Synthesis of Fluorescent Nanoscale Salts/Metal-Organic Frameworks for Live-Cell Imaging

Article abstract of DOI:10.1021/acs.cgd.7b01574

The reaction between disulfonic acid, i.e., 1,5-naphthalenedisulfonic acid (NDS), Cu(NO₃)₂·3H₂O, and variety of ditopic pyridine analogues viz., 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene (B4PVA), 9,10-bis((E)-2-(pyridin-3-yl)vinyl)anthracene (B3PVA), and 3,3′-(peroxybis(methylene))dipyridine (3PBP), resulted in the formation of salts/metal-organic frameworks (MOFs), i.e., [NDS^2-·B4PVA²⁺·S] (FNP 1a), [NDS^2-·3PBP²⁺·MeOH·H₂O] (FNP 1b), [Cu·NDS·B4PVA] (FNP 1c), [Cu·NDS·B3PVA] (FNP 1d), and [Cu·NDS·3PBP] (FNP 1e), by the diffusion method where S in FNP 1a is a squeezed solvent molecule. Sulfonates with six oxygen atoms are involved in coordination with metal center and formed hydrogen bond interactions. X-ray structural analysis showed supramolecular architecture of the salts/MOFs where ligands act as a linear linker. The approximate particle size was calculated by powder X-ray diffraction patterns of the compounds using the Debye-Scherrer equation. The morphological characterization of the FNPs were performed by using scanning electron microscopy. The emission properties of these salts/MOFs may due the intraligand charge transfer (ILCT) and ligand to metal charge transfer phenomena. These nanocrystals were evaluated in live-cell imaging assays using HeLa and MCF-7 as a model cell-line.

Full text of DOI:10.1021/acs.cgd.7b01574

Subscriber access provided by UNIVERSITY OF TOLEDO LIBRARIES
Synthesis of fluorescent nanoscale salts/MOFs for live-cell imaging
Udai Pratap Singh, NEETU SINGH, RITU VARSHNEY, Partha Roy, and Ray J Butcher
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01574 • Publication Date (Web): 28 Mar 2018
Downloaded from http://pubs.acs.org on March 28, 2018
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 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 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.
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 29
Crystal Growth & Design
1
2
3
4
1
Synthesis of fluorescent nanoscale salts/MOFs for live-cell imaging
a
a
b
b
c
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
3
4
5
6
7
8
9
0
1
2
Udai P. Singh * Neetu Singh , Ritu Varshney , Partha Roy and Ray J. Butcher
a
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee – 247667, India. E-
mail: udaipfcy@iitr.ac.in; Tel: +91-1332-285329
b
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Department of Biotechnology, Indian Institute of Technology Roorkee, Roorkee – 247667,
India.
c
Department of Chemistry, Howard University, Washington, DC 20059, USA
ABSTRACT
1
1
1
The reaction between disulfonic acid i.e. 1,5ꢀnaphthalenedisulfonic acid (NDS),
Cu(NO ) .3H O and variety of ditopic pyridine analogues viz., 9, 10ꢀbis((E)ꢀ2ꢀ(pyridinꢀ4ꢀ
3
2
2
yl)vinyl)anthracene (B4PVA), 9, 10ꢀbis((E)ꢀ2ꢀ(pyridinꢀ3ꢀyl)vinyl)anthracene (B3PVA) and 3,3'ꢀ
2
ꢀ
13
(peroxybis(methylene))dipyridine (3PBP) resulted in the formation of salts/MOFs i.e. [NDS
2
+
2ꢀ
2+
1
1
1
4
5
6
.B4PVA .S] (FNP 1a), [NDS .3PBP .MeOH.H O] (FNP 1b), [Cu.NDS.B4PVA] (FNP 1c),
2
[Cu.NDS.B3PVA] (FNP 1d) and [Cu.NDS.3PBP] (FNP 1e) by diffusion method where S in
FNP 1a is squeezed solvent molecule. Sulfonates with six oxygen atoms involve in coordination
with metal center and formed hydrogen bond interactions. Xꢀray structural analysis showed
supramolecular architecture of the salts/MOFs where ligands act as a linear linker. The
approximate particle size was calculated by PXRD pattern of the compounds using Debye
Scherrer equation. The morphological characterization of the FNPs were performed by using
scanning electron microscopy (SEM). The emission properties of these salts/MOFs may due the
intraligand charge transfer (ILCT) and ligand to metal charge transfer (LMCT) phenomena.
These nanocrystals were evaluated in liveꢀcell imaging assays using HeLa and MCFꢀ7 as a
model cellꢀline.
17
1
1
8
9
20
2
2
2
1
2
3
24
2
2
2
5
6
7
INTRODUCTION
Metal organic frameworks (MOFs) are crystalline porous hybrid inorganicꢀorganic materials
1
prepared from an assembly of metal ions with organic linkers through strong covalent bonds .
28
Their define porosity and tunable chemical functionality make them attractive for the
2
ꢀ6
7ꢀ10
11ꢀ15
2
3
9
0
applications like gas storage , catalysis
and separation
etc.. Apart from their use as bulk
materials in above applications, MOFs are also potential candidates in bioimaging for living
31
cells. However, because of their micro porosity (generally, pore size of <2 nm), the potential
1
ACS Paragon Plus Environment

Crystal Growth & Design
Page 2 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
5
6
7
8
9
0
1
2
applications of these materials are limited. To overcome this limitation, one can either create
mesoporous channels within MOF or reduce the crystals to nanosize.
Recently organic salts and inorganic photoactive materials on the nanometerꢀscale have received
16ꢀ
considerable attention owing to their application in many fields including lightꢀemitting diode
1
8
19
20
21,22
23ꢀ25
26ꢀ28
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
, wavelengthꢀtunable lasers , catalysis , solar cells
, drug delivery
and bioimaging
etc.. The majority of nanomaterials are either purely organic (such as liposomes) or inorganic
29ꢀ31
(such as quantum dots) in composition
. Furthermore, the external surface of fluorescent
MOF nanocrystals also provides the potential to functionalize the core shell nanostructures for
3
2ꢀ34
35ꢀ37
biomedical sensing
and imaging
. Thus, it is very important to synthesize nanoscale
1
1
1
fluorescent MOFs for the application in liveꢀcell imaging. In literature different methods have
been used for the synthesis of nanosized MOFs, like surfactantꢀmediated hydrothermal
3
8
39,40
41
syntheses , waterꢀinꢀoil microemulsions
, microwaveꢀassisted solvo/hydrothermal synthesis
4
2
13
and coordination modulation . Apart from these methods, the key parameters used for the
control of particle size and shape still remains a challenge as the, introduction of new
functionality and maintaining intrinsic features are main limitation for the uses of nanoscale
1
1
1
4
5
6
4
3ꢀ48
metalꢀorganic frameworks (NMOFs)
. Although organic nanomaterial and nanoscale metal–
17
organic frameworks (NMOFs)/nanoscale coordination polymers (NCPs) have been used in the
4
9ꢀ51
1
1
8
9
biomedical applications, but still the results in liveꢀcell imaging are not much satisfactory
.
Luminescent probes are highly recommended for the successful detection of intracellular cell as they
52ꢀ54
20
give intracellular signal noninvasively in liveꢀcell imaging . Besides this property, the fluorescent
2
2
2
1
2
3
probes also possess intrinsic advantages over other type of detecting methods in terms of selectivity,
55ꢀ57
sensitivity and easy application . An increasing number of studies have used NMOFs as
molecular imaging probes and drug nanocarriers. Compared with conventional nanocarriers (e.g.,
organic nanocarriers of lipids/polymers, silica nanomaterials, and inorganic zeolites), NMOFs
possess some unique properties that allow them to perform as promising nanoplatforms for
bioimaging. The presence of relatively labile metal ligand bonds in NMOFs makes them
biodegradable, therefore it rapidly degrades the complex material and deliver the drug or probe.
The utilization of the various nanoꢀsized MOFs based on iron (III) carboxylate nanoparticles
24
2
2
2
5
6
7
28
2
3
9
0
with different organic linkers and structures (MILꢀ100, MILꢀ101), in biomedicine is usual due to
58ꢀ60
their acceptable in vitro and in vivo toxicological results
. Iron (III) carboxylate MOFs shows
31
several fascinating features i.e. high pore volume and tunable pore size for the efficient payloads
2
ACS Paragon Plus Environment

Page 3 of 29
Crystal Growth & Design
1
2
3
4
1
of entrapped drugs. There are several reports on lanthanide complexes emitting in the NIR
6
1ꢀ63
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
3
4
5
6
7
8
9
0
1
2
because these complexes have exciting properties for biological imaging
.
In this report, we have design fluorescent nanoparticles (FNPs) by using 1,5ꢀ
naphthalenedisulfonic acid (NDS) and Nꢀheterocyclic ditopic pyridyl based highly fluorescent
sensitizer (Scheme 1). These FNPs have significantly less particle size (~35ꢀ80 nm) and showed
important cytotoxicity values (10 µg/ml) which is supposed to be linkers based antitumor
activity. It was envisaged that all these FNPs are highly fluorescent and suitable for liveꢀcell
imaging. They enter into cells without any further change in functionalization and the
fluorescence property of these nanoparticles can be used for fluorescenceꢀbased cell imaging
applications.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
1
1
EXPERIMENTAL SECTION
Materials and general methods
13
All the reagents and starting materials were of reagentꢀgrade. Anthracene, naphthaleneꢀ1,5ꢀ
disulfonic acid (NDS), triethylphosphite, nicotinaldehyde and isonicotinaldehyde were purchased
from SigmaꢀAldrich, Sweden. Analytically pure metal salt i.e. Cu(NO ) ·3H O was obtained
1
1
1
4
5
6
3
2
2
from Himedia, Mumbai, India and used without further purification. The tetraethyl anthraceneꢀ
6
4
17
9,10ꢀdiylbis(methylene)diphosphonate (ADP) was synthesized according to literature method.
Synthesis
1
1
8
9
9, 10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene (B4PVA)
20
Tetraethylanthraceneꢀ9,10ꢀdiylbis(methylene)diphosphonate (ADP) (6.00 g, 12.53 mmol)
was dissolved in 150 mL THF and cooled the solution at 0 ºC followed by the slow addition of
NaH (1.20 g, 50.10 mmol). Stirred the reaction mixture for 1 h at room temperature under
nitrogen atmosphere, added 4ꢀpyridinecarboxaldehyde (9.44 mL, 108.60 mmol) at 0 ºC. Stirred
the resulting solution further for 24 h at room temperature. Filtered the yellow precipitate and
2
2
2
1
2
3
24
2
2
5
6
washed with THF. Yield: 42.0 % (2.51 g).
1
H NMR (400 MHz, CDCl ): d (ppm) 8.69 (d, 4H), 8.32 (dd, 4H), 8.15 s, 4H), 7.56 (d, 4H), 7.52
3
2
7
(dd, 4H), 6.90 (d, 2H).
28
9, 10-bis((E)-2-(pyridin-3-yl)vinyl)anthracene (B3PVA)
3
ACS Paragon Plus Environment

Crystal Growth & Design
Page 4 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
The compound B3PVA was synthesized by the same procedure as employed for the
B4PVA by using nicotinaldehyde (9.44 mL, 108.60 mmol) in place of 4ꢀ
pyridinecarboxaldehyde. Yield: 67.0% (3.33 g).
1
H NMR (400 MHz, CDCl ): d (ppm) 6.94 (d, 2H), 7.41 (dd, 2H), 7.52 (dd, 4H), 8.04 (t, 4H),
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
8.37 (dd, 4H), 8.61 (d, 2H), 8.88 (s, 2H).
6
7
3,3'-(peroxybis(methylene))dipyridine (3PBP)
Isonicotinaldehyde (5.00 mL, 57.53 mmol) was dissolved in 80 mL THF and cooled the
solution at 0 ºC followed by the slow addition of NaH (1.38 g, 57.53 mmol). Stirred the mixture
in nitrogen atmosphere for 30 min at room temperature. The resultant solution was further stirred
under UVꢀ light for 12 h at room temperature with continuous stirring. Filtered the pale yellow
8
9
10
1
1
1
2
crystalline material, washed several times with THF. Yield: 68.0 % (1.88 g).
1
H NMR (400 MHz, CDCl ): d (ppm) 3.49 (s, 4H), 9.00 (s, 2H), 8.69 (s, 2H), 8.24 (d, 2H), 7.42
3
1
3
(m, 2H).
14
NDS.B4PVA (FNP 1a)
1
1
1
5
6
7
The aqueous solution of NDS (0.20 g, 0.55 mmol) was layered onto THF solution of ligand,
B4PVA (0.21 g, 0.55 mmol). The fluorescent red colored crystals appeared on the walls of
crystallization tube were filtered, washed with water and THF. Yield: 45.0 % (0.09 g).
Elemental Anal. Calcd. % for C H N O S : C, 67.84; H, 4.19; N, 4.16; S, 9.53. Found: C,
18
38
28
2
6 2
1
2
2
2
2
2
9
0
1
2
3
4
67.73; H, 4.05; N, 4.04; S, 9.41.
NDS.3PBP (FNP 1b)
FNP 1b was synthesized by the same procedure as employed for FNP 1a by using ligand,
3PBP (0.12 g, 0.55 mmol) in place of B4PVA. Yield: 66.0 % (0.18 g).
Elemental Anal. Calcd. For C H N O S : C, 52.58; H, 3.61; N, 5.57; S, 12.76. Found: C,
2
2
18
2
8 2
52.65; H, 3.46; N, 5.46; S, 12.58.
25
Cu.NDS.B4PVA (FNP 1c)
2
2
2
6
7
8
The aqueous mixture of Cu(NO ) 3H O (0.13 g, 0.55 mmol) and NDS (0.20 g, 0.55 mmol)
3 2· 2
was layered onto THF solution of ligand B4PVA (0.21 g, 0.55 mmol) with the layer separation
of DMF. The brown colored crystals appeared on the walls of crystallization tube were filtered,
washed with water and THF. Yield: 53.8 % (0.07 g).
29
4
ACS Paragon Plus Environment

Page 5 of 29
Crystal Growth & Design
1
2
3
4
1
Elemental Anal. Calcd. % for C H CuN O S : C, 72.93; H, 4.27; N, 5.15; S, 5.90. Found: C,
1
32 92
8
12 4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
3
4
5
6
7
8
9
0
1
2
72.81; H, 4.36; N, 5.07; S, 5.77.
Cu.NDS.B3PVA (FNP 1d)
FNP 1d was synthesized by the same procedure as employed for the FNPꢀ1c by using
ligand, B3PVA (0.21 g, 0.55 mmol) in place of B4PVA. Yield: 52.3 % (0.68 g).
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Elemental Anal. Calcd. % for C H CuN O S : C, 72.93; H, 4.27; N, 5.15; S, 5.90. Found: C,
1
32 92
8
12 4
72.83; H, 4.16; N, 5.23; S, 5.78.
Cu.NDS.3PBP (FNP 1e)
FNP 1e was synthesized by the same procedure as employed for the FNP 1c by using ligand,
3PBP (0.12 g, 0.55 mmol) in place of B4PVA. Yield: 50.0 % (0.24 g).
1
1
1
Elemental Anal. Calcd. % for C H CuN O S : C, 47.69; H, 4.71; N, 6.54; S, 7.49. Found: C,
3
4
40
4
14 2
47.81; H, 4.63; N, 6.48; S, 7.56.
13
Sample Characterization
1
1
1
4
5
6
All the samples were carefully dried under vacuum for several hours prior to elemental analysis
on Elementar Vario EL III analyzer. Powder Xꢀray diffraction (PXRD) patterns for all the FNPs
were measured on a Bruker D8 diffractometer (CuKα, λ = 1.540 Å) at 296 K. UVꢀVis absorption
spectra were measured in the range 200 to 800 nm by using UV 1800, Shimadzu UV
spectrophotometer with the slit width 1.0 nm. The fluorescence emission spectra were recorded
on a RFꢀ5301PC spectrofluorophotometer (Shimadzu) with the excitation wavelength of 410 nm
for FNP 1a, FNP 1c and FNP 1d and 300 nm for FNP 1b and FNP 1e with the slit width 2.5 nm
for both the excitation and emission. The fluorescence decay profiles were recorded by exciting
the sample at 410 nm in the nanoseconds time domain in solvent DMF using a Horiba Jobin
Yvon “fluorocube FL” life time system equipped with new LED (635 nm) source. The DSC and
TG analyses were performed using PerkinꢀElmer Pyris Diamond DSC and Pyris Diamond
thermogravimetry analyzers, respectively. The sample was heated in nitrogen atmosphere, with a
17
1
1
8
9
20
2
2
2
1
2
3
24
2
2
2
5
6
7
−1
1
heating rate of 10 °C min and scan was recorded within the temperature range of 30ꢀ600 °C. H
1
3
and C NMR spectra for the ligand B4PVA, B3PVA and 3PBP were recorded in deuterated
1
28
chloroform (CDCl ) on a JEOL ECXꢀ400ꢀII. Chemical shifts of HꢀNMR spectra were given in
3
2
3
9
0
parts per million (ppm) with respect to TMS. The signal solvent from CDCl , 7.26 and 77.0 ppm
3
1
13
are set as a reference peak in H NMR and C NMR spectra respectively. Proton coupling
5
ACS Paragon Plus Environment

Crystal Growth & Design
Page 6 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
5
6
7
8
9
0
1
2
patterns are described as singlet (s), doublet (d), triplet (t), quartet (q), and multiplet (m). HRMS
were recorded on a Bruker microTOF ™ꢀQꢀII mass spectrometer (ESIꢀMS).
The Xꢀray data of all FNPs were collected on a Bruker Kappa Apex four circleꢀCCD
diffractometer using graphite monochromated MoKα radiation (λ = 0.71070 Å) at 296 K.
Structure solution and refinement were done by direct method and developed by conventionally
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
6
5
alternating cycles of leastꢀsquares refinement on SHELXTL program . SAINT and SADABS
6
6,67
software packages
were employed for data reductions and absorption corrections,
respectively. All the nonꢀhydrogen atoms were refined anisotropically. The hydrogen atoms were
granted to hop on their respective parent atoms according to their positions generated
theoretically and refined isotropically with fixed thermal factors. In FNP 1a and FNP 1c the
solvent molecules were highly disordered and was impossible to refine using conventional
discreteꢀatom models; thereby, the share of partial solvent electron densities was rejected by the
1
1
1
6
8.
13
SQUEEZE program in PLATON Crystallographic data (excluding structure factors) for the
structures reported in this paper have been deposited with the Cambridge Crystallographic Data
Centre (CCDC) as deposition Nos. CCDC 1584722ꢀ1584726,1828635 .
1
1
1
4
5
6
RESULTS AND DISCUSSION
17
The NMR and HRMS data for ligands B4PVA and B3PVA are very similar to the reported data
6
9
1
13
1
1
8
9
in literature . The H, C NMR and HRMS data (Figure. S1, S2 and S3) suggest the structure of
the ligand 3PBP which was further confirmed by single crystal Xꢀray structure (Figure S4).
Suitable crystals for single crystal Xꢀray analysis were grown from different solvent like
methanol, tetrahydrofuran (THF), dimethylformamide (DMF) and water. The crystallographic
data for ligand 3PBP and FNP 1aꢀ1e are given in Table S1 whereas; selected bond distances and
bond angles are listed in Table S2ꢀS4.
20
2
2
2
1
2
3
24
Structural description
2
2
2
5
6
7
FNP 1a, 1c and 1d crystallizes in the monoclinic crystal system with C2/c space group whereas
FNP 1b crystallizes in monoclinic crystal system with P2 /c space group. FNP 1e crystallizes in
1
triclinic crystal system with Pꢀ1 space group.
28
NDS.B4PVA (FNP 1a) comprised of half molecules each of monocationic ligand B4PVA and
monoanion NDS in the asymmetric unit (Figure S5). Both the component in unit cell are
connected with each other through charge assisted hydrogen bond interactions N(1)−H(1N)···O
with the bond distance 1.900 Å and extended to 1D helical structure, which are further linked
6
2
3
3
9
0
1
ACS Paragon Plus Environment

Page 7 of 29
Crystal Growth & Design
1
2
3
4
5
6
1
into the 2D sheet of NDS.B4PVA through C−H···O interactions between anthracene moieties of
the B4PVA and sulfonate oxygen of NDS. Subsequently, N−H···O and C−H···O interactions
resulted in the generation of two type of cyclic motif along aꢀaxis (Figure S6). Moreover, the
anthracene rings of B4PVA ligand insert into the cavity formed by these interactions between
B4PVA and NDS which are extended adjacent sheet into 3D supramolecular architecture. The
framework was stabilized by C−H···π and π···π interactions with the bond distances 2.298 Å and
3.600 Å respectively between anthracene moieties of one B4PVA, pyridine ring of another
B4PVA ligand, resulted in the formation of 1D channel along cꢀaxis which was occupied by
squeezed solvent molecule (Figure S7).
2
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
3
4
5
6
7
8
9
0
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
The asymmetric unit of solvate FNP 1b exhibited one 3PBP ligand, one crystallographic
dependent NDS molecule, one water and methanol molecule as shown in Figure 1. The structure
is sustained by transfer of proton from NDS molecule to 3PBP ligand. The formation of charge
assisted hydrogen bond was not observed in this case. Therefore, 3PBP self assembled and
formed the 1D tape (Figure S8) through hydrogen bond (N1−H1A···N2, 1.891 Å) between two
3PBP ligand. There is no direct interaction between both the ligands. Furthermore, the 1D tape of
sulfonates is extended to 2D sheet using C5−H46···O3 interaction (bond distance 2.652 Å)
between naphthyl ring of NDS and sulfonated oxygen. Structural analysis revealed that the
interaction of neighboring 2D sheet via., C−H···O interaction through the proton on pyridyl ring
of 3PBP in 1D chain and the sulfonate oxygen from 2D sheet of NDS raises the dimensionality
from 2D to 3D supramolecular organic framework (Figure S9). Various intermolecular hydrogen
bonding is involved in this solvate and formed the tetramer motif via O6−H45···O4 (1.657 Å)
and O6−H3W···O5 (2.024 Å) interactions.
11
1
1
1
2
3
4
15
1
1
1
6
7
8
19
2
2
2
2
0
1
2
3
Cu.NDS.B4PVA (FNP 1c) possess twoꢀfold interpenetrated structure. The asymmetric unit of
FNP 1c consists of one Cu(II) center coordinated with two crystallographically dependent
B4PVA ligand, half molecule NDS and two THF molecule. The local coordination environment
around Cu(II) center is depicted in Figure 2. The Cu(II) is coordinated equatorially by four
nitrogen atoms of the pyridyl group of bidentate B4PVA ligand and the axial position is
occupied by sulfonate oxygen atoms of NDS resulting slightly distorted octahedral geometry.
The average bond distance of Cu(II)ꢀN1, Cu(II)ꢀN2 and Cu(II)ꢀN3 lies in the ranges of 1.983ꢀ
2.062 Å whereas Cu(II)ꢀO1 bond distance is 2.733 Å which are very similar to reported data for
24
2
2
5
6
27
2
2
3
8
9
0
7
ACS Paragon Plus Environment

Crystal Growth & Design
Page 8 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
70,71
1
2
copper complexes
. The NꢀCu(II)ꢀN and angle around the metal center ranges from 88.99º to
95.30º. Further the structural analysis revealed that the Cu(II) ion coordinated by bidentate
B4PVA ligand at the equatorial position extend the structure to twoꢀdimensional layer structure
with larger cavity. The axially coordinated sulfonate oxygens extended the 2D layered structure
into 3D porous structure with rectangular cavities as shown in Figure 3. A number of weak
interactions viz., C−H···O (2.530 Å) between olefinic proton of B4PVA and sulfonate oxygen of
NDS and C−H···π (2.887 Å) interaction between proton present at the pyridyl ring of B4PVA
and πꢀelectron cloud of naphthyl ring of NDS are also involved. Further the 3D network
interpenetrated into the cavity of another 3D framework led to the formation of twoꢀfold
interpenetrated slightly porous structure (Figure 4) and the resultant cavity is occupied by THF
molecule. THF connected through host framework with C−H···O (2.658 Å) and C−H···π (2.392
Å) interactions.
3
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
6
7
8
9
10
11
1
1
2
3
Single crystal Xꢀray study of Cu.NDS.B3PVA (FNP 1d) revealed that the microporous MOF
with the ligand B3PVA possess nonꢀinterpenetrated structure. The asymmetric unit consists of
one Cu(II) center coordinated with one B3PVA and half NDS molecule. The local coordination
environment of Cu(II) is depicted in Figure 5.
14
1
1
1
5
6
7
The Cu(II) displayed a regular octahedral geometry by linking four equatorial N atoms of
B3PVA ligands and two oxygen atoms of axial NDS molecules. Like in FNP 1c, the Cu(II) is
coordinated by bidentate B3PVA at the equatorial position extended into 2D layer but there is
large difference in bond length of axially coordinated oxygen atom from sulfonate anion (Figure
S10). The average bond distance of Cu(II)−N1 and Cu(II)−O1 are 2.039 Å and 2.393 Å
respectively and the NꢀCu(II)ꢀN angle around the metal center ranges from 85.74º to 92.67º. The
difference in bond length of axially coordinated atom in FNP 1c and FNP 1d is may be due to
the C−H···π interactions between πꢀelectron cloud of naphthyl ring in NDS. The naphthyl ring of
NDS is slightly tilted in the cavity of 2D layer present in FNP 1d and prevents the framework
from the interpenetration. The adjacent 2D layer connected through NDS molecule and lead to
the formation of 3D metalꢀorganic frameworks with small rectangular cavities (Figure 6). It also
showed C−H···O, C−H···S and π···π interactions along with C−H···π such as C33−H33A···O1,
2.581 Å; C33−H33A···O1, 2.381 Å, C10−H10A···O3 2.490; C10−H10A···S1, 2.912 Å and
π···π, 3.220 Å interaction between two pyridyl ring.
18
1
2
2
9
0
1
22
2
2
2
3
4
5
26
2
2
2
3
7
8
9
0
8
ACS Paragon Plus Environment

Page 9 of 29
Crystal Growth & Design
1
2
3
4
1
Structural analysis of FNP 1e revealed that the asymmetric unit consists of one Cu(II) center, one
half molecule of 3PBP, half molecule of uncoordinated NDS, two coordinated water molecules
and two lattice water molecules, one of the water molecule presents on special axis. As shown in
Figure S11, the Cu ion adopts regular octahedral geometry, the two equatorial position are
coordinated with 3PBP and all other equatorial and axial positions are occupied by water
molecules. The bond length of CuꢀN is 2.008 Å and CuꢀO is in the range of 1.988ꢀ 2.453 Å.
Each 3PBP links Cu(II) ions through pyridyl nitrogen (N1A) and lead to the formation of a 1D
chain. The sulfonate oxygen of lattice NDS involves in the hydrogen bonding with coordinated
water molecules through O−H···O and C−H···O interactions and resulted in the formation of
layered structure (Figure S12).
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
3
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
6
7
8
9
10
1
1
1
1
2
3
In order to check the purity of bulk sample of five nanoꢀsize salts/MOFs, powder Xꢀray
diffraction measurements of 1aꢀ1e were performed to confirm whether the crystal structures of
nanoparticle are the actual model of their respective bulk materials and it was found that the
peaks for synthesized nanoparticle are in good agreement with the simulated one (Figure S13).
Morphological study
14
1
1
5
6
The morphological characterization of nanoscale salts/NMOFs were performed by using SEM.
SEM image displayed the self assembly of B4PVA and 3PBP with NDS into regular block and
rod shape morphology respectively whereas NMOFs i.e. 1c, 1d, 1e showed irregular shape of
particles (Figure S14 & S15). Further their approximate particle size was calculated by PXRD
pattern of the compounds using Debye Scherrer equation:
17
1
1
2
8
9
0
21
τ = K λ/ βcosϴ
2
2
2
3
In the powder Xꢀray diffraction pattern, we pick the strongest intensity peak of the salts/MOFs to
specify the influence of particle size for PXRD. The full width half maxima (FWHM) of the
peak at 4.14, 10.44 and 4.89 are 0.11, 0.15 and 0.23 for 1a, 1c and 1d respectively whereas 3PBP
salt and MOF showed almost similar FWHM value 0.10 at the peak 9.58 and 5.90 respectively.
Therefore, the particles size of 1b and 1e are approximately same. The larger particle size can
achieve the smaller full width half maxima value. According to Debye Scherrer formula the size
of the nanoparticles of 1a, 1b, 1c, 1d and 1e was <100 nm, which make these particles suitable
for the application in liveꢀcell imaging. The development of fluorescent nanoparticles for
2
4
25
2
2
6
7
28
2
3
9
0
9
ACS Paragon Plus Environment

Crystal Growth & Design
Page 10 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
5
6
7
8
9
0
1
2
biomedicines is still scarcely reported, and only in recent years has some progress been made in
7
2
this direction .
Emission spectra
The emission spectra of B4PVA, B3PVA and 3PBP and their respective salts/NMOFs were
measured at room temperature. The emissions for the fluorescent linkers B4PVA, B3PVA with a
πꢀconjugated backbone has been observed with the emission wavelength at 558 nm and for the
linker 3PBP emission wavelength at 356 nm. Hence the strongest emission of the fluorescent
linkers is usually from the excited singlet state to singlet ground state with the transition n → π*
or π → π* in nature. The excitation spectra of FNP 1b and FNP 1c are attained by monitoring the
emission at 558 nm and are dominated by broad band centered at about 487ꢀ655 nm upon
excitation at 410 nm (Figure S16, S17 & S18). In comparison with their respective fluorescent
linker B4PVA, B3PVA, the quenching in FNP 1a and FNP 1b marked blue shift are presumably
due to the multitude of weak interactions, such as hydrogen bonding and πꢀstacking in FNP 1a
and unique coordination of B4PVA and acid coligand NDS linkers to the metal centers whereas
enhancement in FNP 1c was observed with large blue shift of the peak which may be due to the
more rigid coordination of 3ꢀpyridyl ring of B3PVA ligand and acid coligand NDS to the Cu(II)
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
1
1
13
1
1
1
4
5
6
7
3ꢀ75
17
center
. The excitation spectra of FNP 1c and FNP 1d are attained by monitoring the emission
1
1
8
9
at 356 nm upon excitation at 300 nm and are dominated by a broad band centered at about 375ꢀ
445 nm in the close proximity to ultraviolet region. Compared to the 3PBP ligand, the
enhancement in fluorescence of FNP 1d and FNP 1e was observed whereas large enhance in
fluorescence intensity was observed for MOF nanomaterial FNP 1e with respect to 3PBP ligand.
This may be due to the conformational rigidity of ligand, thus reducing the nonꢀradiative decay
of the intraligand π→π* excited state. Further fluorescent properties of nanocrystals encouraged
us to use these particles for liveꢀcell imaging.
20
2
2
2
1
2
3
24
2
2
2
5
6
7
Fluorescence lifetime
The excited state information of the fluorescent nanoꢀsize salts/MOFs was measured by
fluorescence lifetimes (τ ) and the corresponding decay curves are shown in Figure S19 & S20.
F
28
Their fluorescence decay profile were recorded with excitation and emission wavelength 410 nm
and 558 nm for the salts or NMOFs of B4PVA and B3PVA ligands whereas for the salts and
NMOF of ligand 3PBP, same was recorded with excitation and emission wavelength 300 nm and
445 nm respectively. All the fluorescence life times profiles were obtained by fitting the decay
10
2
3
9
0
31
ACS Paragon Plus Environment

Page 11 of 29
Crystal Growth & Design
1
2
3
4
1
profiles in threeꢀexponential form and the calculated results are tabulated in Table S5. The FNP
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
3
4
5
6
7
8
9
0
1
2
1a and FNP 1b has tow component of (τ ) 2.01 ns and 2.56 ns respectively. Compared with the
F
NMOFs i.e., FNP 1c, FNP 1d and FNP 1e for which tow component are 3.19 ns, 3.24 ns and
4.73ns respectively, the shorter fluorescence lifetime for salts i.e. FNP 1a and FNP 1b was
observed. The πꢀπ stacking geometries in anthracene fluorophores was observed in FNP 1c and
FNP 1d favors the formation of ring aggregates, which are further responsible for longer
flourescence lifetimes for NMOFs in comparison to their respective salts.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Themogravimetric analysis
To examine the thermal stability of 1aꢀ1e, TG analyses was carried out and it was found that
FNP 1c and 1d showed almost similar stability behavior towards thermal decomposition (Figure
S21 & S22). It was analyzed that the NDS salt with 3PBP are stable upto 220 ºC. In contrast to
FNP 1b, FNP 1a was more stable as it represented more stable framework and hence
decomposes around 280 ºC. The first mass loss may be for methanol molecule which starts at 80
ºC and completed around 120 ºC. Later mass loss nearly at 280 ºC corresponds to the loss of
organic part of the sulfonic acid. In the case of FNP 1a, the first mass loss corresponds to
discharge of methanol molecule around 84 ºC with loss of 3.84 % (experimental) and 3.96 %
observed, second mass loss account for the release of water molecule around at 120 ºC with mass
loss of 3.43 %. The next weight loss at 227 ºC attributed to the loss of the organic component of
the sulfonic acid.
1
1
1
13
1
1
1
4
5
6
17
1
1
8
9
20
On the other hand, FNP 1c and FNP 1e, were stable upto 340 ºC showed almost similar
stability whereas FNP 1d was stable upto 430 ºC which may be due to the formation of stable
framework in case of FNP 1d. The primary mass loss attributed to the loss of extra framework
residual solvent molecules present in their respective lattice. The next loss represents the loss of
organic component of the metalꢀorganic framework.
2
2
2
1
2
3
24
2
2
2
5
6
7
Cell culture
MCFꢀ7 (human breast adenocarcinoma), HeLa (human cervical adenocarcinoma) cell lines
were purchased from National Centre for Cell Sciences (NCCS), Pune, India. Both the cell lines
were maintained in Dulbecco's Modified Eagle Medium (DMEM) supplemented with 10 % heat
inactivated fetal bovine serum and 1 % antibiotic mix (100 U/ml of penicillin and 100 µg/ml
28
2
3
3
9
0
1
streptomycin) at 37 ℃ in CO incubator.
2
Cell viability assay
11
ACS Paragon Plus Environment

Crystal Growth & Design
Page 12 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
76
3
1
2
3
4
5
6
7
8
9
0
1
2
MTT assay was accomplished as portrayed previously (Mossman, 1986) . Briefly, 5 X 10
MCFꢀ7/ HeLA cells per well were seeded in 96ꢀwell plates. Further, cells were treated with 1, 10
and 100 ꢁg/ml of FNP 1a, FNP 1b, FNP 1c, FNP 1d and FNP 1e dissolved in DMSO/H O (v/v =
2
1: 9). After incubation for 48 h the cultures were analyzed by MTT ([3ꢀ(4, 5ꢀDimethylꢀ2ꢀ
thiazolyl)ꢀ2, 5ꢀdiphenyltetrazolium bromide]) assay by the addition of 10 µl of 5 mg/ml MTT
and further incubating at 37ꢂ°C for 4 h. The MTTꢀcontaining medium was then aspirated and
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
7
7
precipitated formazan crystals were dissolved in 200 µl of DMSO . The absorbance was
measured on a FLUO star optima Plate Reader (BMG Labtech, Germany) at 570 nm. The cell
viability percentage was calculated by following formula;
1
1
1
Percentage Cell Viability = (Mean OD of treated cells / Mean OD of untreated cells) X 100
Confocal microscopy
4
5 X 10 MCFꢀ7/HeLa cells were seeded on each cover slip placed in the well of 12 well
13
plates and incubated for 24 h. Thereafter cells were treated with FNP 1a, FNP 1b, FNP 1c, FNP
1d and FNP 1e solution in 5 respective wells for 1 h. After 1h incubation, the probe medium of
each well was removed and the cells were washed two times by PBS. Thereafter the cells were
visualised under Confocal Laser Scanning Microscope (LSM 780, Carl Zeiss, Germany).
Statistical analysis
1
1
1
4
5
6
17
1
1
8
9
Data are précised as mean ± standard deviation (SD) of triplicate independent experiments
and statistically evaluated using oneꢀway ANOVA and followed by Tukey post hoc test using
Graph Pad Prism 6 (Graph Pad Software, San Diego, CA, USA). A pꢀvalue of less than 0.05 was
measured to be statistically significant.
20
2
2
2
1
2
3
Application of fluorescent nanoparticles (FNPs) in biological system
In order to show its application in biological samples, we perform an experiment to evaluate
the nanocrystal in liveꢀcell imaging assays using HeLa and MCFꢀ7 as a model cell line. Firstly,
24
2
2
2
5
6
7
the cytotoxicity of all the fluorescent nanocrystals was determined by using standard methyl
78,79
thiayl tetrazolium (MTT) assay
. It must be assumed that the viability of unprocessed HeLa
and MCFꢀ7 cells was assumed to be 100%. The MTT assay results showed minimal cytotoxicity
at the concentration of 10 µg/ml towards cell proliferation, upto 100% HeLa cell and MCFꢀ7
were alive as shown in Figure 7 & 8. The toxicity demonstrated by these FNPs is equal to or
significantly lesser than the toxicity of various other MOF formulations presently being
28
2
3
9
0
8
0ꢀ82
31
developed for bioꢀimaging or drug delivery
.
12
ACS Paragon Plus Environment

Page 13 of 29
Crystal Growth & Design
1
2
3
4
1
Next the confocal fluorescence and brightfield images of HeLa and MCFꢀ7 cells were
determined by laser scanning confocal microscopy (λexc = 410 nm), HeLa cell and MCFꢀ7 cells
incubated with 10 µg/ml of each FNP 1a, FNP 1b, FNP 1c, FNP 1d and FNP 1e for 1 h at 37 ºC,
a clear strong fluorescence signal in the green channel were observed (Figure 9 & 10). It means
FNPs are quick to respond to intracellular cell imaging under ambient conditions. In contrast, the
individual difference in fluorescence intensities in HeLa and MCFꢀ7 cell confirmed that the
fluorescent nanoparticles (FNPs) are membraneꢀpermeable.
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
3
4
5
6
7
8
9
0
1
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
CONCLUSION
In summary, we have synthesized five fluorescent nanoꢀsize salts/NMOFs of NDS with
various highly fluorescent pyridyl analogues i.e. B4PVA, B3PVA and 3PBP by diffusion
method. The approximate size and exact morphology of the salts and NMOFs were analyzed by
SEM image which displayed the self assembly of B4PVA and 3PBP with NDS into regular
block and rod shape morphology respectively whereas their respective MOF i.e., FNP 1c, 1d, 1e
showed irregular shape of particles and the particles are approximately nano in size (lesser than
100 nm). We have also calculated the approximate size of the FNPs from Debye Scherrer
formula. These FNPs have highly fluorescent behavior and suitable for biological applications
arising from their pyridylvinylꢀcontaining MOFꢀscaffolds. Upon incubation of these fluorescent
nanoparticles with the HeLa and MCFꢀ7 cell line, they showed lesser cytotoxic effect at the
concentration of 10 µg/ml, indicating a high degree of biocompatibility of these FNPs. HeLa cell
and MCFꢀ7 cells incubated with 10 µg/ml of each FNP 1a, FNP 1b, FNP 1c, FNP 1d and FNP
1e for 1 h at 37 ºC, showed a clear strong fluorescence signal in the green channel
ACKNOWLEDGEMENT
1
1
1
13
1
1
1
4
5
6
17
1
1
8
9
20
2
2
2
1
2
3
Authors are grateful to the CSIR, New Delhi, India for financial assistance. Neetu Singh
thankfully acknowledged UGC, New Delhi for providing fellowship.
24
2
2
2
5
6
7
References
1. Judeinstein, P.; Sanchez, C. Hybrid Organic–Inorganic Materials: A Land of
Multidisciplinarity. J. Mater. Chem. 1996, 6, 511ꢀ525.
2. Duriska, M. B. S.; Neville, M.; Lu, J.; Iremonger, S. S.; Boas, J. F.; Kepert, C. J.; Batten,
S. R. Systematic Metal Variation and Solvent and HydrogenꢀGas Storage in
Supramolecular Nanoballs. Angew. Chem. 2009, 121, 9081ꢀ9084.
13
28
2
3
9
0
31
ACS Paragon Plus Environment

Crystal Growth & Design
Page 14 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
5
6
7
8
9
0
1
2
3. Panda, T.; Pachfule, P.; Chen, Y.; Jiang, J.; Banerjee, R. Amino Functionalized Zeolitic
Tetrazolate Framework (ZTF) With High Capacity for Storage of Carbon Dioxide. Chem.
Commun. 2011, 47, 2011ꢀ2013.
4. Murray, L. J.; Dincă, M.; Long, J. R. Hydrogen Storage in Metal–Organic Frameworks.
Chem. Soc. Rev. 2009, 38, 1294ꢀ1314.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5. Falkowski, J. M.; Wang, C.; Liu, S.; Lin, W. Actuation of Asymmetric Cyclopropanation
Catalysts: Reversible SingleꢀCrystal to SingleꢀCrystal Reduction of Metal–Organic
Frameworks. Angew. Chem., Int. Ed. 2011, 123, 8833ꢀ8837.
6. Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A.; Snurr,
R. Q.; O’Keeffe, M.; Kim, J.; Yaghi, O. M. Ultrahigh Porosity in MetalꢀOrganic
Frameworks. Science 2010, 329, 424ꢀ428.
1
1
1
7. Sen, R.; Saha, D.; Koner, S. Controlled Construction of Metal–Organic Frameworks:
Hydrothermal Synthesis, Xꢀray Structure, and Heterogeneous Catalytic Study. Chem.
Eur. J. 2012, 18, 5979ꢀ5986.
13
1
1
1
4
5
6
8. Song, F.; Wang, C.; Lin, W. A Chiral Metal–Organic Framework for Sequential
Asymmetric Catalysis. Chem. Commun. 2011, 47, 8256ꢀ8258.
17
9. Uemura, K.; Kitaura, O. R. Y.; Nagaoka, M.; Kitagawa, S. NanochannelꢀPromoted
Polymerization of Substituted Acetylenes in Porous Coordination Polymers. Angew.
Chem., Int. Ed. 2006, 45, 4112ꢀ4116.
1
1
8
9
20
10. Jiang, H.ꢀL.; Akita, T.; Ishida, T.; Haruta, M.; Xu, Q. Synergistic Catalysis of Au@Ag
Core−Shell Nanoparticles Stabilized on Metal−Organic Framework. J. Am. Chem. Soc.
2011, 133, 1304ꢀ1306.
2
2
2
1
2
3
11. Chen, B.; Wang, L.; Xiao, Y.; Fronczek, F. R.; Xue, M.; Cui, Y.; Qian, G. A
Luminescent Metal–Organic Framework with Lewis Basic Pyridyl Sites for the Sensing
of Metal Ions. Angew. Chem. Int. Ed. 2009, 48, 500ꢀ503.
24
2
2
2
5
6
7
12. Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Luminescent Functional Metal–Organic
Frameworks. Chem. Rev. 2012, 112, 1126ꢀ1162.
28
13. Xiao, Y.; Cui, Y.; Zheng, Q.; Xiang, S.; Qian, G.; Chen, B. A Microporous Luminescent
2
+
2
3
9
0
Metal–Organic Framework for Highly Selective And Sensitive Sensing of Cu in
Aqueous Solution. Chem. Commun. 2010, 46, 5503ꢀ5505.
14
ACS Paragon Plus Environment

Page 15 of 29
Crystal Growth & Design
1
2
3
4
1
14. Chen, B.; Wang, L.; Zapata, F.; Qian, G.; Lobkovsky, E. B. A Luminescent Microporous
Metal−Organic Framework for the Recognition and Sensing of Anions. J. Am. Chem.
Soc. 2008, 130, 6718ꢀ6719.
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
3
4
5
6
7
8
9
0
1
2
15. Nagarkar, S. S.; Joarder, B.; Chaudhari, A. K.; Mukherjee, S.; Ghosh, S. K. Highly
Selective Detection of Nitro Explosives by a Luminescent Metal–Organic Framework.
Angew. Chem., Int. Ed. 2013, 52, 2881ꢀ2885.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
16. Liu, Y.; Deng, C.; Tang, L.; Qin, A.; Hu, R.; Sun, J. Z.; Tang, B. Z. Specific Detection
of dꢀGlucose by a TetraphenyletheneꢀBased Fluorescent Sensor. J. Am. Chem. Soc. 2011,
133, 660ꢀ663.
1
1
1
17. Zhao, J.; Yang, D.; Zhao, Y.; Yang, X. J.; Wang, Y. Y.; Wu, B. AnionꢀCoordinationꢀ
Induced TurnꢀOn Fluorescence of an OligoureaꢀFunctionalized Tetraphenylethene in a
Wide Concentration Range. Angew.Chem., Int. Ed. 2014, 53, 6632ꢀ6636.
18. Chen, G.; Li, W.; Zhou, T.; Peng, Q.; Zhai, D.; Li, H.; Yuan, W. Z.; Zhang, Y.; Tang, B.
Z. ConjugationꢀInduced Rigidity in Twisting Molecules: Filling the Gap Between
AggregationꢀCaused Quenching and AggregationꢀInduced Emission. Adv. Mater. 2015,
27, 4496ꢀ4501.
13
1
1
1
4
5
6
17
19. Klimov, V. I.; Ivanov, S. A.; Nanda, J.; Achermann, M.; Bezel, I.; McGuire, J. A.;
Piryatinski, A. SingleꢀExciton Optical Gain in Semiconductor Nanocrystals. Nature
2007, 447, 441ꢀ446.
1
1
8
9
20
20. Haruta, M. When Gold Is Not Noble: Catalysis by Nanoparticles. Chem Record 2003, 3,
75–87.
2
2
2
1
2
3
21. Gur, I.; Fromer, N. A.; Geiger, M. L.; Alivisatos, A. P. AirꢀStable AllꢀInorganic
Nanocrystal Solar Cells Processed from Solution. Science 2005, 310, 462ꢀ465.
22. Gratzel, M. Solar Energy Conversion by DyeꢀSensitized Photovoltaic Cells. Inorg. Chem.
2005, 44, 6841ꢀ6851.
24
2
2
2
5
6
7
23. ValletꢀRegí, M.; Balas, F.; Arcos, D. Mesoporous Materials for Drug Delivery. Angew.
Chem. 2007, 119, 7692ꢀ7703.
28
24. ValletꢀRegí, M.; Balas, F.; Arcos, D. Mesoporous Materials for Drug Delivery. Angew.
Chem., Int. Ed. 2007, 46, 7548ꢀ7558.
2
9
15
ACS Paragon Plus Environment

Crystal Growth & Design
Page 16 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
5
6
7
8
9
0
1
2
25. Zhang, L.; Gu, F. X.; Chan, J. M.; Wang, A. Z.; Langer, R. S.; Farokhzad, O. C.
Nanoparticles in Medicine: Therapeutic Applications and Developments. Clin.
Pharmacol.Ther. 2008, 83, 761ꢀ769.
26. Gao, X.; Cui, Y.; Levenson, R. M.; Chung, L. W.; Nie, S. In vivo Cancer Targeting and
Imaging with Semiconductor Quantum Dots. Nat. Biotechnol. 2004, 22, 969ꢀ976.
27. Sonnichsen, C.; Reinhard, B. M.; Liphardt, J.; Alivisatos, A. P. A Molecular Ruler Based
on Plasmon Coupling of Single Gold and Silver Nanoparticles. Nat. Biotechnol. 2005, 23,
741ꢀ745.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
28. Skrabalak, S. E.; Chen, J.; Sun, Y.; Lu, X.; Au, L.; Cobley, C. M.; Xia, Y. Gold
Nanocages: Synthesis, Properties, and Applications. Acc. Chem. Res. 2008, 41, 1587ꢀ
1595.
1
1
1
29. Rocca, J. D.; Liu, D.; Lin, W. Nanoscale Metal–Organic Frameworks for Biomedical
Imaging and Drug Delivery. Acc. Chem. Res. 2011, 44, 957ꢀ968.
13
1
1
1
4
5
6
30. Juzenas, P.; Chen, W.; Sun, Y. P.; Coelho, M. A. N.; Generalov, R.; Generalova, N.;
Christensen, I. L. Quantum Dots and Nanoparticles for Photodynamic and Radiation
Therapies of Cancer. Advanced Drug Delivery Reviews 2008, 60, 1600ꢀ1614.
31. Yu, W. W.; Chang, E.; Drezek, R.; Colvin, V. L. WaterꢀSoluble Quantum Dots for
Biomedical Applications. Biochemical and Biophysical Research Communications 2006,
348, 781ꢀ786.
17
1
1
8
9
20
32. Rawat, M.; Singh, D.; Saraf, S.; Saraf, S. Nanocarriers: Promising Vehicle for Bioactive
Drugs. Biol. Pharm. Bull. 2006, 29, 1790ꢀ1798.
2
2
2
1
2
3
33. Xu, Z. P.; Zeng, Q. H.; Lu, G. Q.; Yu, A. B. Inorganic Nanoparticles as Carriers for
Efficient Cellular Delivery. Chemical Engineering Science 2006, 61, 1027ꢀ1040.
34. Sokolova, V.; Epple, M. Inorganic Nanoparticles as Carriers of Nucleic Acids into Cells.
Angew. Chem., Int. Ed. 2008, 47, 1382ꢀ1395.
24
2
2
2
5
6
7
35. Taylor, K. M. L.; Reiter, W. J.; Lin, W. ManganeseꢀBased Nanoscale Metal−Organic
Frameworks for Magnetic Resonance Imaging. J. Am. Chem. Soc. 2008,130, 14358ꢀ
14359.
28
2
3
9
0
36. DeKrafft, K. E.; Xie, Z.; Cao, G.; Tran, S.; Ma, L.; Zhou, O. Z.; Lin, W. Iodinated
Nanoscale Coordination Polymers as Potential Contrast Agents for Computed
Tomography. Angew. Chem., Int. Ed. 2009, 48, 9901ꢀ9904.
31
16
ACS Paragon Plus Environment

Page 17 of 29
Crystal Growth & Design
1
2
3
4
1
37. Taylor, K. M. L.; Jin, A.; Lin, W. SurfactantꢀAssisted Synthesis of Nanoscale
Gadolinium Metal–Organic Frameworks for Potential Multimodal Imaging. Angew.
Chem., Int. Ed., 2008, 47, 7722ꢀ7725.
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
3
4
5
6
7
8
9
0
1
2
38. Lin, W.; Rieter, W. J.; Taylor, K. M. L. Modular Synthesis of Functional Nanoscale
Coordination Polymers. Angew. Chem. Int. Ed. 2009, 48, 650ꢀ658.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
39. Rieter, W. J.; Taylor, K. M. L.; An, H.; Lin, W.; Lin, W. Nanoscale Metal−Organic
Frameworks as Potential Multimodal Contrast Enhancing Agents. J. Am. Chem. Soc.
2006, 128, 9024ꢀ9025.
40. Rieter, W. J.; Pott, K. M.; Taylor, K. M. L.; Lin, W. Nanoscale Coordination Polymers
for PlatinumꢀBased Anticancer Drug Delivery. J. Am. Chem. Soc. 2008, 130, 11584ꢀ
11585.
1
1
1
41. Ni, Z.; Masel, R. I. Rapid Production of Metal−Organic Frameworks via Microwaveꢀ
Assisted Solvothermal Synthesis. J. Am. Chem. Soc. 2006, 128, 12394ꢀ12395.
42. Guo, H.; Zhu, Y.; Qiu, S.; Lercher, J. A.; Zhang, H. Coordination Modulation Induced
Synthesis of Nanoscale Eu Tb ꢀMetalꢀOrganic Frameworks for Luminescent Thin
13
1
1
1
4
5
6
1
ꢀx
x
Films. Adv. Mater. 2010, 22, 4190ꢀ4192.
17
43. Li, Y. A.; Zhao, C. W.; Zhu, N.; Liu, Q.; Chen, G.; Liu, J.; Zhao, X.; Ma, J.; Zhang, S.;
Dong, Y. Nanoscale UiOꢀMOFꢀbased Luminescent Sensors for Highly Selective
Detection of Cysteine and Glutathione and their Application in Bioimaging. Chem.
Commun. 2015, 51, 17672ꢀ17675.
1
1
8
9
20
2
2
2
1
2
3
44. Wang, Y.; Yang, X.; Zhong, Y.; Gong, X.; Li, Z.; Li, H. Development of a Red
Fluorescent LightꢀUp Probe for Highly Selective and Sensitive Detection of Vicinal
DithiolꢀContaining Proteins in Living Cells. Chem. Sci. 2016, 7, 518ꢀ524.
45. Jones, C. G.; Stavila, V.; Conroy, M. A.; Feng, P.; Slaughter, B. V.; Ashley, C. E.;
Allendorf, M. D. Versatile Synthesis and Fluorescent Labeling of ZIFꢀ90 Nanoparticles
for Biomedical Applications. ACS Appl. Mater. Interfaces 2016, 8, 7623ꢀ7630.
46. Wang, L.; Wang, W.; Zheng, X.; Li, Z.; Xie, Z. Nanoscale Fluorescent Metal–Organic
Framework@Microporous Organic Polymer Composites for Enhanced Intracellular
Uptake and Bioimaging. Chem. Eur. J. 2017, 23, 1379ꢀ1385.
24
2
2
2
5
6
7
28
2
9
17
ACS Paragon Plus Environment

Crystal Growth & Design
Page 18 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
5
6
7
8
9
0
1
2
47. Chowdhuri, A. R.; Bhattacharya, D.; Sahu, S. K. Magnetic Nanoscale Metal Organic
Frameworks for Potential Targeted Anticancer Drug Delivery, Imaging and as an MRI
Contrast Agent. Dalton Trans. 2016, 45, 2963ꢀ2973.
48. Lu, Y.; Yan, B.; Liu, J. L. Nanoscale Metal–Organic Frameworks as Highly Sensitive
2
+
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Luminescent Sensors for Fe In Aqueous Solution and Living Cells. Chem. Commun.
2014, 50, 9969ꢀ9972.
49. Pashow, K. M. L. T.; Rocca, J. D.; Xie, Z. G.; Tran, S.; Lin, W. B. Postsynthetic
Modifications of IronꢀCarboxylate Nanoscale Metal−Organic Frameworks for Imaging
and Drug Delivery. J. Am. Chem. Soc. 2009, 131, 14261ꢀ14263.
1
1
1
50. Liu, D. M.; Huxford, R. C.; Lin, W. B. Phosphorescent Nanoscale Coordination
Polymers as Contrast Agents for Optical Imaging. Angew. Chem., Int. Ed. 2011, 50,
3696ꢀ3784.
13
51. Rocca, J. D.; Liu, D. M.; Lin, W. B. Nanoscale Metal–Organic Frameworks for
Biomedical Imaging and Drug Delivery. Acc. Chem. Res. 2011, 44, 957ꢀ968.
52. Terai, T.; Nagano, T. Fluorescent Probes for Bioimaging Applications. Current Opinion
in Chemical Biology 2008, 12, 515ꢀ521.
1
1
1
4
5
6
17
53. De Silva, A. P.; Gunaratne, H. Q. N.; Gunnlaugsson, T.; Huxley, A. J. M.; McCoy, C. P.;
Rademacher, J. T.; Rice, T. E. Signaling Recognition Events with Fluorescent Sensors
and Switches. Chem. Rev. 1997, 97, 1515ꢀ1566.
1
1
8
9
20
54. Callan, J. F.; De Silva, A. P.; Magri, D. C. Luminescent Sensors and Switches in the
Early 21st Century. Tetrahedron 2005, 61, 8551ꢀ8588.
2
2
2
1
2
3
55. Maeda, H.; Katayama, K.; Matsuno, H.; Uno, T. 3′ꢀ(2,4ꢀDinitrobenzenesulfonyl)ꢀ2′,7′ꢀ
dimethylfluorescein as a Fluorescent Probe for Selenols. Angew. Chem., Int. Ed. 2006,
45, 1810ꢀ1813.
24
2
2
2
5
6
7
56. Chen, H.; Dong, B.; Tang, Y.; and Lin, W. Construction of a NearꢀInfrared Fluorescent
TurnꢀOn Probe for Selenol and Its Bioimaging Application in Living Animals. Chem.
Eur. J. 2015, 21, 11696ꢀ11700.
28
57. Zhang, B.; Ge, C.; Yao, J.; Liu, Y.; Xie, H.; Fang, J. Selective Selenol Fluorescent
Probes: Design, Synthesis, Structural Determinants, and Biological Applications. J. Am.
Chem. Soc. 2015, 137, 757ꢀ769.
2
3
9
0
18
ACS Paragon Plus Environment

Page 19 of 29
Crystal Growth & Design
1
2
3
4
1
58. McKinlay, A.; Morris, C.; Russell, E.; Horcajada, P.; Férey, G.; Gref, R.; Couvreur, P;
Serre, C. BioMOFs: Metal–Organic Frameworks for Biological and Medical
Applications. Angewandte Chemie Int. Ed. 2010, 49, 6260ꢀ6266.
59. Rocca, D.; Liu, J. D.; Lin, W. Nanoscale Metal–Organic Frameworks for Biomedical
Imaging and Drug Delivery. Acc. Chem. Res. 2011, 44, 957ꢀ968.
60. TamamesꢀTabar, C.; Cunha, D.; Imbuluzqueta, E.; Ragon, F.; Serre, C.; BlancoꢀPrieto
M. J.; Horcajada, P. Cytotoxicity of Nanoscaled Metal–Organic Frameworks. J. Mater.
Chem. B 2014, 2, 262ꢀ271.
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
3
4
5
6
7
8
9
0
1
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
61. Liu, J.; Bu, W.; Pan, L. Shi, J. NIRꢀTriggered Anticancer Drug Delivery by Upconverting
Nanoparticles with Integrated AzobenzeneꢀModified Mesoporous Silica. Angew. Chem.
Int. Ed. 2013, 52, 4375ꢀ4379.
1
1
1
62. Feng, W.; Han, C.; and Li, F. UpconversionꢀNanophosphorꢀBased Functional
Nanocomposites. Adv. Mater. 2013, 25, 5287ꢀ5303.
13
1
1
1
4
5
6
63. Deng, K.; Hou, Z.; Li, X.; Li, C.; Zhang, Y.; Deng, X.; Cheng, Z.; and Lin, J. Aptamerꢀ
Mediated Upꢀconversion Core/MOF Shell Nanocomposites for Targeted Drug Delivery
and Cell Imaging. Sci. Rep. 2015, 5, 7851.
17
64. Zhang, H. C.; Guo, E. Q.; Zhang, Y. L.; Ren, P. H.; Yang, W. Donor−Acceptorꢀ
Substituted AnthraceneꢀCentered Cruciforms: Synthesis, Enhanced TwoꢀPhoton
Absorptions, and Spatially Separated Frontier Molecular Orbitals. J. Chem. Mater. 2009,
21, 5125ꢀ5135.
1
1
8
9
20
2
2
2
1
2
3
65. Sheldrick, G. M. “SHELXTLꢀNTꢀ2000 version 6.12, reference manual”, University of
Göttingen, Göttingen, Germany.
66. Sheldrick, G. M. SADABS, University of Göttingen, Germany (1996).
67. Sheldrick, G. M. ActaCryst., Sect. A: Found. Crystallogr., 46, 467 (1990).
68. Spek, A. L., PLATON99, A Multipurpose Crystallographic Tool; Utrecht University:ꢂ
Utrecht, the Netherlands, 1999.
24
2
2
2
5
6
7
69. Bai, L.; Bose, P.; Gao, Q.; Li, Y.; Ganguly, R.; Zhao, Y. HalogenꢀAssisted Piezochromic
Supramolecular Assemblies for Versatile Haptic Memory. J. Am. Chem. Soc. 2017, 139,
436ꢀ441.
28
2
3
9
0
70. Günay, G.; Yesilel, O. Z.; Darcan, C.; Keskin, S.; Büyükgüngör, O. Synthesis, Crystal
Structures, Molecular Simulations for Hydrogen Gas Adsorption, Fluorescent and
19
31
ACS Paragon Plus Environment

Crystal Growth & Design
Page 20 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
2
3
4
5
6
7
8
9
0
1
2
Antimicrobial Properties of Pyrazineꢀ2,3ꢀDicarboxylate Complexes. Inorganica Chimica
Acta 2013, 399, 19ꢀ35.
71. Lee, HꢀJ.; Kwon, H.; Sim, J.; Song, D.; Kim, Y.; Kim, J.; Kim, K.; Lee, E. Synthetic
Control of Coincidental Formation of an NꢀHeterocyclic Carbene–Copper(I) Complex
and Imidazolium Cations within Metal–Organic Frameworks. CrystEngComm 2017, 19,
1528ꢀ1534.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
72. GimenezꢀMarques, M.; Hidalgo, T.; Serre, C.; Horcajada, P. Nanostructured Metal–
Organic Frameworks and their BioꢀRelated Applications. Coord. Chem. Rev. 2016, 307
(2), 342ꢀ360.
1
1
1
73. Dong, Y.; Xu, B.; Zhang, J.; Tan, X.; Wang, L.; Chen, J.; Lv, H.; Wen, S.; Li, B.; Ye, L.;
Zou, B.; Tian, W. Piezochromic Luminescence Based on the Molecular Aggregation of
9,10ꢀBis((E)ꢀ2ꢀ(pyridꢀ2ꢀyl)vinyl)anthracene. Angew. Chem., Int. Ed. 2012, 51, 10782ꢀ
10785.
13
1
1
1
4
5
6
74. Zhang, J.; Chen, J.; Xu, B.; Wang, L.; Ma, S.; Dong, Y.; Li, B.; Ye, L.; Tian, W.
Remarkable Fluorescence Change based on the Protonation–Deprotonation Control in
Organic Crystals. Chem. Commun. 2013, 49, 3878ꢀ3880.
17
75. Dong, Y.; Xu, B.; Zhang, J.; Lu, H.; Wen, S.; Chen, F.; He, J.; Li, B.; Ye, L.; Tian, W.
Supramolecular Interactions Induced Fluorescent Organic Nanowires with High Quantum
Yield based on 9,10ꢀdistyrylanthracene. CrystEngComm 2012, 14, 6593ꢀ6598.
76. Mosmann, T. Rapid Colorimetric Assay for Cellular Growth and Survival: Application to
Proliferation and Cytotoxicity Assays. J Immunol Methods. 1983, 65, 55ꢀ63.
77. Varshney, R.; Gupta, S.; Roy, P. Cytoprotective Effect of Kaempferol against Palmitic
AcidꢀInduced Pancreatic βꢀCell Death Through Modulation Of Autophagy Via
AMPK/Mtor Signaling Pathway. Molecular and Cellular Endocrinology 2017, 448, 1ꢀ20.
78. Ma, X.; Truc, N. K.; Borah, P.; Ang, C. Y.; Zhao, Y. Functional Silica Nanoparticles for
RedoxꢀTriggered Drug/ssDNA Coꢀdelivery. Advanced Healthcare Materials 2012, 1,
690ꢀ697.
1
1
8
9
20
2
2
2
1
2
3
24
2
2
2
5
6
7
28
79. Zhang, Q.; Liu, F.; Nguyen, K. T.; Ma, X.; Wang, X.; Xing, B.; Zhao, Y. Multifunctional
Mesoporous Silica Nanoparticles for CancerꢀTargeted and Controlled Drug Delivery.
Adv. Funct. Mater. 2012, 22, 5144ꢀ5156.
2
3
9
0
20
ACS Paragon Plus Environment

Page 21 of 29
Crystal Growth & Design
1
2
3
4
1
80. FoucaultꢀCollet, A.; Gogick, K. A.; White, K. A.; Villette, S.; Pallier, A.; Collet, G.;
Kieda, C.; Li, T.; Geib, S. J.; Rosi, N. L.; Petoud, S. Lanthanide Near Infrared Imaging in
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
3
4
5
6
7
8
9
0
1
2
3
+
Living Cells with Yb Nano Metal Organic Frameworks. Proc. Natl. Acad. Sci. U. S. A.
2013, 110, 17199ꢀ17204.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
81. TamamesꢀTabar, C.; Cunha, D.; Imbuluzqueta, E.; Ragon, F.; Serre, C.; BlancoꢀPrieto,
M. J.; Horcajada, P. Cytotoxicity of Nanoscaled Metal–Organic Frameworks. J. Mater.
Chem. B 2014, 2, 262ꢀ271.
82. Hu, Q.; Yu, J.; Liu, M.; Liu, A.; Dou, Z.; Yang, Y. A Low Cytotoxic Cationic Metal–
Organic Framework Carrier for Controllable Drug Release. J. Med. Chem. 2014, 57,
5679ꢀ5685.
1
1
1
21
ACS Paragon Plus Environment

Crystal Growth & Design
Page 22 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Scheme 1
ACS Paragon Plus Environment

Page 23 of 29
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 1. Crystal structure of NDS.3PBP (FNP 1b)
Figure 2. Crystal structure of Cu.NDS.B4PVA (FNP 1c)
ACS Paragon Plus Environment

Crystal Growth & Design
Page 24 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 3. Simplified perspective view of porous 3D framework (B4PVA (blue color rod)
and NDS (yellow color rod)) in FNP 1c
Figure 4. Simplified representation of 2-fold interpenetrated structure in FNP 1c
ACS Paragon Plus Environment

Page 25 of 29
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 5. Crystal structure of Cu.NDS.B3PVA (FNP 1d)
Figure 6. 3D view of network for FNP 1d along c-axis
ACS Paragon Plus Environment

Crystal Growth & Design
Page 26 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Control
10 g/ml
125
00
1
g/ml
100 g/ml
1
*
75
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
*
50
25
0
a
b
c
d
e
1
1
1
1
1
P
P
P
P
P
N
N
N
N
N
F
F
F
F
F
Figure 7. Cell viability of HeLa cells after being treated with FNP 1a-1e in DMSO/H
: 9) solvent for 24 h. “ * ” Represents statistically significant (p < 0.05) results as compared to
normal control cells.
2
O (v/v =
1
Control
10 g/ml
1
25
00
75
1 g/ml
100 g/ml
1
*
5
0
25
0
a
b
1
c
d
e
1
1
1
1
P
P
P
P
P
N
N
N
N
N
F
F
F
F
F
Figure 8. Cell viability of MCF-7 cells after being treated with FNP 1a-1e in DMSO/H O (v/v
2
= 1: 9) solvent for 24 h. “ * ” Represents statistically significant (p < 0.05) results as compared to
normal control cells.
ACS Paragon Plus Environment

Page 27 of 29
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 9. CLSM images of HeLa cells, after being treated with 10 µg/ml containing FNP 1a-1e
for 1 h
ACS Paragon Plus Environment

Crystal Growth & Design
Page 28 of 29
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 10. CLSM images of MCF-7 cells, after being treated with 10 µg/ml containing FNP 1a-
1
e for 1 h
ACS Paragon Plus Environment

Page 29 of 29
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
“
For Table of Contents Use Only”
Synthesis of fluorescent nanoscale salts/MOFs for live-cell imaging
a
a
b
b
c
Udai P. Singh * Neetu Singh , Ritu Varshney , Partha Roy and Ray J. Butcher
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
aDepartment of Chemistry, Indian Institute of Technology Roorkee, Roorkee – 247667, India. E-
mail: udaipfcy@iitr.ac.in; Tel: +91-1332-285329
bDepartment of Biotechnology, Indian Institute of Technology Roorkee, Roorkee – 247667,
India.
cDepartment of Chemistry, Howard University, Washington, DC 20059, USA
In this report, we have design five fluorescent nanoparticles (FNPs) such as salts or metal-
organic frameworks having long lived luminescent lifetimes and minimal photodamage to living
organisms for invitro bioimaging by using 1,5-naphthalenedisulfonic acid (NDS) and N-
heterocyclic ditopic pyridyl based highly fluorescent sensitizer FNPs show promising cell-
imaging applications.
ACS Paragon Plus Environment