chemical sensor dan fia

7/30/2019 Chemical Sensor Dan FIA

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Chemical Sensors dan Flow

Injection Analysis (FIA)


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Ion Selective Electrodes


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Potentiometric sensors

A large subset of electrochemical sensors

Principle: electric potential develops at the surface ofa solid material immersed in solution containing ions

that exchange at the surface. The potential is proportional to the number or

density of ions in the solution.

A potential difference between the surface of the

solid and the solution occurs because of chargeseparation at the surface.


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The contact potential, analogous to that used to set up avoltaic cell cannot be measured directly.

If a second electrode is provided, an electrochemical cell issetup and the potential across the two electrodes is directly

measurable. To ensure that the potential is measured accurately, and

therefore that the ion concentration is properly representedby the potential, it is critical that the current drawn by themeasuring instrument is as small as possible (any current is a

load on the cell and therefore reduces the measuredpotential).


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For a sensor of this type to be useful, the potentialgenerated must be ion specific that is, theelectrodes must be able to distinguish betweensolutions.

These are called ion-specific electrodes ormembranes.

The four types of membranes are:

Glass membranes, selective for H

+

, Na+

and NH4+

andsimilar ions.


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Polymer-immobilized membranes: In this type of membrane,an ion-selective agent is immobilized (trapped) in a polymermatrix. A typical polymer is PVC

Gel-immobilized enzyme membranes: the surface reaction is

between an ion specific enzyme which in turn is eitherbonded onto a solid surface or immobilized into a matrix -mostly for biomedical applications

Soluble inorganic salt membranes: either crystalline orpowdered salts pressed into a solid are used. Typical salts are

LaF3 or mixtures of salt such as Ag2S and AgCl. Theseelectrodes are selective to F, S and Cl and similar ions.


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Classification of ion-selective electrodes

A: Fundamental ISEs

A.1. Solid-state membrane (Glass & precipitate)

A.2. Liquid membrane

A.2.1. Ion-exchanger based

A.2.2. Ionophore based

B. Sensitized ISEs

B.1. Gas sensing probes

B.1.1. Permeable membrane covered

B.1.1.1. Differential gas sensorsB.1.2. Air-gap separated

B.2. Enzyme modified ISEs


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Glass membrane sensors

By far the oldest of the ion-selective electrodes,

Used for pH sensing from the mid-1930s and is ascommon as ever.

The electrode is a glass made with the addition ofsodium (Na2O) and aluminum oxide (Al2O3),

Made into a very thin tube-like membrane.

This results in a high resistance membrane which

nevertheless allows transfer of ions across it. The basic method of pH sensing is shown in Figure

8.7a.


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pH sensor


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pH sensor

Consists of the glass membrane electrode on the left and areference electrode on the right.

The reference electrode is typically an Ag/AgCl electrode ina KCl aqueous solution or a saturated Calomel electrode

(Hg/Hg2Cl2 in a KCl solution). The reference electrode is normally incorporated into the

test electrode so that the user only has to deal with asingle probe as shown in Figure 8.7b.

The sensor is used by first immersing the electrode into a

conditioning solution of Hcl (0.1.mol/liter) and thenimmersing it into the solution to be tested. The electricoutput is calibrated in pH.

A sensor of this type responds to pH from 1 to 14.


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pH probe with reference electrode


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Glass membrane sensors

Modifications of the basic configuration, both in

terms of the reference electrode (filling) as well as

the constituents of the glass membrane lead to

sensitivity to other types of ions as well as to sensorscapable of sensing dissolved gas in solutions,

particularly ammonia but also CO2, SO2, HF, H2S and

HCN


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Soluble inorganic salt membrane

sensors

Based on soluble inorganic salts which undergo ion-exchange interaction in water and generate therequired potential at the interface.

Typical salts are the lanthanum fluoride (LaF3) andsilver sulfide (Ag2S).

The membrane may be either

a singe crystal membrane,

a sintered disk made of powdered salt a polymer matrix embedding the powdered salt

each has its own application and properties


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sensors

The structure of a commercial sensor used to sensefluoride concentration in water is shown next

The sensing membrane, made in the form of a thin

disk grown as a single crystal. The reference electrode is created in the internal

solution (in the case: NaF/NaCl at 0.1 mol/liter).

The sensor shown can detect concentrations of

fluoride in water between 0.1 and 2000 mg/l. This sensor is commonly used to monitor fluoride in

drinking water (about 1mg/l).


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sensors for fluoride


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sensors

Membranes may be made of other materials such assilver sulfide.

The latter is easily made into thin sintered disks frompowdered material and may be used in lieu of the

single crystal. Other compounds may be added to affect the

properties of the membrane and hence sensitivitiesto other ions.

This leads to selective sensors sensitive to ions ofchlorine, cadmium, lead and copper and are oftenused to sense for dissolved heavy metals in water.


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Polymeric salt membranes

Polymeric membranes are made by use of apolymeric binder for the powdered salt

About 50% salt and 50% binding material.

The common binding materials are PVC,polyethylene and silicon rubber.

In terms of performance these membranes

are quite similar to sintered disks.


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Polymer-immobilized ionophore

membranes

A development of the inorganic salt membrane

Ion-selective, organic reagents are used in theproduction of the polymer by including them in theplasticizers, particularly for PVC.

A reagent, called ionophore (or ion-exchanger) isdissolved in the plasticizer (about 1% of theplasticizer).

This produces a polymer film which can then be usedas the membrane replacing the crystal or disk insensors.


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membranes

The construction of thesensor is simple

Shown in Figure 8.9 andincludes an Ag/AgClreference electrode.

The resulting sensor is a

fairly high resistance sensor.


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membranes

A different approach to buildingpolymer-immobilized ionophoremembranes is shown in Figure 8.10.

It is made of an inner platinum wire onwhich the polymer membrane is coated

The wire is protected with a coating ofparaffin.

This is called a coated wire electrode. To be useful a reference membrane

must be added.


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Membrane Solution

Cation (p)

Anion(Permselective)

Cation (i)

(ionselective)Regulated by the

selectivity coefficient

R-

(TTFMPB)

M+

N+

M+

time

i0

iM+

Current

density

iM+

Q

Ion-exchanger

based membranesCF

3CF3

B

CF3

CF3

CF3

CF3

CF3

CF3

tetrakis[3,5-

bis(trifluoromethyl)phenyl]borat

e (TTFMPB)

+

+

aq

N - +

org

Nk =

R N

+

+

aq

M - +

org

Mk =

R M

i0

iN+

iN+


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Dissociated cation exchanger

R+>Cs+>Rb+> K+>Na+>Li+

Dissociated anion exchanger:

ClO4-> SCN

-> I

-> Sal

-> NO3

-> Br

-> Cl

-> HCO3

-> OAc

-> SO4

->HPO4

2-

B

-

K+

N

+

+

+

+ +

- + +

aqorg- + + - + + Maq aq ionexch.org org - + +

Naqorg

+ +

aq aq

M N- + - +

org org

R N M kR M + N = R N + M K = =

kR M N

M Nk = k =

R M R N

CF3

CF3

B

CF3

CF3

CF3

CF3

CF3

CF3

Hofmeister selectivity sequence

pz


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Membrane Solution

Cation (p)

Anion

Cation (i)Regulated by the


R- M+

N+

B

M+

)aKaln(Fz

RTEE i

p

z

i

pot

i,pp

p

0

p

+

+

+ +

- + +

aqorg- + + - + + Maq aq ionexch.org org - + +

Naqorg

+ +

aq aq

M N- + - +

org org

R N M kR M + N = R N + M K = =

kR M N

M Nk = k =

R M R N

logKM+,N+

pot

logKionexch.

-4 -2 0 2 4

4

2

0

-2

-4 Li+

Na+

K+

(CH3)4N+

(C

2

H

5

)

4

N+

Hofmeister selectivity sequence


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Membrane Solution

Cation (p)

Anion

Cation (i)

Regulated by the


Ca2+

Mg2+

2

2

2

2

+

+

aq

Ca

org

org org org

org org

Cak =

CaDDP

Ca DDP CaDDP

CaDDPK

Ca DDP

2

2

2

2

+

+

aq

Mg

org

org org org

org org

Mgk =

MgDDP

Mg DDP MgDDP

MgDDPK

Mg DDP

Deviations from

Hofmeister selectivity

sequence

ASSOCIATION WITHTHE ION-

EXCHANGER

O

PO

O

O

Ionophore / ion-exchanger

Ca-DDP

O

PO

O DOPP

Plasticizer for Ca

selectivity

complete

association (org)

Decanol

OH

Plasticizer for divalent (Ca2++Mg2+)

selectivity complete dissociation

pot -4 pot

Ca,Mg Ca,Mg K 10 (DOPP) K 1 (Decanol)

aqjpot JS

i, j aqi IS

k K

K = f ;k K


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Membrane Solution

Ionophore-Cation (p)

ionophore

+

Cation (p)

Cation (p)

Anion

Cation (i)

R-

M+

N+

K+

K+

B

Regulated by the



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Ionophore based, mobile site

ion-selective membrane:

PVC (33%) (PVC-COOH, PVC-OH, PVC-NH2, silicone rubber, poly-urethane,methacrylate polymers)

Plasticizer (66%) (phtalate esters, sebacate esters,o-NPOE, adipic acidesters)

1% Ionophore (chromoionophore)

50% (mol) Lipophilic ion additive(NaTPB, KTpClPB,KTbTFMPB)

CF3

CF3

B

CF3

CF3

CF3 CF3

CF3

CF3

K+

B Na+B Cl

Cl

Cl

Cl

K+

Cl Cl Cl


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N

O N

O

N

CF3

CF3

B

CF3

CF3

CF3

CF3

CF3

CF3

K+

PVC (33 %)

Plasticizer: DOS (66 %)

Ionophore (1%)

Lipophilic Anion (< 1% )(10-90 mol % with respect of the ionophore)

O

O

O

O

H+ selective chromoionophore ETH 5294K+ selective ionophore valinomycin

NO2

O

Cl Cl Cl

n


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Potential difference

A-

Ionophore

complex

M+ Primary cation

ionophore

Anion

R-Lipohylic

additive

200 m

M+

M+

M+

M+

M+

M+

A-

A

-

A-

A

-

A-

M+

A-

A-A

-

A-

A-R- R

-

R-R-

N+

N+

N+N+

N+

N+N+ Interfering cation

M+M+

M+

M+

M+

d dd

membrane

R-

R-=

M+

M+ M+

M+

M+A-

A-

A-

0 logaq

org

aS

a

( )

( )

logaq rigt

M right left

aq left

aS

a


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Potassium ionophores


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Calcium ionophores

Hydrogen ionophores


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Fig. 13.14. 14-Crown-4 ether that selectively binds lithium ion.

The crown ether cavity size is just right for complexing lithium ion.

It is placed in a PVC plastic membrane.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)


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Fig. 13.15. Ionophores for H+, Na+, and Ca2+.

Amide-based ionophores in PVC membranes are good complexers of these ions.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)


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Typical ISE Calibration GraphNB: X-axis units are the logarithm of the Molar Activity of the Ion


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NewHg2+

-selective Chromo-andFluoroionophore Based upon

8-Hydroxyquinoline

So Yun Moon and Suk-Kyu Chang

Department of ChemistryChung-Ang University


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Introduction

Binding Site

N

OH

NB

N

F F

Signaling Unit

Selectivity :

Transition and

Heavy Metal

Ions

High Quantum Yield

Longer Wavelength

Narrow Absorption Band

New Ionophore Having

Hg2+-selective

Chromogenicand

Fluorogenic

Signaling Behavior

+


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Synthesis of Ionophore 1

N CHO

OH

N

OHN

B

N

F

F

i), ii), iii)

i) 2,4-Dimethylpyrrole, ii) chloranil, iii) NEt3, BF3-OEt2

1


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0

0.5

1

1.5

2

350 450 550 650Wavelength (nm)

Abso

rbance

Cu2+

Hg2+

Zn2+

Host only

UV Absorption Spectra of 1 in dioxane-

H2O (1 : 3, v/v) with various metal ions.

[1] = 1 x 10-4 M, [M2+] = 1 x 10-2 M

Color changes in 1 upon the

complexation with Hg2+ ion.

[1] = 1 x 10-4 M, [M2+] = 1 x 10-2 M

No metal

ion Hg

2+ Pb2+

Hg2+-selective Chromogenic Behavior of 1


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0

0.5

1

1.5

2

350 450 550 650

Wavelength (nm)

Absorb

ance

UV Absorption Spectraof 1 UponAddition of

Increasing Amount of Hg2+ in the Presence of

Physiological Background Metal Ions

Figure 3.UV Absorption Spectra of 1

in dioxane-H2O (1 : 3, v/v) . [1] = 1 x 10-4 M,

Equiv.

0.0

0.51.0

2.0

3.0

4.0

5.0

50


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Hg2+-selective Fluorogenic Behavior of 1

0

1

2

3

4

5

6

490 540 590 640Wavelength (nm)

Fluorescence

Intensity(a.u.)

Hg2+

Cu

2+

1 only

Pb2+

Zn2+

, Ni2+

No metal

ionHg2+

Pb

2+

Fluorescence spectra of 1 in dioxane-

H2O (1 : 3, v/v) with various metal ions.

[1] = 5 x 10-5 M, [M2+] = 5 x 10-4 M

Fluorescent change of 1 upon the

complexation with Hg2+ ion.

[1] = 5 x 10-5 M, [M2+] = 5 x 10-4 M


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Fluorescence Spectra of 1 Upon Addition ofIncreasing

Amount of Hg2+ in the Presence of Physiological

Background Metal Ions

0

2

4

6

8

490 540 590 640

Wavelength (nm)

FluorescenceIntensity

(a.u.)

Equiv.

0.0

0.2

5

0.5

0.6

0.71.0

1.2

2.0

5.0

50

Ion

mM

Na

138

Mg1

Ca

3

K

Metal Ions

in blood

Fluorescence Spectra of 1 in dioxane-H2O

(1 : 3, v/v) . [1] = 5 x 10-5 M,


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Conclusion

1. New Hg2+-selectiveFluorogenic sensor was synthesized by

conjugating 8-Hydroxyquinoline with BODIPY function.

2. Remarkable Hg2+-selective Fluorescence Quenching

(ON-OFF type switching effect).

3. Also exhibited a Hg2+-Selective Chromogenic Behavior:

No metal ions : Yellow, Hg2+ : Red, Cu2+ : Light Reddish

Yellow.

4. Selectivity : Hg2+

>> Cu2+

> Pb2+

Ni2+

Zn2+

Ca2+

.5. It can be used as a new ion sensor for the detection of toxic

Hg2+ in a variety of chemical and biological systems.


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Novel Hg

2+

-selective PyrenylacetamideIonophore Derived from

p-tert-Butylcalix[4]arene-diaza-crown Ether

Ju Hee Kim and Suk-Kyu Chang

Department of Chemistry

Chung-Ang University


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Introduction

Fluorescence-ON

Fluorescence-OFF

Monomer Emission (< 20% Water)

Excimer Emission ( 50% Water)

ExcimerON Excimer OFF

Hg2+N

O

N

O

Pyrene Moiety

Hg2+


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Design and Synthesis of Ionophore from

p-tert-Butylcalix[4]arene-aza-crown Ether

K2CO3, KI, CH3CN

NH

OCl

OHO O

But

But

N N

HO

But Bu

t

N

O

HN

O

H

2 45%

OHO O

But

But

NH HN

HO

But Bu

t

1


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0

1

2

3

4

5

6

7

350 400 450 500 550 600

Monomer and Excimer Fluorescence Spectra of

Calix-aza-crown Pyrenylacetamide 2

MonomerExcimer

Fluorescence spectra of 2 in various solvent system.

[Ligand] = 1 x 10-5 M, MeOH : H2O (v/v) = 8:2 (),9:1 (), 10:0 (), 5:5 (), 4:6 (), 1:9 ().

Fluorescenceint

ensity(a.u.)

Wavelenghth (nm)

0

1

2

3

4

5

6

7

8

0 20 40 60 80 100

Ratio of H2O (%)

The changes of intensity ratios

(I474/I385) as a function of H2O

composition.


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Changes in Monomer Emission Intensity of2

Mg Ni Hg Cu Co Cd Ca Zn

100% MeOH

90% MeOH

80% MeOH

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

FluorescenceIntensityChange((I0-I)/I0

)

The effects of H2O/MeOH composition on the

selectivity toward representative transition and

heavy metal ions. [2] = 1 x 10-5 M, [M2+] =1 x 10-3

M


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Fluorescence Titration of 2 with Hg2+ Ions

in the Presence of Background Metal Ions

0

1

2

3

4

5

6

300 350 400 450 500 550

In MeOH/H2O (9 : 1, v/v) [2] = 1 x 10-5 M : (); 2 only, ();

2 in the presence of background metal ions ():3, (): 10,():15, and (): 50 equiv of Hg2+ ions.

Fluorescenceintensity(a.u.)

Wavelength (nm)


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Changes in Fluorescence Intensityof Excimer 2

with Various Metal Ions

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

zinc pb ni mg hg cu co cd ca baFluorescenceIntensityC

hange((I0-I)/I0

)

In MeOH-H2O (5 : 5, v/v). [2] = 1 x 10-5 M, [M2+]

=1 x 10-3 M


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Fluorescence Titration with Hg2+ in Physiological

Metal Ionsin Excimer Emission Region

0

1

2

3

4

5

6

350 400 450 500 550 600

Wavelength (nm)

Fluorescenceintensity(a.u.)

Fluorescence spectra of 2 in MeOH/H2O

(1 : 1, v/v) .

() : 2, () : 1, () : 5, () : 10, () : 30, () : 70,

Ion mMNa 138Mg 1Ca 3K 4Fe 0.02Zn 0.02Cu 0.015Co 0.002Ni 0

Metals in Blood


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Conclusion

1. Novel Hg2+-selectivechemosensor was synthesized by conjugating

Calix-aza-crown Ether with Pyrenylacetamide functions.

2. In 10% aq. MeOH solution: Hg2+-selective Monomer Emission

Quenching of Pyrene Moiety (ON-OFF).

3. In 50% aq. MeOH solution: Hg2+-selective Excimer Emission

Quenching (ON-OFF).

4. Selectivity : Hg2+ >> Cu2+ >Pb2+ Zn2+ Mg+ Ca2+ .

5. New ION SENSORfor the detection of toxic Hg2+Ionsin avariety of chemical and biological systems.


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HPTS- Optical pH Sensor

pH sensitive

fluorescent dye

Absorbance /Excitation changes with

pH

Emission at 520 nm

Excitation Ratiometric


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pH SENSOR ASSEMBLY FOR

OPTICAL CHEMICAL SENSOR

White microfiltration membrane backing

PEG-dye copolymer hydrogel

Transfer adhesive

Note: All Optical Chemical Sensors Are Based on

Same Concept as pH Sensor


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pH Sensor Calibration in Cell Suspension

0.0

0.5

1.0

1.5

2.0

2.5

3.0

6 6.5 7 7.5 8 8.5 9

clear buffer

e.coli/LB suspension(OD

600nm= 0.25)

IntensityRatio

pH


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Optical Sensors

Fluorescent Biosensors

Total Internal Reflection

Surface Plasmon Resonance

Interferometry


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Fluorescent biosensor design

Bissel et al. Topics in Current Chemistry, Vol. 168 , Springer Verlag (1993), pp. 223-261

The fundamental design of a fluorescent biosensorconsists of a receptor binding site and a fluorophoreconnected by a linker.

The linker provides a means for triggering a change

in the fluorescence of the attached fluorophore.

LinkerFluorophore Receptor/Binder


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Fluorescent biosensorsThe principal of operation is that there must be a

fluorescent switch. The switch is triggered bya binding event. The binding molecule can quenchfluorescence or cause a conformational change thatunquenches fluorescence. One of the most common

quenching mechanisms is electron transfer:hn

DAD1AD+A-DAhn

DAIn the scheme above the donor D acts as afluorescence quencher.


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Energy diagram for a fluorescent sensor

D 1A

Electron transfer quenching of a fluorescent


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Electron transfer quenching of a fluorescentsensor

D 1A D+ A-

Es


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Fluorescent sensors

Cooper and James SPIE (1999), 3602, 194-201

Crown ethers bind sodium with good selectivity.In the fluorescent molecule shown below the bindingof sodium results in fluorescence quenching.

Boronic ester based biosensors:


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Boronic ester-based biosensors:The classical mechanism

Cooper and James SPIE (1999), 3602, 194-201

Formation of a boron-nitrogen bond can occur byformation of boronic esters. This interaction dramaticallyreduces fluorescence quenching by the amine nitrogenlone pair. The result is a switch from a non-fluorescent

to fluorescent state upon binding to a saccharide.

Novel mechanism for fluorescence triggering


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B

N

PBE-OTMA

O

O

B

N

O

O

+ H2O+

H

HO

_

PBA-OTMA

BOH

OH

N

+ H2O

BOH

OH

N

H2O

Hydrolysis Less Favored

Hydrolysis Strongly Favored

Novel mechanism for fluorescence triggering

In aprotic solvents (DMSO, CH3CN, CHCl3),


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fluorescence of the ester is lower than that of the acid

0

50

100

150

200

250

300

350

400

380 400 420 440 460 480 500

nm

I

0 mM

5.71 mM

Fluorescence profile of acid in anhydrous DMSO decreased with the addition ofcis-1, 2-

cyclopentane diol

N

B

OH

HO

Addition of water increase the fluorescence


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intensity

H+

N

B-

O

O

OHDMSO and Water

A H d l i M h i f Fl t St t S it hi


66/100

A Hydrolysis Mechanism for Fluorescent State Switching

NH

HO

+N

B

OH

HOB

O

O

Weakly fluorescent

light

Strongly fluorescent

Diol

(Saccharide)

-

Franzen, Ni and Wang J. Phys. Chem. 2003, 107, 12942


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Implantable glucose sensor

Detector

Laser diodeFluorescentmolecules

Power supply and transmitter

SMSI, Inc.


68/100


Detector

Laser diodeFluorescentmolecules


SMSI, Inc.


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Detector

Laser diodeGlucose quenchesfluorescence


SMSI, Inc.

Cell Surface Target Molecules


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Cell Surface Target Molecules

OHO

OO

O

O

O

O

NHAc

OH

Me

HOOH

OH

CH2OH

Me

HO

OH

HOOH

OH

OHO

OO

O

OH

O

NHAc

OH

Me

HOOH

OH

OHHO

OH

NHAc

OH

OO

OHO

OOH

Me

HOOH

O

OH

OHHO

OO

COOHOH

AcNH

OH

OH

OHNHAc

OH

O O OH

OO

OH

OHHO

O

OOH

Me

HOOH

O

COOH

OH

AcNH

OH

OH

OH

Lewis Y tetrasaccharide

Lewis X trisaccharide

sialy Lewis X tetrasaccharidesialy Lewis a tetrasaccharide

The Approach


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The Approach

OHOH OH OH

B B

HO OH HO OH

Carbohydrate

Receptor, nonfluorescentor weakly fluorescent

OO O O

B

B

Carbohydrate-

receptor complexStrongly fluorescent

- 2 H2O

Bidentate design


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Bidentate design

Computer-aided design can be used to generatestructures that have the appropriate geometry. A recentexample is shown above for sensing of pyranose.

He and Druekhammer, Angew. Chem. 2001, 40, 1714

Some Synthesized Diboronic Acids


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y

12a

compounds

-(CH2)10-

12b

12c OO

12d

12e -(CH2)3-

12f

12h -(CH2)2-

12i -(CH2)6-

12j -(CH2)20-

12k

12l O

12m -(CH2)12-

12n

12o

12p -(CH2)5-

12q

12g

compoundsLINKER LINKER

12r O

12s

12t

12u

12v

12w

12x

12y

12z

S

N

-(CH2)14-

-(CH2)4-

compounds LINKER

Fluorescent Cell Targeting Assay


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5 M Boronic Acid Targeting Molecule

Fluorescent Cell Targeting AssaySialyl Lewis X Sialyl Lewis Y Control

12q

12a


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Synthesis Cation Sensing Material

0.05g, 0.32mmol

2.00g, PS latex

Ion exchange resin,

solvent

0.10g, 1.4mmol

Parafilm

spacer, 125

um

Quartz disk

1. CCA Self-assemble

diffraction film

2. PCCA

365 nm

90 min3. Hydrolyzed

PCCA

0.15g, 0.64mmol

0.20g, 1.04mmol


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Results and DiscussionCu2+ sensor

757 nm


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Results and DiscussionProposed Mechanism of Sensing Cu

2+

Cu2+

Low concentration- Cu2+

+ Cu2+

Cu(hydroxyquinolate)2

Log (Kf) = 21.87

Shrink blue shrift

bisligand

Cu(hydroxyquinolate)

Log (Kf) = 10.70

Breaking crosslonk red shrift

monoligand


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Results and DiscussionFormation of the liganded complexes

5-acetamido-8-hydroxyquinoline in acetate-buffered

saline

8-hydroxyquinoline-functionalized

CCA-free hydrogel

380

250-270

Other result: AA shows NO Cu2+ is retained by PCCA w/o 8-


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Results and DiscussionDiffraction wavelength vs. concentration

S = Cu2+ mol/ 2 ligandmol

Outmost layer effect

1

M


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Results and Discussion

5-acetamido-8-hydroxyquinoline colloid-free 8-hydroxyquinoline-

containing hydrogel

Cu2+ stoichiometryA= cl

1.86E04

1.82E04

2.80E03

1.05E03


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Results and DiscussionWash effect

Retention of bisligand Cu2+

sites after extensive washing

with pH 4.2 buffered salineLigand only hrdrogel50 mM Cu2+ treatedn hydrogel

Washed hydrogel

Dosimeter for ultratrace concentration of Cu2+


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Results and DiscussionSense > 1M Cu2+

Response of washed Cu2+cross-linked 8-hydroxyquinoline PCCACS

Two runs showing reproducible and

reversible nature of the sensor response

to Cu2+

Reversible sensor for > 1M Cu2+

cross-

linked


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Results and DiscussionNonspecific metal cation sensor

K1=109.57

K3=1018.27

K1=1010.70

K3=1021.87

Cu2+ Ni2+


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Results and DiscussionNonspecific metal cation sensor

Co2+ Zn2+

air

N2

N2 : K1=108.11

K3 =1015.05 Oxidation Co

2+ Co3+K1=10

8.65

K3=1016.15


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ConclusionsNovel sensing material is formed to evaluatemetal concentrations in drinking water.Metal cation concentrations can bedetermined visually from the color of thediffracted light or detected by reflectancemeasurements using a spectrophotometer.


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Conclusions

At low metal concentrationsbisligand

complexes form crosslink the gelshrink

blue shift observed

At higher metal concentrationsmonoligand

complexes formcross-links break red shift

observed


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ConclusionsAt trace concentration (10-21 M), used asdosimeters; at low concentration (> 1M),used as reversible sensorDetects metal cations such as Cu2+,Ni2+,Co2+, Co3+, Ca2+, Zn2+ AND other cationsuch as Th4+,Sm3+, Fe3+, Gd3+, and Er3+which has similar 8-hydroxyquinolineassociation constants


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Design and Synthesis of NovelQuinoline-based Contrast

Agents for Diagnostic Imaging

Kendra D. Salter and Mark D. Kernen

Department of ChemistryThe University of Tennessee at Martin

Design and Synthesis of Novel Quinoline-based ContrastAgents for Diagnostic Imaging


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Developments in lanthanide coordination chemistry: Smart CA platforms

Compounds such as the gadolinium tetraamide complex above ha

to be effective at catalyzing the rate of relaxation of bulk water prin their hydration spheres, making them excellent MRI contrast a

when given in doses of 2 to 3 g per patient.

Dual sensing smart probes for specific analytes that allow for b

luminescent and MR ima in use of Eu Tb and Gd can serve to



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Tissue imaging has

been performed using

lanthanide complexes

alone or in conjunction with

selective dyes.

Pandya, S; Yu, J. and Parker, D. Dalton Trans. 2006, 2757.

Eu-complex RNA-select dye co-lo



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Design principles: Luminescent lanthanide sensors and sensitized em

Complex without target analyte

In the presence of analyte, coordination

sphere and energy transfer changes

result in significant changes in either the

optical signal (or MRI signal, depending on the

lanthanide chosen).



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Developments in luminescent lanthanide complexes: Next-generation sensor platforms

The DO3A cyclen is frequently applied in

the synthesis of lanthanide complexes,and has a history of use in early and modern

MRI contrast agents.

Similarly, the DO3AM triamide can also be

employed as a complexing platform.



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Our work on lanthanide complexes: quinoline-cyclen dual sensor syn

O-substituted quinoline linker syntheses:



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Our work on lanthanide complexes: quinoline-based dual-mode CA sy

Coupling to cyclen and completion of the complex:



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Our work on lanthanide complexes: quinoline-based dual sensor synt

Coupling to cyclen and completion of the complex:


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Flow Injection Analysis

Flow Injection Analysis (FIA)

I FIA l i i j t d i t i li id t t hi h i t b


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In FIA, a sample is injected into a moving liquid stream to which various reagents can be

added. After suitable time, the reacted sample reaches a spectrophotometric cell detector.


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(Left) Schematic diagram of FIA, showing two different reagent addition schemes.

(Right) FIA system with enlarged view of chemistry section.


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A dialysis flow module.

The membrane is supported

between two grooved Teflon

blocks.

FIA apparatus for the determination of caffeine

in acetylsalicylic acid preparation.


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FIA of ppb levels of H O in air

chemical sensor dan fia

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