S1

Supplementary Information

A glycosylation strategy to develop low toxic naphthalimide

fluorescent probe for the detection of Fe3+ in aqueous medium

Contents list

S1. Additional figures S2. Additional SynthesisS3. Spectra of the compoundsS4. Cartesian coordinates of optimized structures

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017

S2

S1. Additional figures

Fig .S1 The absorption spectra of Nap-PZ (a), Nap-OH (b) and Nap-Glc (c) (10 μM) upon addition of 5

equiv various metal ions Ce3+, Eu3+, Ba2+, Ca2+, Cd2+, Co2+, Fe2+, Mg2+, Mn2+, Ni2+, Pb2+, Zn2+,Ag+, K+, Li+, Na+, NH4+.

Fig .S2 (a) Fluorescence changes of Nap-PZ (10 µM) in an aqueous solution upon addition of 0-10 equiv

Fe3+ with excitation at 405 nm. Inset: the color changes of Nap-PZ (10 µM) in the presence of Fe3+ (5

equiv) under UV light of 365 nm. (b) Plots of fluorescence intensity as a function of Fe3+ concentrations.

Fig.S3 Fluorescence changes of Nap-OH (10 µM) with 0-5 equiv Fe3+. Inset: the color changes of the Nap-

OH solution in the presence of 5 equiv Fe3+ under UV light of 365 nm. (b) Plots of fluorescence intensity

as a function of Fe3+ concentrations from 0– 20 µM.

S3

Fig.S4 Fluorescence intensity change of Nap-Glc (10 M) before and after addition of Fe3+ in different pH,

slit width: 1.5 3 nm.

Fig.S5 ESI-MS spectrum of Nap-Glc-Fe3+

S4

Nap-Glc

Nap-Glc-Fe3+

Fig.S6 Optimized structure of Nap-Glc and Nap-Glc-Fe3+

LUMO

HOMO

-2.611 ev

HOMO-2-6.318 ev

-5.216 ev

PET

PET "ON"Fluorescence "OFF"

LUMO-2.308 ev

-5.772 ev

S0-S1f =0.3326

HOMO

-6.879 evHOMO-2

S1-S0f =0.0000

CT

S0-S5f =0.0491

CT

Figure S7 Excitation energies of frontier molecular orbitals of Nap-Glc obtained from TD-DFT calculations

with the optimized geometries of ground state.

S5

Table S1 Selected Vertical excitation energies (Eex) and corresponding Oscillator Strengths(f), the main

configurations, and the CI coefficients of the low-lying electronic excited states of Nap-Glc obtained from

TD-DFT calculation on the optimized Ground state geometries with PCM solvation model.

Expa.Nap-Glc

λ(nm) /Eex(ev) f Configuration (%)

S0-S1 409.43/3.03 0.3326 HOMO→LUMO 97 405

S0-S5 304.56/4.07 0.0491 HOMO-2→LUMO 68

S0-S10 272.46/4.55 0.1588 HOMO→LUMO +1 42

HOMO→LUMO +2 45

a: Experiment result (Exp.)

Table S2 Selected Vertical excitation energies (Eex) and corresponding Oscillator Strengths (f), the main

configurations, and the CI coefficients of the low-lying electronic excited states of Nap-Glc-Fe3+ obtained

from TD-DFT calculation on the optimized Ground state geometries with PCM solvation model.

Expa.Nap-Glc-

Fe3+

λ(nm) /Eex(ev) f Configuration (%)

S0-S11 376.80/3.29 0.0130 α-HOMO-2→α-LUMO 34 385

α-HOMO-1→α-LUMO -33

α-HOMO→α-LUMO -11

a: Experiment result (Exp.)

Table S3 Selected Vertical emission energies (Eem) and corresponding Oscillator Strengths (f), the main

configurations, and the CI coefficients of the low-lying electronic excited states of Nap-Glc obtained from

TD-DFT calculation on the optimized ground state geometries with PCM solvation model.

Nap-Glcλ(nm) /Eem(ev) f Configuration (%)

S1-S0 678.68/1.83 0.0000 LUMO→HOMO 99

S3-S0 378.52/3.28 0.4579 LUMO→HOMO -2 99

S2.Additional SynthesisSynthesis of compound 3

Propargylamine (1.16 mL, 18.16 mmol) was dissolved in 8 mL of dichloromethane, then cold to

−10℃, 8 mL of saturated aqueous sodium bicarbonate (NaHCO3) was added. The mixture was vigorously

stirred and bromoacetyl bromide (1.9 mL, 21.79 mmol) was slowly added. The reaction mixture was

slowly allowed to warm to room temperature (RT). After 3 h the reaction mixture was separated. The

organic layer was dried by sodium sulfate (Na2SO4) and the solvent was removed under reduced

pressure to afford a brown solid (1.4 g, yield: 43.81%).1H NMR (600 MHz, CDCl3) δ 4.11 (dd, J = 5.3, 2.6 Hz,

2H), 3.93 (s, 2H), 2.31 (t, J = 2.6 Hz, 1H). 13C NMR (151 MHz, CDCl3) δ 165.58, 78.44, 72.33, 30.03, 28.61.

S6

Synthesis of compound 5

A mixture of 2-bromoethanol (0.5 g, 4 mmol) and sodium azide (0.39 g, 6 mmol) in 5 mL water was

refluxed for 24 h, and then cooled to room temperature. The solution was extracted with CH2Cl2 and the

organic layer was dried with sodium sulfate, and then filtered. After the removal of the solvent under

vacuum, compound 5 was obtained as a crude pale yellow liquid (0.32 g, yield: 91.84%), which was used

in the next step directly. 1H NMR (600 MHz, CDCl3) δ 3.84 – 3.67 (m, 1H), 3.48 – 3.34 (m, 1H), 2.46 (s, 0H). 13C NMR (151 MHz, CDCl3) δ 61.47, 53.53.

Synthesis of compound 6

The compound 6was synthesized according to the reference1, showed in the Scheme S1. 1H NMR

(600 MHz, CD3OD) δ 4.60 (s, 1H), 4.52 (d, J = 8.7 Hz, 1H), 3.90 (dd, J = 12.1, 2.0 Hz, 1H), 3.71 (dd, J = 12.1,

5.6 Hz, 1H). 13C NMR (151 MHz, MeOD) δ 90.59, 78.66, 76.63, 73.37, 69.70, 61.12.

(1) Ac2O, HClO4

(2) P, Br, H2O

OAcOAcO N3

OAc

OAc

7

OHOHO N3

OH

OH

OHOHO

OH

OH

OH

OHOHO

OHBr

OH

6

MeONaNaN3DMSO MeOH

Scheme S1 Synthetic route of compound 6

References1. V. Percec, P. Leowanawat, H. J. Sun, O. Kulikov, C. D. Nusbaum, T. M. Tran, A. Bertin, D. A.

Wilson, M. Peterca, S. Zhang, N. P. Kamat, K. Vargo, D. Moock, E. D. Johnston, D. A. Hammer, D. J. Pochan, Y. Chen, Y. M. Chabre, T. C. Shiao, M. Bergeron-Brlek, S. Andre, R. Roy, H. J. Gabius and P. A. Heiney, J Am Chem Soc, 2013, 135, 9055-9077.

S7

S3. Spectra of the compounds1H NMR Spectrum of compound 2

13C NMR Spectrum of compound 2

S8

1H NMR Spectrum of compound 4

13C NMR Spectrum of compound 4

S9

1H NMR Spectrum of compound 6

13C NMR Spectrum of compound 6

S10

1H NMR Spectrum of Nap-PZ

13C NMR Spectrum of Nap-PZ

S11

HRMS Spectrum of Nap-PZ

Elemental composition search on mass 323.16

m/z= 318.16-328.16m/z Theo. Mass Delta

(ppm)Compositionm/z Theo. Mass Delta

(ppm)Composition

323.16283 323.16283 -0.00 C 19 H 21 O 2 N 3

323.16149 4.15 C17H19O N6 323.16417 -4.15 C21H23O3 323.16015 8.29 C16H23O5N2 323.16014 8.31 C15H17N9 323.16602 -9.86 C8H21O5N9

nap-ppz #21 RT: 0.14 AV: 1 NL: 1.86E8T: FTMS + c ESI Full ms [150.00-1000.00]

150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z

0

5

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ance

324.16992z=1

C 19 H22 O2 N3 = 324.17065-2.25679 ppm

274.27362z=1 402.18384

z=1

362.32578z=1

167.07260z=1

960.46735z=?

642.62842z=?

512.50262z=1

602.32153z=1

710.35443z=1

892.67499z=1

801.49829z=?

1H NMR Spectrum of Nap-OH

O N O

N

NH

S12

13C NMR Spectrum of Nap-OH

HRMS Spectrum of Nap-OHElemental composition search on mass 505.24

m/z= 500.24-510.24m/z Theo. Mass Delta

(ppm)Compositionm/z Theo. Mass Delta

(ppm)Composition

505.24320 505.24320 -0.01 C 26 H 31 O 4 N 7

505.24187 2.64 C25H35O8N3 505.24455 -2.67 C28H33O5N4 505.24052 5.30 C23H33O7N6 505.24640 -6.33 C16H37O12N6 505.24774 -8.98 C18H39O13N3

nap-oh #16 RT: 0.11 AV: 1 NL: 3.73E7T: FTMS + c ESI Full ms [280.00-1000.00]

300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z

0

5

10

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bund

ance

506.25034z=1

C 26 H32 O4 N7 = 506.25103-1.36941 ppm

318.29987z=1

528.23224z=1

362.32611z=1

481.17044z=1374.36246

z=1 637.30487z=1544.20624

z=1437.19299

z=1 754.43756z=1

986.41467z=?

675.26080z=1

920.45532z=?

798.46344z=1

875.65808z=?

S13

1H NMR Spectrum of Nap-Glc

13C NMR Spectrum of Nap-Glc

S14

HRMS Spectrum of Nap-Glc

Elemental composition search on mass 623.27

m/z= 618.27-628.27m/z Theo. Mass Delta

(ppm)Compositionm/z Theo. Mass Delta

(ppm)Composition

623.26981 623.26981 -0.00 C 30 H 37 O 8 N 7

623.26848 2.14 C29H41O12N3 623.26713 4.30 C27H39O11N6 623.26445 8.60 C24H41O14N5 623.27569 -9.43 C23H41O13N7

nap-glc-fe_full #20 RT: 0.14 AV: 1 NL: 1.67E7T: FTMS + c ESI Full ms [150.00-1000.00]

150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z

0

5

10

15

20

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Rel

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bund

ance

624.27716z=1

462.22437z=1

336.17032z=?

176.00835z=2

274.27374z=? 434.21829

z=1662.23291

z=1725.21973

z=1481.17032

z=1803.23358

z=1935.91327

z=?596.27148

z=1891.15314

z=?

S4 Cartesian coordinates of optimized structuresNap-Glc ground state geometry

C -2.94366500 -2.72058900 -0.01042800

C -3.38915200 -1.46643300 0.47795600

C -4.70338400 -1.26591800 1.04411600

C -1.68370600 -2.87078400 -0.56026600

C -2.46722400 -0.37499400 0.46565400

C -1.18448400 -0.54618500 -0.11671200

C -0.80744100 -1.77464900 -0.63586400

C -2.81437400 0.86454800 1.06194800

C -4.05165100 0.99896200 1.67188000

C -4.98285300 -0.04832000 1.66565300

H -5.95412500 0.11947400 2.11381700

H -4.30573400 1.94743600 2.13269100

H -1.36371300 -3.84226900 -0.92206100

H 0.17966100 -1.87790200 -1.07238900

S15

N -0.62393900 1.78002100 0.44597700

C 0.32804400 2.90610500 0.42521300

C 0.16813400 3.79596700 -0.81221000

H 1.32999900 2.47699800 0.45877700

H 0.15510500 3.48407900 1.33351200

C 1.15997800 4.96253900 -0.80362100

H 0.31369100 3.18552600 -1.71054800

H -0.85880300 4.17707200 -0.84414100

H 1.03456100 5.59015900 -1.69100700

H 1.01770400 5.59792900 0.07759500

H 2.19538500 4.60422900 -0.79198000

C -6.74838900 -2.28133600 1.95283600

C -6.12942000 -2.71227400 -0.34324700

C -7.40983600 -3.65687600 2.01466400

H -7.50773100 -1.53177400 1.67591800

H -6.35688700 -2.02448000 2.94024600

C -6.79746700 -4.08131400 -0.27020800

H -6.86066800 -1.97252300 -0.70698100

H -5.30184500 -2.73840900 -1.05154000

H -8.25703100 -3.60562500 2.70339100

H -6.68448200 -4.38976900 2.41585900

H -7.19544000 -4.33494400 -1.25865200

H -6.03871200 -4.84376100 -0.00908600

N -5.64034900 -2.30699500 0.99214900

N -7.89974000 -4.05437800 0.69281700

C -8.62353700 -5.31302100 0.72363800

H -8.84221700 -5.61128000 -0.30951300

H -8.03390700 -6.13705900 1.16813200

C -9.97283400 -5.20415600 1.44799900

O -10.58769000 -4.14504800 1.57963000

N -10.45182800 -6.38447600 1.90886700

H -9.94366000 -7.24642800 1.75987300

C -11.77204000 -6.48845800 2.51284800

H -11.89714500 -5.68955000 3.24966000

H -12.55143700 -6.33513500 1.75284700

C -11.93770300 -7.83152300 3.16075500

C -12.77907500 -8.23273500 4.17414700

H -13.50926500 -7.71032400 4.77157300

N -11.21427300 -8.91780800 2.75863700

N -11.56009800 -9.96141000 3.46666000

N -12.51167500 -9.55494500 4.33187700

C -13.15686600 -10.49444900 5.23536200

C -12.14019000 -11.38810400 5.95615700

H -13.69581500 -9.88874500 5.97634200

S16

C -12.89933400 -12.41039200 6.79871500

H -11.54981500 -11.92119100 5.19862700

C -14.84562300 -12.17379500 5.25153300

C -13.91075400 -13.17518000 5.95207900

H -13.44787700 -11.87073400 7.58858100

H -15.39741400 -11.60481200 6.01657900

H -13.37871600 -13.75337400 5.18878600

H -3.59479400 -3.58172200 0.08201400

O -14.05260900 -11.26855700 4.45984700

O -11.31732900 -10.56267200 6.76242700

H -10.81595900 -11.16153400 7.33593700

O -11.92661000 -13.26891200 7.37826000

H -12.41749400 -13.93489000 7.88243300

O -14.62467700 -14.03687800 6.83694300

H -14.91436000 -14.80913200 6.33333600

C -15.86925600 -12.82826200 4.34016600

H -16.40667500 -12.03998600 3.79523100

H -16.59509700 -13.35288800 4.97669800

O -15.20673600 -13.72335300 3.45470300

H -15.88261400 -14.17089800 2.92901800

C -0.22741100 0.58292700 -0.16137800

C -1.87335700 1.99574100 1.05290600

O 0.87581300 0.49255000 -0.69769000

O -2.13776100 3.09176400 1.54633800

Nap-Glc-Fe3+ ground state geometry

C 4.45264500 -0.88192000 -2.46168900

C 4.33548800 -0.55857100 -1.07906400

C 3.23015600 -0.88906200 -0.22520400

C 5.55713500 -0.52221500 -3.20590700

C 5.33697800 0.32742600 -0.54975900

C 6.47576500 0.66984000 -1.32820000

C 6.59689100 0.22812400 -2.63214200

C 5.18934800 0.90245700 0.73534400

C 4.04228200 0.65467300 1.45994500

C 3.09244000 -0.26645800 1.00925800

H 2.20223700 -0.41412000 1.58330400

H 3.91363700 1.13624300 2.42257300

H 5.60462300 -0.79706400 -4.25432200

H 7.47271300 0.50841500 -3.20610000

N 7.35689300 2.03597500 0.52212600

C 8.41017900 2.90495900 1.08118000

C 8.21236800 4.38194300 0.72192000

H 9.36160800 2.54135800 0.69105900

S17

H 8.39145700 2.76920500 2.16299800

C 9.32057300 5.26084200 1.30941400

H 8.19293900 4.48218400 -0.36906000

H 7.23525600 4.71022000 1.09400300

H 9.16729300 6.31160000 1.04545000

H 9.34600300 5.19155100 2.40266100

H 10.30567100 4.96258600 0.93346700

C 2.69872900 -3.16678000 0.65280100

C 2.20731700 -2.69220200 -1.73349500

C 1.48418800 -4.13740000 0.76123800

H 2.65708600 -2.60043000 1.57869700

H 3.66440700 -3.61657900 0.42882900

C 1.15843800 -3.80410300 -1.62853800

H 1.67665400 -1.90381800 -2.26178000

H 3.14425400 -3.04732000 -2.15043100

H 0.96970200 -3.86685400 1.68098200

H 1.72155000 -5.19554000 0.65071200

H 0.37872000 -3.51083000 -2.32306700

H 1.52154500 -4.81859000 -1.77769600

N 2.36136700 -2.08605500 -0.37567400

N 0.56424100 -3.64498500 -0.27632000

C -0.88016800 -3.92564100 -0.16698800

H -1.22949200 -3.35921600 -1.04225700

H -1.15410200 -4.97870200 -0.13390500

C -1.24537800 -3.05750500 1.04041400

O -1.35423800 -3.29186200 2.20482800

N -1.31817900 -1.71119800 0.44456000

H -1.72740200 -1.74089200 -0.49816500

C -1.79864800 -0.57194700 1.21345100

H -1.79821200 -0.81386400 2.27008900

H -1.08414600 0.22387100 0.99209600

C -3.17699400 -0.24439700 0.77457700

C -4.24714800 0.29853300 1.44356300

H -4.38984500 0.61234500 2.46514000

N -3.55517500 -0.44922300 -0.52315900

N -4.79431200 -0.07809300 -0.68460900

N -5.22611600 0.38535900 0.50614800

C -6.55601000 0.95386200 0.65619100

C -7.63266600 0.07269900 0.01002100

H -6.74260000 1.01883300 1.73689100

C -8.97768400 0.78872600 0.11516900

H -7.38243900 -0.05520800 -1.05196400

C -7.75899700 2.96394700 0.24223800

C -8.89173900 2.19723100 -0.46291900

S18

H -9.24748300 0.86897600 1.18177500

H -7.98890600 3.03600100 1.31709500

H -8.65887800 2.13575400 -1.53165000

H 3.64927800 -1.38376000 -2.97197700

O -6.52821300 2.23822400 0.06501000

O -7.65327200 -1.17085200 0.68755200

H -8.45182400 -1.62928700 0.38677800

O -9.92620900 -0.01579600 -0.56990100

H -10.76468900 0.46852600 -0.54338500

O -10.16156100 2.80901000 -0.25230000

H -10.29196600 3.47395700 -0.94119000

C -7.56049200 4.37607500 -0.28146200

H -6.64887100 4.79114200 0.17040600

H -8.41191900 4.98083200 0.06074000

O -7.47923000 4.34416400 -1.70077500

H -7.40690200 5.25533500 -2.01290700

C 7.54329200 1.53577400 -0.77110900

C 6.21546000 1.80923900 1.29755900

O 8.55885900 1.81396900 -1.40374800

O 6.09239400 2.34048500 2.39838100

N 0.37972700 -1.24198400 2.81337900

O 0.35669400 -0.05309200 2.56801900

O 0.91514300 -2.05559200 1.84320400

O 0.10493300 -1.80605600 3.85064100

N -0.74424900 -0.55478900 -2.07512500

O -1.07387800 0.18938100 -1.18064800

O -0.88102300 -0.42316000 -3.26858400

O -0.14752100 -1.76306600 -1.69544900

Fe 0.55033000 -1.76911000 0.06552300

N 1.16457900 0.76559400 -0.71374200

O 0.68141500 0.12722400 0.35639600

O 1.25119100 1.97271200 -0.63530400

O 1.51348200 0.07410900 -1.68212000

(The End)