocysteine. These biothiols are known as playing essential roles to maintain homeostasis and work as indicators of many diseases. This work presents a bioluminescent probe (named AMCM) to detect biothiols in live mammalian cells and in vivo with a limit of detection of 0.11 μM for cysteine in solution and high selectivity for biothiols, making it suitable for real-time biothiol detection in biological systems. Upon application to live cells, AMCM showed low cytotoxicity and sensitively reported bioluminescence in response to changes of biothiol levels. Furthermore, a bioluminescence resonance energy transfer system consisting of AMCM combined with the near-infrared fluorescent protein iRFP713 was applied to in vivo imaging, with emitted tissue-permeable luminescence in living mice. In summary, this work demonstrates that AMCM is of high practical value for the detection of biothiols in living cells and for deep tissue imaging in living animals.

  • Disposable electrochemical biosensor based on surface-modified screen-printed electrodes for organophosphorus pesticide analysis

    Hua Q., Ruecha N., Hiruta Y., Citterio D.

    Analytical Methods (Analytical Methods)  11 ( 27 ) 3439 - 3445 2019.07

    ISSN  17599660

     View Summary

    © 2019 The Royal Society of Chemistry. A disposable enzymatic electrochemical biosensor for amperometric organophosphorus pesticide determination based on a screen-printed carbon electrode (SPCE) platform was successfully developed. The working electrode consists of acetylcholine esterase (AChE) immobilized onto the surface of multi-walled carbon nanotube (MWCNT), chitosan (CS) and gold nanoparticle (AuNP)-modified SPCE. Ferricyanide was used as a redox mediator in solution. Two linear dynamic response ranges from 0.01 to 10 μg L-1 and from 10 to 100 μg L-1 were found for paraoxon-ethyl, with a detection limit of 0.03 μg L-1 (calculated as the amount of pesticide resulting in 10% of enzyme inhibition). High sensitivity was achieved due to a synergistic effect of AuNPs and MWCNTs deposited on the SPCE surface. Moreover, 83% of enzyme activity was retained after a dry storage period of 49 days (4 °C). Finally, the results of the electrochemical biosensor for paraoxon-ethyl-spiked spinach sample analysis showed a good agreement with those obtained from conventional HPLC.

  • Molecular imaging of retinoic acids in live cells using single-chain bioluminescence probes

    Kim S., Fujii R., Nishihara R., Bose R., Citterio D., Suzuki K., Massoud T., Paulmurugan R.

    ACS Combinatorial Science (ACS Combinatorial Science)  21 ( 6 ) 473 - 481 2019.06

    ISSN  21568952

     View Summary

    © 2019 American Chemical Society. Retinoic acid (RA) is a key metabolite necessary for embryonic development and differentiation in vertebrates. We demonstrate the utility of genetically encoded, ligand-activatable single-chain bioluminescence probes for detecting RAs from different biological sources. We examined 13 different molecular designs to identify an efficient single-chain probe that can quantify RA with significant sensitivity. The optimal probe consisted of four components: the N- and C-terminal fragments of artificial luciferase variant-16 (ALuc16), the ligand binding domain of retinoic acid receptor α (RARα LBD), and an LXXLL interaction motif. This probe showed a 5.2-fold greater bioluminescence intensity in response to RA when compared to the vehicle control in live mammalian cells. The probe was highly selective to all-trans-RA (at-RA), and highly sensitive in determining at-RA levels in cells derived from tumor xenografts created using MDA-MB-231 cells engineered to stably express the probe. We also detected RA levels in serum and cerebrospinal fluid. Using this probe, the detection limit for at-RA was 10-9.5 M, with a linear range of two orders. We present a highly useful technique to quantitatively image endogenous at-RA levels in live mammalian cells expressing novel single-chain bioluminescence probes.

  • Printed low-cost microfluidic analytical devices based on a transparent substrate

    Fujisaki S., Shibata H., Yamada K., Suzuki K., Citterio D.

    Analyst (Analyst)  144 ( 8 ) 2746 - 2754 2019.04

    ISSN  00032654

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    © 2019 The Royal Society of Chemistry. This work describes the development of a microfluidic analytical device prepared on a transparent OHP film substrate, named the microfluidic transparent film-based analytical device (μTFAD). Printing technologies including wax printing for microchannel patterning and inkjet printing for chemical assay component deposition have been employed for the μTFAD fabrication. The fully printed μTFAD allowed gravity-assisted pump-free transportation of the sample liquid (50 μL) and an absorbance measurement-based iron ion (Fe 2+ ) assay using nitroso-PSAP as the colorimetric reagent within a wax-patterned microfluidic structure. By measuring absorbance values at the Fe 2+ -nitroso-PSAP complex-specific wavelength (756 nm), a response curve with a linear range of 0-200 μM was obtained. The limit of detection (1.18 μM) obtained with the proposed μTFADs was comparable to the results achieved with a conventional 96-well microplate assay (0.92 μM) and lower than that in the case of digital colour analysis-assisted filter paper spot tests (7.71 μM) or the absorbance analysis of refractive index-matched translucent filter paper spots (37.2 μM). In addition, highly selective Fe 2+ detection has been achieved in the presence of potentially interfering metal ions (Cu 2+ , Co 2+ , Ni 2+ ) without the use of any masking reagents, owing to the selection of the target complex-specific wavelength in the absorbance measurement on μTFADs.

  • Equipment-Free Detection of K <sup>+</sup> on Microfluidic Paper-Based Analytical Devices Based on Exhaustive Replacement with Ionic Dye in Ion-selective Capillary Sensors

    Soda Y., Citterio D., Bakker E.

    ACS Sensors (ACS Sensors)  4 ( 3 ) 670 - 677 2019.03

     View Summary

    © 2019 American Chemical Society. A distance-based analysis of potassium ion (K + ) is introduced that is performed on a microfluidic paper-based analytical device (μPAD) coupled to an ion-selective capillary sensor. The concept is based on two sequential steps, the selective replacement of analyte ion with an ionic dye, and the detection of this dye in a distance-based readout on paper. To achieve the first step, the capillary sensor holds a poly(vinyl chloride) (PVC) membrane film layer plasticized by dioctyl sebacate (DOS) that contains the potassium ionophore valinomycin, a lipophilic cation-exchanger and the ionic indicator Thioflavin T (ThT) on its inner wall. Upon introduction of the sample, K + in the aqueous sample solution is quantitatively extracted into the film membrane and replaced with ThT. To convert the ion exchange signal into a distance-based analysis, this solution was dropped onto the inlet area of a μPAD to flow the ThT along a channel defined by wax printing, resulting in the electrostatic binding of ThT to the cellulose carboxylic groups. The initial amount of K + determines the amount of ThT in the aqueous solution after ion-exchange, and consequently the distance of ThT-colored area reflects the sample K + concentration. The ion exchange reaction was operated in a so-called "exhaustive sensing mode" and gave a distinct response in a narrow range of K + concentration (1-6 mM) that cannot be achieved by the classical optode sensing mode. The absence of hydrogen ions from the equilibrium competition of the capillary sensor contributed to a complete pH-independence, unlike conventional optodes that contain a pH sensitive indicator. A very high selectivity for K + over Na + and Ca 2+ has been confirmed in separate solutions and mixed solutions tests. K + measurements in pooled serum samples at concentrations between 2 and 6 mM are successfully demonstrated on a temperature controlled support.

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Papers, etc., Registered in KOARA 【 Display / hide

Reviews, Commentaries, etc. 【 Display / hide

  • Paper-based analytical devices

    Citterio D., Kaneta T.

    Analytical Sciences (Analytical Sciences)  34 ( 1 ) 5 - 6 2018

    ISSN  09106340

  • Toward Practical Application of Paper-Based Microfluidics for Medical Diagnostics: State-of-the-Art and Challenges

    Yamada Kentaro, Shibata Hiroyuki, Suzuki Koji, Citterio Daniel

    Lab on a Chip (The Royal Society of Chemistry)  17 ( 7 ) 1206 - 1249 2017.02

    Introduction and explanation (scientific journal), Joint Work,  ISSN  1473-0197

  • Paper-Based Microfluidic Devices - Towards Low-Cost and Convenient Test Chips

    Yamada, Kentaro; Citterio, Daniel

    Chemistry & Chemical Industry (2016), 69, 120-122 (The Chemical Society of Japan)  69   120 - 122 2016

    Introduction and explanation (others), Joint Work

  • Inkjet-Printed Microfluidic Paper Devices

    Ishii, Masanori; Kido, Kota; Ota, Riki; Shibata, Hiroyuki; Yamada, Kentaro; Suzuki, Koji; Citterio, Daniel

    Journal of the Imaging Society of Japan (The Imaging Society of Japan)  55   94 - 105 2016

    Introduction and explanation (others), Joint Work

  • Inkjet Printed Microfluidic Paper-Based Analytical Devices (µPADs)

    Yamada, Kentaro, Henares, Terence G., Suzuki, Koji, Citterio, Daniel

    Angewandte Chemie International Edition (Wiley)  54 ( 18 ) 5294 - 5310 2015.04

    Introduction and explanation (scientific journal), Joint Work,  ISSN  1521-3773

Presentations 【 Display / hide

  • Paper- and Thread-Based Immunoassay Devices with Colorimetric Bioluminescence Signaling

    Citterio Daniel

    Pittcon 2019 (Philadelphia, USA) , 2019.03, Oral Presentation(guest/special), The Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy

  • Capillary Flow-Driven Analytical Devices for Sample-in-Signal-Out Assaying of Clinically Relevant Analytes

    Citterio Daniel

    Flow Analysis XIV (Bangkok, Thailand) , 2018.12, Oral Presentation(key), The Chemical Society of Thailand

  • Paper-Based Analytical Device for the Detection of Antibodies in Biological Samples

    Citterio Daniel

    PERCH - CIC Congress X (Pattaya, Thailand) , 2018.07, Oral Presentation(guest/special), Department of Chemistry, Faculty of Science, Mahidol University

  • Paper-Based Devices for Antibody Detection in Whole Blood with Bioluminescent Sensing Proteins

    Citterio Daniel

    78th Discussions on Analytical Chemistry (Ube) , 2018.05, Oral Presentation(guest/special), Japan Society for Analytical Chemistry

  • Paper-Based Devices for Antibody Detection in Whole Blood with Bioluminescent Sensing Proteins

    Citterio Daniel

    Europt(r)ode 2018 (Naples, Italy) , 2018.03, Oral Presentation(general)

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Research Projects of Competitive Funds, etc. 【 Display / hide

  • Microfluidic thread-based sensor for the detection of therapeutic antibodies in blood at point-of-care


    MEXT,JSPS, Grant-in-Aid for Scientific Research, チッテリオ, ダニエル, Grant-in-Aid for Scientific Research (B), Principal Investigator


Courses Taught 【 Display / hide











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Courses Previously Taught 【 Display / hide

  • Practical English for Applied Chemistry

    Keio University, 2016, Full academic year, Major subject, Lecture, Within own faculty

  • Laboratories in Basic Chemistry

    Keio University, 2016, Autumn Semester, Major subject, Laboratory work/practical work/exercise, Within own faculty

  • Laboratories in Applied Chemistry

    Keio University, 2016, Spring Semester, Major subject, Laboratory work/practical work/exercise, Within own faculty

  • Introduction to Functional Materials

    Keio University, 2016, Spring Semester, Major subject, Lecture, Within own faculty

  • Practical Instrumental Analysis

    Keio University, 2016, Spring Semester, Major subject, Lecture, Within own faculty

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Memberships in Academic Societies 【 Display / hide

  • Chemical Society of Japan (CSJ), 

  • Japan Society for Analytical Chemistry (JSAC), 

  • American Chemical Society (ACS), 

  • Royal Society of Chemistry (RSC) (Fellow), 


Committee Experiences 【 Display / hide

  • 2017.04

    Permanent Steering Committee of Europt(r)ode, Europt(r)ode