Subscriber access provided by University of Otago Library

Communication
Cationic Polymerization of Vinyl Ethers Controlled by Visible Light
Veronika Kottisch, Quentin Michaudel, and Brett P. Fors
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b10150 • Publication Date (Web): 22 Nov 2016
Downloaded from http://pubs.acs.org on November 22, 2016

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 free 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 accessible to all
readers and 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.

Journal of the American Chemical Society 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 6 Journal of the American Chemical Society

1
2
3
4
5
6
7 Cationic Polymerization of Vinyl Ethers Controlled by Visible Light
8
9 Veronika Kottisch,† Quentin Michaudel,† and Brett P. Fors*
10
11 Cornell University, Ithaca, New York, 14853, United States
12
13
14 Supporting Information Placeholder
15
16 ABSTRACT: Photoinitiated cationic polymerizations metathesis polymerization (ROMP) based on
17 are widely used in industrial processes; however, photoredox catalysis.6 Through light irradiation, these
18 gaining photocontrol over chain growth would expand reactions can be turned on or off at will, paving the way
19 the utility of these methods and facilitate the design of for applications requiring spatio-temporal control.
20 novel complex architectures. We report herein a cationic Photocontrolled cationic polymerizations have yet to
21 polymerization regulated by visible light. This receive the attention of their radical counterparts despite
22 polymerization proceeds under mild conditions: a an impressive body of work on the photoinitiation of
23 combination of a metal-free photocatalyst, a chain- cationic transformations. Photoinitiated cationic
24 transfer agent (CTA), and light irradiation allows for the Light On
polymerizations of vinyl OMe Activation
ethers and oxiranes are indeed
25 synthesis of various poly(vinyl ether)s with good control industrially relevant, and such systems commonly rely
26 over molecular weight and dispersity as well as excellent on the generation of acids or reactive cations through
27 chain-end fidelity. Significantly, photoreversible cation light irradiation.7 More recently, Nicewicz8a and
28 formation in this system enables efficient control over 8b
SpokoynyS have separately reported new systems for
29 polymer chain growth with light. photoinitiated
P n
S Z cationic polymerizations.
O However,
Pn these
30 OR
methods provide controlBFonly over polymer chain
31 MeO 4 OMe
Applications for polymers are constantly expanding, initiation, and the regulation of chain growth with light
32
33 in part owing to the increasing degree of control that can remains a notable challenge.1 Herein, we address this
Light
be Off
exerted during the synthesisLight of Onthese complex unmet need and report the discovery of a
34
macromolecules. The recent merging of photoredox photocontrolled
Deactivation Light Off of
“living” cationic polymerization
35 OMe
36 chemistry and controlled radical polymerizations has led vinyl ethers (Figure 1).
37 to the development of novel reactions that produce Scheme 1. Design of a Photoreversible Cationic
38 polymers with precise average molar masses and narrow Polymerization of Vinyl Ethers.
39 dispersity
S (Đ), and most interestingly, afford spatio-
40 Pn temporal control over chainPn growth.1 The Activation Light On
S Z
41 implementation of Othese reactions for patterning
OR has
OMe
42 delivered a bottom-up BF 4 alternative to classic top-down
MeO OMe
43 photolithography techniques and has the potential to
2
44 provide unique polymer
1 architectures. Consequently, it
45 remains highly desirable to broaden
Deactivation the scope of
Activation
S
46 polymerizations that allow photoregulation over chain
Pn Pn
47 growth and increase the number of polymeric S Z
O OR
48 architectures that can be created with these methods. BF 4
49 MeO OMe
The vast majority of the photocontrolled
50
polymerizations developed to date are based on radical 1
51
processes. Several elegant photocontrolled atom transfer
52
radical polymerizations (ATRP),3 photoinduced
53
organotellurium-mediated radical polymerizations Light Off Deactivation
54
(TERP),4 and photoinduced electron transfer reversible
55 The ability to form carbocations reversibly in situ with
56 addition–fragmentation chain transfer (PET-RAFT)5
light is key to achieving photoregulation in cationic
57 polymerizations have allowed for the polymerization of
polymerizations. In 2015, Kamigaito and co-workers
58 a variety of acrylate, methacrylate, and styrenic
and Sugihara and co-workers independently disclosed
59 derivatives. In a different approach, Boydston and
controlled cationic RAFT polymerizations that used
60 coworkers disclosed a metal-free ring opening
ACS Paragon Plus Environment
 Journal of the American Chemical Society Page 2 of 6

unique chain-transfer agents (CTA) initiated with strong polymerization, which we attributed to photoinitiation
1 acids.1c,9 We postulated that the oxidation of these CTAs by the direct oxidation of the monomer (Table 1, entry
2 with an appropriate photocatalyst followed by mesolytic 9).6,8a,12
3 cleavage would photoreversibly yield a carbocation that
4 Monitoring the polymerization of IBVE under
could participate in the RAFT process.10 Significantly, optimized reaction conditions revealed a small induction
5
this reaction would give rise to a “living” cationic period followed by fast monomer consumption to give
6
polymerization process in which chain growth is full conversion after 2 h (Figure 1a). As expected for a
7
regulated by light (Scheme 1). system with living characteristics, Mn grew linearly with
8
9 Table 1. Photocontrolled Cationic Polymerization of Isobutyl conversion and Đ steadily decreased from 1.41 to 1.19
10 Vinyl Ether as the reaction proceeded (Figure 1b). These data further
1 (x mol %)
11 +
Me S NEt 2 Me
n
S NEt 2 corroborate the involvement of a controlled chain-
12 OiBu OiBu S
DCM, rt
OiBu OiBu S growth process.
450 nm LEDs
13 2a
(a) 100
14 a 80

Conversion (%)
15 Entry 1 Mn (exp) Mn (theo) Đ
16 (mol %) (kg/mol) (kg/mol) 60
17 1 0.01 2.6 2.3 1.29 40
18
19 2 0.02 5.6 5.0 1.19 20
20 3 0.02 10.0 10.0 1.21 0
21 4 0.02 17.5 20.0 1.21 0 20 40 60 80 100 120
22
5 0.01 35.0 40.0 1.30 Time (min)
23
(b) 2.0
24 6 0.02 26.0 40.0 1.37 8
25 1.8
7b

Dispersity
0.02 — 5.0 — 6
26
Mn (kg/mol)

8c — — 5.0 — 1.6
27 4
28 9d 0.02 52.2 — 3.96 1.4
29 a
Reaction conditions: IBVE (1 equiv), 1 (0.01–0.02 2 1.2
30 mol %), 2a (0.0025–0.02 equiv) at room temperature (rt)
31 0 1.0
in DCM with blue light-emitting diode (LED) 0 20 40 60 80 100
32
irradiation. bCarried out in the absence of light. cCarried Conversion (%)
33
out in the absence of 1. dCarried out in the absence of 2a.
34 Figure 1. Polymerization of IBVE: (a) conversion vs. time;
35 To test our hypothesis, we investigated the
(b) Mn and Đ vs. conversion.
36 polymerization of isobutyl vinyl ether (IBVE) with 2a as
37 the CTA (Table 1). An examination of strongly We next investigated our hypothesis that cation
38 oxidizing photocatalysts showed that 0.01 mol % 2,4,6- photoactivation is reversible, which would provide
39 tri-(p-methoxyphenyl)pyrylium tetrafluoroborate (1)11 temporal control over the chain-growth process. A
40 converted 47% of the monomer after exposure to visible reaction containing monomer, catalyst, and a CTA was
41 light for 3 h to yield a 2.6 kg/mol poly(IBVE) with a Đ exposed to light for 30 min and then stirred in the dark
42 of 1.29 (Table 1, entry 1). Increasing the concentration for the same time period. This cycle was repeated three
43 of 1 to 0.02 mol % led to full conversion and yielded 5.6 times, and aliquots were obtained at each switching
44 kg/mol polymer with a narrower Đ of 1.19 (Table 1, point for analysis with NMR and size-exclusion
45 entry 2). These results demonstrate that a controlled chromatography (SEC). The plot representing
46 cationic polymerization process promoted by light takes conversion versus time (Figure 2a) clearly shows that
47 place. In further support of a controlled process, polymerization proceeded only under visible-light
48 modulation of the CTA-to-monomer ratio enabled the irradiation. Moreover, these results demonstrate that the
49 synthesis of polymers with controlled number-average reaction was arrested by removing the external stimulus
50 molecular weight (Mn) and narrow Đ values (Table 1, and efficiently reinitiated by re-exposure to light. The
51 entries 2–5). Notably, all of the reactions were run to full SEC traces further support these data and show that the
52 conversion and showed excellent agreement between polymers grew only during periods of light exposure
53
theoretical and experimental molar masses. Furthermore, (Figure S12). These data illustrate that the catalyst
54
better control was observed at lower catalyst loadings system provides photocontrol over polymer chain
55
when larger Mn values were targeted (Table 1, entries 5 growth and that we have developed a truly
56
and 6). Control experiments without light or 1 (Table 1, photoregulated cationic polymerization process.13
57
58 entries 7 and 8) did not yield any polymer. Additionally, To further demonstrate the temporal control of these
59 reactions in the absence of 2a led to uncontrolled polymerizations, we investigated the influence of light
60
ACS Paragon Plus Environment
Page 3 of 6 Journal of the American Chemical Society

intensity on polymerization rates. Using neutral density Table 2. Optimized Polymerization Conditions for Other
1 filters, we observed a linear relationship between Vinyl Ethers with Photocatalyst 1 and CTA 2b
2 transmission and initial reaction rates (Figure 2b), which
3 S SEt 1 (x mol %) Me S SEt
shows that light intensity can be used to control the rate + Me
n
4 of polymer chain growth. OR OiBu S
DCM, rt
OiBu OR S
5 450 nm LEDs
2b
6
Entrya Monomer 1 Mn (exp) Mn (theo) Đ
7 (a) 40
8 (mol%) (kg/mol) (kg/mol)
OFF
Conversion (%)

9 30
1 EVE 0.02 5.4 5.0 1.16
10 OFF
11 20 2 EVE 0.01 9.6 10.0 1.20
12 3 Cl-EVE 0.02 5.0 5.0 1.28
13 10 OFF
4 Cl-EVE 0.02 8.8 10.0 1.30
14
15 0 5 PVE 0.01 4.8 5.0 1.27
16 0 30 60 90 120 150 180 210 240 270
6 BVE 0.02 5.8 5.0 1.23
17 Time (min) a
(b) Reaction conditions: vinyl ether (1 equiv), 1 (0.01–
18
0.02 mol %), 2b (0.01–0.02 equiv) at room temperature
Initial Reaction Rate (min )

1.0
-1

19
20 (rt) in DCM with blue light-emitting diode (LED)
0.8
21 irradiation. Reactions were run to full conversion.
22 0.6 Finally, photoluminescence quenching experiments
23 0.4 were conducted to gain a better understanding of the
24 polymerization mechanism. Strong quenching of 1* by
25 0.2 2a was observed at millimolar concentrations, and
26 0.0 significant quenching by IBVE was measured at molar
27 0.0 0.2 0.4 0.6 0.8 1.0 concentrations similar to those of the polymerization
28
Transmission conditions (Figures S15–S19). These observations
29
Figure 2. Temporal control of polymerization: (a)
suggest that 1* may oxidize either the CTA or IBVE as
30
monomer conversion vs. time with intermittent light previously reported by Nicewicz8a and Boydston.6 Given
31 these experimental data and literature precedents, we
exposure; (b) influence of light intensity on initial reaction
32 postulate that polymerization is activated by either the
rate.
33 direct oxidation of the CTA14 with the excited catalyst or
34 We then sought to apply this new methodology to the oxidation of the monomer6,8a,12 followed by electron
35 other vinyl monomers. Interestingly, CTA 2a yielded no transfer from the CTA (Figure 4). Mesolytic
36 polymer when used with other vinyl ethers. We 2b (1.4 mol %)
37 therefore decided to use CTA 2b, from which we 1 (0.02 mol %) Me S SEt
38 expected to obtain a more active propagating cation.9a n
39 DCM, rt
Gratifyingly, the use of 2b under our standard conditions OEt 450 nm LEDs OiBu OEt S
40 and low catalyst loadings of 1 led to the polymerization DCM, rt
41 of ethyl vinyl ether (EVE), 2-chloroethyl vinyl ether (Cl- 450 nm LEDs
Me b S SEt OiBu
42 EVE), n-propyl vinyl ether (PVE), and n-butyl vinyl n m
43 ether (BVE). In all cases, good agreement between OiBu OEt OiBu S
44
experimental and theoretical Mn and narrow Đ values 1.0
45 pEVE
were observed (Table 2).
46 0.8 Mn = 4.3 kg/mol
47 With conditions in hand that provide well-controlled Đ = 1.15
48 vinyl ether homopolymers, we probed the chain-end 0.6
49 fidelity of these materials through the synthesis of block pEVE-b-pIBVE
50 copolymers. Using our standard conditions with 2b as 0.4 Mn = 10.7 kg/mol
the CTA, we synthesized 4.3 kg/mol poly(EVE) Đ = 1.20
51
0.2
52 followed by the addition of IBVE to yield 10.7 kg/mol
53 poly(EVE-b-IBVE) diblock copolymer (Figure 3). The 0.0
54 SEC trace shows a monomodal distribution with low Đ 11 12 13 14 15 16 17
55 (1.20) and little to no tailing. This result demonstrates Retention Time (min)
56 that our method can be used for the one-pot synthesis of
57 block polymers and that the products maintain excellent Figure 3. Synthesis of poly(ethyl vinyl ether) and
58 chain-end fidelity even at full conversion. poly(ethyl vinyl ether-block-isobutyl vinyl ether).
59
60
ACS Paragon Plus Environment
 Journal of the American Chemical Society Page 4 of 6

fragmentation of the oxidized CTA10 would then result Uchiyama, M.; Satoh, K.; Xu, J.; Boyer, C.; Kamigaito, M.;
1 Qiao G. G. Adv. Sci. 2016, 3, 1500394.
in a carbocation that would polymerize via a
2 (2) (a) Poelma, J. E.; Fors, B. P.; Meyers, G. F.; Kramer, J. W.;
degenerative chain-transfer mechanism, thereby Hawker, C. J. Angew. Chem., Int. Ed. 2013, 52, 6844. (b)
3 allowing for narrow Đ and controlled Mn values. The Discekici, E. H.; Pester, C. W.; Treat, N. J.; Lawrence, J.;
4 reduction of the radical CTA with the reduced Mattson, K. M.; Narupai, B.; Toumayan, E. P.; Luo, Y.;
5 McGrath, A. J.; Clark, P. G.; Read de Alaniz, J.; Hawker, C. J.
photocatalyst to the dithiocarbamate (for 2a) or
6 ACS Macro Lett. 2016, 5, 258. (c) Yan, J.; Pan, X.; Schmitt, M.;
trithiocarbonate (for 2b) anion would allow for the Wang, Z.; Bockstaller, M. R.; Matyjaszewski, K. ACS Macro
7
regeneration of 1 and concomitant chain capping. This Lett. 2016, 5, 661. (d) Pester, C. W.; Narupai, B.; Mattson, K.
8
final step closes the catalytic cycle and enables the M.; Bothman, D. P.; Klinger, D.; Lee, K. W.; Discekici, E. H.;
9 Hawker, C. J. Adv. Mater. 2016, 28, 9292.
10 photoreversible formation of a cation, which gives rise
(3) For selected examples, see: (a) Fors, B. P.; Hawker, C. J. Angew.
11 to temporal control over polymer chain growth.15 Chem., Int. Ed. 2012, 51, 8850. (b) Konkolewicz, D.; Schroder,
12 K.; Buback, J.; Bernhard, S.; Matyjaszewski, K. ACS Macro
13 * Lett. 2012, 1, 1219. (c) Anastasaki, A.; Nikolaou, V.; Zhang, Q.;
1
S Burns, J.; Samanta, S. R.; Waldron, C.; Haddleton, A. J.;
14 Pn McHale, R.; Fox, D.; Percec, V.; Wilson, P.; Haddleton, D. M. J.
15 S S S Z
S S Am. Chem. Soc. 2014, 136, 1141. (d) Treat, N. J.; Sprafke, H.;
16 Pn hν 1 Pn Pn Pn Kramer, J. W.; Clark, P. G.; Barton, B. E.; Read de Alaniz, J.;
S Z S Z
Z Fors, B. P.; Hawker, C. J. J. Am. Chem. Soc. 2014, 136, 16096.
17 RO M
18 (e) Pan, X.; Malhotra, N.; Simakova, A.; Wang, Z.;
1 Konkolewicz, D.; Matyjaszewski, K. J. Am. Chem. Soc. 2015,
19 137, 15430. (f) Jones, G. R.; Whitfield, R.; Anastasaki, A.;
20 Haddleton, D. M. J. Am. Chem. Soc. 2016, 138, 7346. (g)
21 Figure 4. Postulated catalytic cycle for the photocontrolled Theriot, J. C.; Lim, C.-H.; Yang, H.; Ryan, M. D.; Musgrave, C.
22 polymerization of vinyl ethers. B.; Miyake, G. M. Science 2016, 352, 1082. (h) Pearson, R. M.;
23 Lim, C.-H.; McCarthy, B. G.; Musgrave, C. B.; Miyake, G. M.
In summary, we developed a cationic polymerization J. Am. Chem. Soc. 2016, 138, 11399.
24
regulated by visible light that requires mild reaction (4) For selected examples, see: (a) Yamago, S.; Ukai, Y.;
25 Matsumoto, A.; Nakamura, Y. J. Am. Chem. Soc. 2009, 131,
conditions, parts-per-million concentrations of a metal-free
26 2100. (b) Nakamura, Y.; Arima, T.; Tomita, S.; Yamago, S. J.
photocatalyst,16 and inexpensive blue light-emitting diodes.
27 Am. Chem. Soc. 2012, 134, 5536.
Narrow Đ and predictable Mn values can be obtained for a (5) For selected examples, see: (a) Xu, J.; Jung, K.; Atme, A.;
28 variety of vinyl ether monomers and block copolymers can Shanmugam, S.; Boyer, C. J. Am. Chem. Soc. 2014, 136, 5508.
29 be synthesized owing to high chain-end fidelity. Linear (b) Chen, M.; MacLeod, M. J.; Johnson, J. A. ACS Macro Lett.
30 responses to light intensity and reversible photoactivation 2015, 4, 566. (c) Shanmugam, S.; Xu, J.; Boyer, C. J. Am. Chem.
31 of the chain end allow temporal control over chain growth. Soc. 2015, 137, 9174. (d) Xu, J.; Shanmugam, S.; Duong H. T.;
32 Boyer, C. Polym. Chem. 2015, 6, 5615. (e) Shanmugam, S.; Xu
This methodology therefore opens the field of J.; Boyer, C. Chem. Sci. 2015, 6, 1341. (f) Shanmugam, S.; Xu,
33 photocontrolled reactions to a brand new class of J.; Boyer, C. Angew. Chem., Int. Ed. 2016, 55, 1036. (g) Xu, J.;
34 monomers and should find numerous applications for the Shanmugam, S.; Fu, C.; Aguey-Zinsou, K.; Boyer, C. J. Am.
35 synthesis of complex polymeric architectures. Chem. Soc. 2016, 138, 3094.
36 (6) (a) Ogawa, K. A.; Goetz, A. E.; Boydston, A. J. J. Am. Chem.
37 ASSOCIATED CONTENT Soc. 2015, 137, 1400. (b) Goetz, A. E.; Boydston, A. J. J. Am.
38 Supporting Information. General experimental Chem. Soc. 2015, 137, 7572. (c) Pascual, L. M. M.; Dunford, D.
considerations, experimental procedures, pictures of G.; Goetz, A. E.; Ogawa, K. A.; Boydston, A. J. Synlett 2016,
39
27, 759. (d) Goetz, A. E.; Pascual, L. M. M.; Dunford, D. G.;
40 experimental setups, and additional supporting data. Ogawa, K. A.; Knorr, Jr., D. B.; Boydston, A. J. ACS Macro
41 This material is available free of charge at the ACS Lett. 2016, 5, 579.
42 publications website. (7) (a) Crivello, J. V.; Lam, J. H. W. Macromolecules 1977, 10,
43 1307. (b) Crivello, J. V. J. Polym. Sci., Part A: Polym. Chem.
AUTHOR INFORMATION 1999, 37, 4241. (c) Dumur, F.; Gigmes, D.; Fouassier, J.-P.;
44
Corresponding Author Lalevée, J. Acc. Chem. Res. 2016, 49, 1980.
45 (8) (a) Perkowski, A. J.; You, W.; Nicewicz, D. A. J. Am. Chem.
46 *bpf46@cornell.edu Soc. 2015, 137, 7580. (b) Messina, M. S.; Axtell, J. C.; Wang,
47 Author Contributions Y.; Chong, P.; Wixtrom, A. I.; Kirlikovali, K. O.; Upton, B. M.;
48 Hunter, B. M.; Shafaat, O. S.; Khan, S. I.; Winkler, J. R.; Gray,
†
49 V.K. and Q.M. contributed equally to this study. H. B.; Alexandrova, A. N.; Maynard, H. D.; Spokoyny, A. M. J.
Am. Chem. Soc. 2016, 138, 6952.
50 Funding Sources (9) (a) Uchiyama, M.; Satoh, K.; Kamigaito, M. Angew. Chem., Int.
51 Ed. 2015, 54, 1924. (b) Sugihara, S.; Konegawa, N.; Maeda, Y.
The authors declare no competing financial interest.
52 Macromolecules 2015, 48, 5120. (c) Uchiyama, M.; Satoh, K.;
53 ACKNOWLEDGMENT Kamigaito, M. Macromolecules, 2015, 48, 5533.
54 This study was supported by Cornell University. BPF (10) (a) Maslak, P.; Narvaez, J. N. Angew. Chem., Int. Ed. 1990, 29,
thanks 3M for a Nontenured Faculty Award. 283. (b) Zhu, Q.; Gentry, E. C.; Knowles, R. R. Angew. Chem.,
55 Int. Ed. 2016, 55,9969.
56 REFERENCES (11) Miranda, M. A.; García, H. Chem. Rev. 1994, 94, 1063.
57 (1) (a) Chen, M.; Zhong, M.; Johnson, J. A. Chem. Rev. 2016, 116 (12) Cationic polymerization of vinyl ethers via anodic oxidation
58 10167. (b) Corrigan, N.; Shanmugam, S.; Xu, J.; Boyer, C. have been reported: Nuyken, O.; Braun, H.; Crivello, J.; In
Chem. Soc. Rev. 2016, 45, 6165. (c) McKenzie, T. G.; Fu, Q.;
59
60
ACS Paragon Plus Environment
Page 5 of 6 Journal of the American Chemical Society

Handbook of Polymer Synthesis, 2nd ed., Kricheldorf, H. R.; (15) The proposed mechanism has similarities to PET-RAFT – see
1 Nuyken, O.; Swift, G., Eds.; CRC Press: New York, NY, 2004. reference 5d.
2 (13) Leibfarth, F. A.; Mattson, K. M.; Fors, B. P.; Collins, H. A.; (16) Trotta, J. T.; Fors, B. P. Synlett 2016, 27, 702.
Hawker, C. J. Angew. Chem., Int. Ed. 2013, 52 ,199.
3
(14) Batanero, B.; Picazo, O.; Barba, F. J. Org. Chem. 2001, 66, 320.
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
 Journal of the American Chemical Society Page 6 of 6

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
6