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\begin{document}

\title{Chiroptical Generation, Switching, and Long-Term Memory in
Supramolecular Azobenzene-Pendant Polymer: Regulation by Cellulose
Peralkyl Esters, D-/L-Glucose Permethyl Esters, Solvents, UV Light
Irradiation, and Thermal Annealing Process}



\author[1]{Shiyuan Yi}%
\author[1]{Laibing Wang}%
\author[1]{Xiaoxiao Cheng}%
\author[2]{Fujiki Michiya}%
\author[1]{Wei Zhang}%
\affil[1]{Soochow University}%
\affil[2]{Nara Institute of Science and Technology}%


\vspace{-1em}



  
  \date{June 15, 2024}


\begingroup
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\selectlanguage{english}
\begin{abstract}
Various optically active polymers are known to afford sophisticated
chirality-related functionalities, i.e. asymmetric catalysis,
chiroptical switching and memory in UV-vis-NIR region, chromatographic
separation of enantiomers, and sensors for molecular chirality.
Recently, material researchers are received much attention to design
chiral supramolecular architectures from achiral polymers upon
intermolecular interactions with help of greener biosources. The present
article reports an instantaneous generation of ambidextrous
supramolecules revealing light-driven chiroptical switching/memory in
UV-vis region when achiral azobenzene-containing vinylpolymers are
non-covalently interacted with alkyl ester derivatives of natural
cellulose and D-/L-glucose. It was recognized that the semi-synthetic
biomaterials efficiently work as chirality-inducing scaffoldings to
several achiral and optically inactive molecules, oligomers, and
polymers. Our successful results shed light on a new approach of how
inexpensive poly-/mono-saccharide derivatives can afford supramolecular
chiroptical systems with the azobenzene pendant polymer as aggregates in
suspension and liquid-crystalline films with minimal energy, time, and
cost.%
\end{abstract}%



\sloppy


\textbf{Cite this paper:} \emph{Chin. J. Chem.} \textbf{2022} ,
\emph{40} , XXX---XXX.

\textbf{DOI: 10.1002/cjoc.202200XXX}

Chiroptical Generation, Switching, and Long-Term Memory in
Supramolecular Azobenzene-Pendant Polymer: Regulation by Cellulose
Peralkyl Esters, D-/L-Glucose Permethyl Esters, Solvents, UV Light
Irradiation, and Thermal Annealing Process

Shiyuan Yi,\emph{\textsuperscript{a}} Laibing
Wang,\emph{\textsuperscript{a}}Xiaoxiao
Cheng,*\textsuperscript{,\emph{a}} Michiya Fujiki
*\textsuperscript{,\emph{c}} and Wei Zhang*\textsuperscript{,\emph{a,b}}

\textsuperscript{a} State and Local Joint Engineering Laboratory for
Novel Functional Polymeric Materials, Jiangsu Engineering Laboratory of
Novel Functional Polymeric Materials, Suzhou Key Laboratory of
Macromolecular Design and Precision Synthesis, College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, Suzhou,
215123, China\textsuperscript{b} School of Chemical and Environmental
Engineering, Anhui Polytechnic University, Wuhu, 241000, China

\textsuperscript{c} Graduate School of Science and Technology, Nara
Institute of Science and Technology, 8916-5 Takayama, Ikoma, Nara
630-0192, Japan\selectlanguage{english}
\begin{longtable}[]{@{}l@{}}
\toprule
\textbf{Comprehensive Summary}\tabularnewline
\midrule
\endhead
Various optically active polymers are known to afford sophisticated
chirality-related functionalities, i.e. asymmetric catalysis,
chiroptical switching and memory in UV-vis-NIR region, chromatographic
separation of enantiomers, and sensors for molecular chirality.
Recently, material researchers are received much attention to design
chiral supramolecular architectures from achiral polymers upon
intermolecular interactions with help of greener biosources. The present
article reports an instantaneous generation of ambidextrous
supramolecules revealing light-driven chiroptical switching/memory in
UV-vis region when achiral azobenzene-containing vinylpolymers are
non-covalently interacted with alkyl ester derivatives of natural
cellulose and D-/L-glucose. It was recognized that the semi-synthetic
biomaterials efficiently work as chirality-inducing scaffoldings to
several achiral and optically inactive molecules, oligomers, and
polymers. Our successful results shed light on a new approach of how
inexpensive poly-/mono-saccharide derivatives can afford supramolecular
chiroptical systems with the azobenzene pendant polymer as aggregates in
suspension and liquid-crystalline films with minimal energy, time, and
cost.\tabularnewline
\textbf{Keywords}\tabularnewline
Azobenzene \textbar{} Supramolecular chirality \textbar{} Chirality
transfer \textbar{} Liquid-crystalline \textbar{}Polymer\tabularnewline
\bottomrule
\end{longtable}

\section*{}

{\label{section}}

Background and Originality Content

A variety of chiral motifs encompassed in all the biosphere on Earth has
been long intriguing subjects among scientific communities; i.e.
homochiral proteins made of achiral glycine and L-amino acids and,
helical nucleic acids composed of achiral nucleobase and D-pentose,
cellulose as a chainlike sequence of D-hexose, and handed spiral vines
and conch.\textsuperscript{1-4} Among a range of chiral motifs at
molecular and macromolecular levels, stimuli-responsive, non-rigid
chiral supramolecular architectures are possible to noncovalently
build-up from combination of achiral and chiral, chiral and chiral, and
achiral and achiral building blocks.

The stimuli-responsivity on chiral supramolecules relies on several
intermolecular interactions, involving conventional strong and
non-conventional weak hydrogen bonds, strong but long-range
electrostatic, weak and short-range \selectlanguage{greek}π-π, \selectlanguage{english}and weak but short-range van
der Waals interactions in addition to non-rigid molecular and
macromolecular frameworks made of covalent bonds, allowing rotational
and pyramidal inversion freedom associated with lower barrier
heights.\textsuperscript{5}

The stimuli-responsive chiral supramolecules conceptionally differ from
inherently rigid chiral molecules and helical polymers consisting of
enantiomerically pure stereogenic centers and sterically overcrowded
stereogenic bonds.\textsuperscript{6-9} In this regard, exploring the
underlying natural laws of chirality induction mechanisms of
chiral-and-achiral building blocks, and realizing the designed on-demand
smart chiral functions to supramolecular materials play important clues
in evolution of the homochiral biosphere, followed by an elegant
bottom-up process of practical chiral materials.\textsuperscript{10}

So far, among rigid and non-rigid polymers, cholesteric liquid
crystalline (Ch*LC) polymers capable of solid films and \selectlanguage{greek}µ\selectlanguage{english}m-size
aggregate/droplet as suspension are classified to chirality-related soft
matters.\textsuperscript{11-13} Generally, the chirality of Ch*LC
polymers (Ch*LCP) arises from stereogenic centers of Ch*LCP itself.
However, doping a small fraction of chiral molecules to achiral nematic
LC molecules and polymeric materials is the most common approach to
induce Ch*LC phases and to achiral nematic LC is the most common
approach to generate supramolecular chirality.\textsuperscript{14-16}

Such chiral amino acids, sugars, synthetic molecules and polymers are
often added to LC polymers, enabling co-assemblages to induce helical
motifs of multiple mesogens, leading to a macroscopically asymmetric
superstructures like Ch*LC phase and chiroptical generation (so-called
chirogenesis).\textsuperscript{17} Actually, the co-assemblages with the
chiral dopants lead to several unique chiroptical properties revealed by
circular polarization as selective reflection bands as one-dimensional
photonic bandgap engineering and induced circular dichroism (ICD) booted
resonantly in optofluidic medium in UV-Vis-near infrared (NIR)
region.\textsuperscript{18} The fatal drawback in the chiral molecular
and polymeric dopants in most Ch*LCPs, however, is a difficulty to
design multiple switching, rewritable memory (RW), and
write-once-read-many (WORM) modulated by condensational physical
stimuli,\textsuperscript{19} like UV-vis light, thermal energy, and
electric and magnetic fields.

Regarding the chirality induction to achiral systems, Li et al. reported
that the chiral dopants determine the sign and magnitude of the pitches
in Ch*LC phase due to its high fluidity.\textsuperscript{20} Our group
demonstrated that chiral molecules designed newly work as effective
dopants in Ch*LCP, allowed for the supramolecular chiroptical induction
and long-term memory.\textsuperscript{21} However, the construction of
Ch*LC polymers often requires the use of expensive and/or
environmentally unfavorable dopants. In this regard, naturally-occurring
chiral bio-resources and semi-synthetic derivatives are promising to
afford inexpensive, renewable, and environmentally friendly, and greener
chirality inducible scaffolds.\textsuperscript{22}

Representative bio-resources are L-/D-amino acids, L-/D-saccharides,
terpenes, and alkaloids. Particularly, cellulose and amylose as
polysaccharides consisting of D-glucose repeating units with\selectlanguage{greek}\emph{β}
-\selectlanguage{english}(1-4) and \selectlanguage{greek}\emph{α} -\selectlanguage{english}(1-4) linkages, respectively, are the most abundant
carbohydrates in most plants due to main components of cell walls and
roots.\textsuperscript{23} The contents of cellulose in plant as dry
matter attains as high as 30--50\%.\textsuperscript{24}

Thus far, a few experiments of cellulose-driven intermolecular chirality
transfer to circular dichroism (CD)-silent and circularly polarized
luminescence (CPL)-silent chromophoric and luminophoric molecules and
polymers suggested three possible mechanisms, as follows.

(i) Multiple weak C-H/O-C, C-H/\selectlanguage{greek}π, \selectlanguage{english}C-H/F-C, and strong N-H/O=C
interactions between cellulose derivatives and achiral
chromophores/luminophores are responsible for the induced chirality in
the chiral-achiral hybridized supramolecular systems.

(ii) Switchable helicity in floppy frameworks, depending on natures of
cellulose peralkyl esters and phenyl carbamoyl derivatives, permits a
left-right preference in fluxional helical backbones, leading to
optically active chromophores-and- luminophores.

(iii) Steric hindrance in certain cellulose derivatives restricts the
rotational freedom of backbone, allowing formation of rigid chiral
structures.\textsuperscript{25} Although mechanistic studies of
cellulose-driven chirality induction in achiral polymers are on-going,
semi-synthetic polysaccharide derivatives efficiently work as chirality
inducible scaffoldings, affording excellent stereoselectivity and
enantioselectivity by minimizing energy, time, chemicals, and cost.

Yet, several unanswered questions remain to us, as follow.

(i) Is natural cellulose made of only D-glucose repeating units
essential for the chirality induction capability?

(ii) How do molecular weights (\emph{M} \textsubscript{n}) and
polydispersity index (\selectlanguage{polish}\emph{Đ} \selectlanguage{english}) of polymers affect chirality and/or
helical transfer capability?

(iii) Are the absolute magnitudes and sign of ICD spectral
characteristics be tunable ?

To address these questions, here we chose cellulose triacetate (CTA) and
cellulose acetate butyrate (CABu), that are readily soluble in common
organic solvents. For comparison, we tested whether the respective
D-/L-glucose permethyl esters (D-Glu and L-Glu) that are soluble in
common organic solvents work as molecular chirality inducible
scaffoldings.

Regarding chirality transfer capability endowed with cellulose alkyl
esters, a helix sense between CTA and CABu is known to be opposite. CTA
and CABu prefer right and left, respectively, although their constitutes
have commonly the same D-glucose repeating units with \selectlanguage{greek}\emph{β} \selectlanguage{english}(1-4)
linkage.\textsuperscript{26}

In Scheme 1, we illustrate schematically how CTA and CAbu work as
ambidextrous chirality inducing scaffoldings to form supramolecularly
hybridized chiral structures with achiral azobenzene-pendant
vinylpolymers (PMMAzo). The azobenzene moiety of molecules and polymers
is established as a mesogen in nematic LC, producing Ch*LC
supramolecular architectures. As expected, D-Glu and L-Glu induced the
opposite ICD characteristics to the achiral polymers. Through our
systematical study in this work, knowledge and understanding allow us to
propose underlying relations and hidden laws between CTA, CABu, and
D-/L-Glu and chiroptical characteristics of supramolecular azobenzene
mesogens, proven by CD and UV-vis spectroscopy.

The present results should shed light on a new protocol for tailored
chiroptical functionality of achiral polymers and switching helicity in
CTA and CABu and switching in chirality of D- and L-Glu, leading to a
new possibility for ambidextrous large-area applications, i.e. displays,
sensors, and photonic devices. The chirality transfer with cellulose
derivatives, inexpensive commodity polymer, to various achiral
semi-commodity and purely synthetic polymers are thus very promising in
future.

Results and Discussion

Results

In this work, achiral methacrylate monomer bearing
4,4'-dialkoxyazobenzene (mesogen) with a flexible hexamethylene linker,
AzoMA (Scheme 1 and Figure S1) and the corresponding vinylpolymers,
PMMAzo, were prepared by the reversible addition-fragmentation
chain-transfer (RAFT) polymerization (Figure S2) in line with our
previous works.\textsuperscript{16} Synthesis of AzoMA, PMMAzo, CTA,
CABu, and D-/L-Glu were described in experimental
section.\textsuperscript{27} All CTA, CABu, and D-/L-Glu were readily
soluble in common organic solvents.

The values of \emph{M} \textsubscript{n} and \selectlanguage{polish}\emph{Đ} \selectlanguage{english}of PMMAzo were
controlled by molar ratios of AzoMA to 4-cyanopentanoic acid
dithiobenzoate (CPADB) as chain transfer agent. The effects of thermal
annealing time, ratios of the chirality/helicity transferable
scaffoldings to PMMAzo, and the \emph{M} \textsubscript{n} and
\selectlanguage{polish}\emph{Đ}\selectlanguage{english}values of PMMAzo affecting the magnitudes and sign in normalized
CD-to-UV-vis signals at CD extremum known as Kuhn's dissymmetry
ratio,\emph{g} \textsubscript{CD} at the first Cotton band around
350--400 nm, as chiroptical probes to evaluate the degree of ordered
supramolecular mesogens were investigated, as summarized in Table 1.

\textbf{Scheme 1} A schematic illustration of the preparation of chiral
PMMAzo film by mixed with cellulose derivatives.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image3/image3}

\end{center}
\end{figure}

First, the mesomorphic properties of PMMAzo polymer was characterized by
differential scanning calorimetry (DSC). From Figure S3, it is clear
that the glass transition temperature (\emph{T} \textsubscript{g}) is 72
\selectlanguage{ngerman}°C, a short-range smectic phase transition at 87 °C
(S\textsubscript{m}-to-N), and a long-range nematic phase transition at
128 °C (\emph{T} \textsubscript{i}), respectively. Second, to further
examine the chirality induction capability of CTA and CABu to PMMAzo as
a composite film, a mixture of PMMAzo and CTA/CABu homogeneously
dissolved in a solution (30 mg/mL) at a desired molar ratio was
deposited onto a quartz plate by a conventional spin-coating technique
at 1900 rpm. As shown in Table 1, nine samples of the composite films
comprising PMMAzo and CABu at the desired molar ratio were obtained. The
(chir)optical datasets of the composite films were measured by UV-vis
and CD spectroscopy.

\textbf{Table 1.} The number-average molecular weight (\emph{M}
\textsubscript{n}) of PMMAzo-1 to PMMAzo-3. Comparisons between the
\emph{g} \textsubscript{CD} values at 1\textsuperscript{st} Cotton band
of the CABu/PMMAzo composite films and their mass ratio with/without
thermal annealing process.\selectlanguage{english}
\begin{longtable}[]{@{}llllll@{}}
\toprule
Entry & Polymer & \emph{M}\textsubscript{n}\emph{\textsuperscript{a}}
(g/mol) & Ratio\emph{\textsuperscript{b}} &
Time\emph{\textsuperscript{c}} (min) &
\emph{g}\textsubscript{CD}\emph{\textsuperscript{d}}
(10\textsuperscript{--2})\tabularnewline
\midrule
\endhead
1 & PMMAzo-1 & 4600 & 2:1 & \textbf{0} & 0.263\tabularnewline
2 & PMMAzo-1 & \textbf{4600} & \textbf{2:1} & \textbf{10} &
2.544\tabularnewline
3 & PMMAzo-1 & 4600 & 2:1 & \textbf{20} & 2.910\tabularnewline
4 & PMMAzo-1 & 4600 & 2:1 & \textbf{30} & 3.338\tabularnewline
5 & PMMAzo-1 & 4600 & \textbf{1:1} & 10 & 3.202\tabularnewline
6 & PMMAzo-1 & 4600 & \textbf{3:1} & 10 & 1.118\tabularnewline
7 & PMMAzo-1 & 4600 & \textbf{4:1} & 10 & 0.743\tabularnewline
8 & PMMAzo-2 & \textbf{8000} & 2:1 & 10 & 1.250\tabularnewline
9 & PMMAzo-3 & \textbf{12000} & 2:1 & 10 & 0.263\tabularnewline
\bottomrule
\end{longtable}

\textsuperscript{\emph{a}} Determined by GPC according to PS standards
in THF. \textsuperscript{\emph{b}} Mass ratio of CABu to PMMAzo polymer
(w/w). \textsuperscript{\emph{c}} Annealing time at
80\textsuperscript{o}C. \emph{\textsuperscript{d}g} \textsubscript{CD}
value at the first Cotton band (350--400 nm).

From Figure 1a, two absorption bands of the film are detected in the
UV-vis spectra. The \selectlanguage{greek}π-π\selectlanguage{english}* transition of \emph{trans} -Azo is responsible
for the strong absorption band between 320 nm and 400 nm, while the n-\selectlanguage{greek}π\selectlanguage{english}*
transition of \emph{cis} -Azo underlies the weak absorption band between
430 nm and 500 nm.\textsuperscript{28} Achiral polymer films naturally
do not have a CD signal, obviously, the CD signal at 300--450 nm can be
observed when cellulose was mixed into the PMMAzo-1 polymer film (entry
1). A positive CD signal at around 390 nm was induced by CTA while a
negative CD was induced by CABu, associated with the zero-cross-point at
350 nm (Figure 1a). The excitonic couplet at 350 nm in the Cotton band
may originate from the splitting of an \emph{H} -band that corresponds
to a chiral interaction of \emph{H} -aggregation among neighboring Azo
chromophores. This interaction could lead to helical rotation within the
nematic phase, producing optically active polymer films. Subsequent
annealing of the polymer film at 80 \selectlanguage{ngerman}°C for ten minutes could result in a
tenfold increase in the CD amplitude, without changing the sign of CD
signal (Figure 1b). Annealing process can promote the formation of
chiral supramolecular structures by inducing molecular rearrangements
and enabling intermolecular interactions. By heating the film to its LC
phase temperature for a period of time, annealing can increase the
molecular mobility, reduce impurities and defects, and facilitate the
ordering and alignment of mesogens.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image4/image4}

\end{center}
\end{figure}

\textbf{Figure 1} . Changes in CD and UV-vis spectra of the composite
films consisiting of CTA/PMMAzo-1 (1:1, w/w, red curves) and
CABu/PMMAzo-1 (1:1, w/w, blue curves, entry 5 in Table 1) (a) before (as
prepared films at room temperature) and (b) after termal annealing
process at 80 \selectlanguage{ngerman}°C for 10 min.

We therefore investigated the effect of annealing time on the induction
of the chiral supramolecular structure of polymer films. As shown in
Figure S4, a 10-minute annealing treatment of the polymer composite film
is enough to obtain a 10-fold increase in maximum helicity over the
pristine one (entries 1-4). Furthermore, the solvent used to dissolve
the polymer is the key for aggregation processes and can strongly
influence aggregation behavior via the specific interactions between
solvent and solute. On the one hand, the basic features of solvents such
as polarity, viscosity, and solubility for the polymers could affect the
interaction tendencies between building blocks of supramolecular
systems. According to our previous works,\textsuperscript{7, 29, 30} the
types of solvents played an important role in the supramolecular
assembly of azobenzene-containing polymers. For example, supramolecular
chirality of azobenzene-containing polymers can be constructed in
chloroform, dichloromethane and 1,2-dichloroethane, but cannot
in\emph{N} ,\emph{N} -dimethylformamide.\textsuperscript{29}
Furthermore, the chiral expression of supramolecular aggregates also
differs in different solvents. On the other hand, supramolecular
chirality is produced by nonsymmetric arrangement of building blocks
through weaker noncovalent bond interaction, which can be easily
influenced by external environmental factors such as solvents, which is
generally dynamic, changing in response to external
stimuli.\textsuperscript{31} Here, CABu and PMMAzo-1 were co-solved in
chloroform (CHCl\textsubscript{3}), dichloroethane
(CH\textsubscript{2}Cl\textsubscript{2}) and tetrahydrofuran (THF) with
the mass concentration of 30 mg/mL, and solvent polarity is also an
important factor determining the chiral expression of composite films.
When the solvent for dissolving the mixture was changed from
CHCl\textsubscript{3} to CH\textsubscript{2}Cl\textsubscript{2} and THF,
there was a more significant increase in chiral expression regardless of
the annealing treatment (Figures 2a and 2b). The \emph{g}
\textsubscript{CD} of the spin-coated film prepared by THF solvent is
the largest among all series (Figure 2c). These results indicate that
THF is the best solvent for dissolving polymers, and its appropriate
polarity can effectively promote the cooperative interaction between
polymer building blocks and chiral CABu semi-synthetic biomaterials
(Figure 2d).\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image5/image5}

\end{center}
\end{figure}

\textbf{Figure 2} Changes in CD and UV-vis spectra of the CABu/PMMAzo-1
composite films (CABu/PMMAzo-1 = 2:1, w/w) (a) before annealing as
prepared films at room temperature and (b) after termal annealing at 80
\selectlanguage{ngerman}°C for 10 min. (c) A comparison of \emph{g} \textsubscript{CD} values at
the first Cotton band (350--400 nm) in three composite films prepared by
chloroform (red), dichloroethane (green), and tetrahydrofuran (blue)
before and after the annealing processes. (d) Possible supramolecular
stacking structure of PMMAzo.

Besides, the relative weight ratios of CABu to PMMAzo significantly
affect \emph{g} \textsubscript{CD} values (entries 2, 5-7 in Table 1).
From Figure 3a, it is evident that all the polymer composite films
showed very strong Cotton effects at room temperature in the absorption
region of the \emph{trans} -azobenzene group, demonstrating that the
CABu successfully induced the helical \selectlanguage{greek}π-\selectlanguage{english}stacks of Azo building units in
polymer side-chains. Further annealing increased the CD amplitude by two
orders of magnitude (Figure 3b). The corresponding\emph{g}
\textsubscript{CD} values were summarized in Figure 3c, the maximum
\emph{g} \textsubscript{CD} values of each polymer films decreased
gradually with the increase of CABu content. This may be attributed to
the fact that proper content of inducer helps to form a more regular
surface, because we found that more inducer would make the film
inhomogeneous (Figure 4d). Apparently, the preference for induced
supramolecular chirality can be tuned by changing the content of chiral
semi-synthetic biomaterials or the type of solvent.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image6/image6}

\end{center}
\end{figure}

\textbf{Figure 3} . Changes of CD and UV-vis spectra of CABu/PMMAzo-1
composite films (a) before annealing as prepared films at room
temperature and (b) after termal annealing at 80 \selectlanguage{ngerman}°C for 10 min. (c) A
comparison of the correspomding \emph{g} \textsubscript{CD} values for
the CABu/PMMAzo-1 composite films before and after the annealing. (d)
Photographs of the CABu/PMMAzo-1 composite films. The mass ratio of
CABu/PMMAzo-1 is 1:1 (red), 2:1 (blue), 3:1 (yellow), and 4:1 (green),
respectively.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image7/image7}

\end{center}
\end{figure}

\textbf{Figure 4} (a) CD and UV-vis spectra of the polymer composite
films with different molecular weights of Azo polymers (entries 2, 8,
9). (b) Photographs of the corresponding composite films. Changes in the
(c) CD spectra and (d) the maximum CD values of the CABu/PMMAzo
composite films (entry 2).

The induced circular dichroism of the polymer films is slightly affected
by the molecular weight of Azo polymers (entries 2, 8 and 9). Despite
differences in molecular weight, all three polymers demonstrated strong
CD signals (Figure 4a). And PAzoMA-1 film (\emph{M} \textsubscript{n} =
4600 gmol\textsuperscript{-1}) exhibited a slightly stronger CD
intensity than the other polymers with varying \emph{M}
\textsubscript{n}s. This may be due to the decrease in the compatibility
of the Azo polymer and CABu as well as the transparency of the polymer
film as the molecular weight of the polymer increases (Figure 4b).
Furthermore, the CABu induced film also showed good chiral memory
properties. As presented in Figures 4c and 4d, the CD signal of the
CABu/PMMAzo-1 composite film was essentially unchanged over two days.
This implies that the well-organized supramolecular helical structures
of Azo units in the film is stable at room temperature, which is helpful
for the further regulation of the chiral film.

It is well-known that chiroptical switch of Azo-containing systems
offers fascinating opportunities, because molecular or supramolecular
chirality might be tunable by \emph{trans} -\emph{cis} process in a
fully reversible manner (Figure 5a).\textsuperscript{32-34} Elegant
chiroptical switches and photo-responsive polymer systems have been
widely reported. In this system, CABu/PMMAzo film can act as carriers
for Azo-based photochromic switch that undergoes\emph{trans}
-to-\emph{cis} photoisomerization under irradiation with ultraviolet
light. The results in Figures 5b and 5c show that the helical stacks of
Azo units undergo an order-disorder-order transition with \emph{trans}
-\emph{cis} -\emph{trans} isomerization. Photo-switching of
CABu/PMMAzo-1 film is, indeed, reversible, even after leaving the
polymer film for several months, and there was nearly no fatigue effect
on the sample after five cycles of alternating UV light irradiation
(\emph{tans} -to-\emph{cis} ) and heating treatment (\emph{cis}
-to-\emph{trans} ). The switch acts as a nanoscale energy converter to
dynamically realize the chiroptical response of chiral signals without
contact.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image8/image8}

\end{center}
\end{figure}

\textbf{Figure 5} (a) The isomerization of Azo units. (b) Changes in CD
spectra and (c) the maximum \emph{g} \textsubscript{CD} values of the
first Cotton band of the CABu/PMMAzo-1 composite films (entry 2) during
365 nm light irradiation and heating-cooling treatment.

We further analysed the mechanism of molecular interaction and
macromolecular geometry during chiral induction using NMR and FTIR
instruments. The transfer of helicity and/or chirality, which induces
left-right imbalance, is attributed to the vast amount of intermolecular
C-H/\selectlanguage{greek}π \selectlanguage{english}interactions between Azo and CTA. Since CABu is a mixture randomly
containing methyl and propyl groups, we used CTA with a relatively
well-defined repeating unit as the chirality inducing scaffolding
(Figure 6a). The FTIR spectra were first recorded on a TENSOR-27
spectrophotometer using KBr as tablet. As presented in Figure 6b,
numerous and dense absorption bands near 1600 cm\textsuperscript{-1}were
observed, corresponding to the benzene ring in PMMAzo polymers. After
irradiation for 3 min with 365 nm UV light, we noticed a slight decrease
in the absorption band of the benzene ring, which can be attributed to
the \emph{trans} -to-\emph{cis} isomerization of Azo units. Furthermore,
changes in NMR spectra of the CTA, PMMAzo and the CTA/PMMAzo composite
mixtures were investigated (Figures 6c and 6d). The protic hydrogen
atoms on the benzene ring are mainly located at 6.9 ppm and 7.8 ppm
(Figure 6c). The proton hydrogen atoms of benzene moved before and after
CTA addition. Meanwhile, clear shift was observed for the protic
hydrogens (C-H) on the achiral methyl ester group near the chiral center
of the glucose residue (Figure 6d), suggesting that the chirality
transfer from celluloses to achiral PMMAzo polymers proceeds through the
intermolecular C-H/\selectlanguage{greek}π \selectlanguage{english}interaction. The chirality transfer mechanism are
also reflected by the emergence of CD signals. Accordingly, this
principle is also applicable to the chiral interaction between the CABu
inducer and the achiral PMMAzo polymer.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image9/image9}

\end{center}
\end{figure}

\textbf{Figure 6} (a) The chemical structures of PMMAzo and CTA. (b)
Changes in FT-IR spectra of CTA/PMMAzo composite films before and after
termal annealing and UV light irradiation at 365 nm. Changes in chemical
shifts of \textsuperscript{1}H NMR spectra in the regions of (c)
azobenzene moiety and (d) methyl ester groups.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image10/image10}

\end{center}
\end{figure}

\textbf{Figure 7} . Changes in CD and UV-vis spectra of the composite
films, consisting of L-Glu/PMMAzo-1 (1/1, w/w, red line) and
D-Glu/PMMAzo-1 (1/1, w/w, blue line) without annealing.

Recently, achiral side-chain Azo units in polymers are found to assembly
into \selectlanguage{greek}π-π \selectlanguage{english}stacking structures with the help of the chiral induction by
limonene.\textsuperscript{35} In this system, we propose that the C-H/\selectlanguage{greek}π
\selectlanguage{english}interaction between cellulose and Azo units may be one of the factors
promoting the occurrence of chirality transfer. In order to further
reveal the mechanism of the chiral induction process, the repeating unit
of CTA, permethylated D-Glu and L-Glu, were synthesized to simplify the
induction system to further verify the conjecture. By utilizing D-Glu
and L-Glu as optical antipodes, we performed the chiral induction
process of achiral PMMAzo-1 in the same manner as CABu. As shown in
Figure 7, the CD spectra of Glu/PMMAzo-1 composite films showed a
intense and mirror-image bisignate Cotton effect. The induction of D-Glu
made the polymer film exhibit a negative CD signal, opposite to the
effect of L-Glu. The results demonstrated that the supramolecular
chirality of the achiral side-chain PMMAzo-1 polymer on thin films could
be successfully induced by the one of the most widely distributed and
important monosaccharides in nature.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image11/image11}

\end{center}
\end{figure}

\textbf{Figure 8} (a) FTIR spectra of D-Glu, PMMAzo-1 polymer and
D-Glu/PMMAzo-1 composite mixtures. (b) Magnified spectra in the range
from 2000 to 1000 cm\textsuperscript{-1}. (c) \textsuperscript{1}H NMR
spectra of D-Glu, PMMAzo-1 polymer and D-Glu/PMMAzo-1 composite
mixtures. (d) Magnified spectra in the range from 2.2 to 2.0 ppm.

The chiral interaction between glucose and the achiral Azo polymer is
easier to be characterized by FTIR and NMR because glucose is the most
basic and well-defined repeating unit of cellulose. Figures 8a and 8b
show the FTIR spectra of D-Glu, PMMAzo-1 polymer and D-Glu/PMMAzo-1
composite polymer mixtures. Three different characteristic absorption
peaks of polymer mixtures were observed during the addition of D-Glu
(Figure 8b). Herein, strong absorption bands near 1750
cm\textsuperscript{-1} were observed, corresponding to the stretching
vibrations of carbon-oxygen (C=O) bonds. And the absorption band around
1600 cm\textsuperscript{-1} is characteristic of the benzene ring.
Additionally, asymmetric stretching vibration of the C-O-C bond was
observed around 1200 \textasciitilde{} 1250 cm\textsuperscript{-1}.
After mixing the polymer with D-Glu, we noted slightly significant blue
shift and red shift of v(C=O) band and v(C-O-C) band, respectively.
Meanwhile, the characteristic absorption peak of the benzene ring
basically does not change in this case. These changes indicate that the
steric environment of the carbonyl group has changed before and after
D-Glu addition.

Furthermore, the \textsuperscript{1}H NMR spectra of D-Glu, PMMAzo-1
polymer and D-Glu/PMMAzo-1 composite mixtures were presented in Figures
8c and 8d. After mixing the polymer with D-Glu, pronounced upfield
shifts was observed for the protic hydrogens (C-H) on the achiral methyl
ester group near the chiral center of the D-Glu. Combining CD, FTIR and
NMR data, the chiral transfer can be attributed to be the result of
pseudochiral intermolecular C-H/O=C hydrogen bonds between D-Glu and the
carbonyl group of PMMAzo segments. As a result, the induction of
circular dichroism from achiral azobenzene-containing polymers through
complexation with CTA (regarded as D-Glu polymer) derivative, which
reflects the transfer of helicity and/or chirality and the imbalance of
left or right \selectlanguage{greek}π-π \selectlanguage{english}stacks, is due to a vast number of intermolecular
C-H/O=C and C-H/\selectlanguage{greek}π \selectlanguage{english}interactions between glucose repeating units and
side-chain Azo units (Scheme 2). This principle also applies to the
interaction between CABu and PMMAzo. However, this capability is
expected to be weaker with CABu and esters in PMMAzo due to the
suppression of C-H/O=C interactions by the bulkier \emph{n} -butylate
groups and the mixture of \emph{n} -butylate and acetyl groups.
Nevertheless, the interactions between chiral inducers and achiral
polymers still need to be deeply explored due to the infinite
intramolecular and intermolecular rotational freedom.\selectlanguage{english}
\begin{figure}[H]
\begin{center}
\includegraphics[width=0.70\columnwidth]{figures/image12/image12}

\end{center}
\end{figure}

\textbf{Scheme} \textbf{2} Proposed models of (left) chiral C-H/O=C and
C-H/\selectlanguage{greek}π \selectlanguage{english}interactions between D-Glu and PMMAzo polymers and (right) \selectlanguage{greek}π-π
\selectlanguage{english}stacks of side-chain Azo building blocks.

Conclusions

In summary, chirality induction of achiral azobenzene-containing polymer
films by natural cellulose derivatives was systematically studied. The
induced circular dichroism of the polymer composite films can be tuned
by adjusting the annealing treatment, the content of the
chirality-inducing scaffolding and the molecular weight of the Azo
polymer. Meanwhile, a chiroptical switch with more than five cycles can
be successfully constructed by the \emph{trans} -\emph{cis}
isomerization of azobenzene units. By using the basic repeating units of
cellulose, permethylated D-Glu and L-Glu, the mechanism of chiral
induction and transfer was elucidated. Chirality transferred from the
chiral semi-synthetic biomaterials to polymer domains and induced the
aggregation chirality of the achiral side-chains through C-H/O=C and
C-H/\selectlanguage{greek}π \selectlanguage{english}interactions between glucose repeating units and PMMAzo polymers.
Using cellulose that are widely distributed in nature to induce strong
circular dichroism in achiral polymers, this work provides an elegant
and facile method to transfer chirality between host and guest
substances, which facilitates the further functionalization of
chiroptical polymer materials with manipulatable properties.

Experimental

\textbf{Synthesis of PMMAzo polymers}

The PMMAzo polymers were obtained by reversible addition-fragmentation
chain transfer (RAFT) polymerization where 4-cyanopentanoic acid
dithiobenzoate (CPADB) and 4,4'-azobis(4-cyanovaleric acid) (ACVA) were
used as the RAFT agent and the initiator, respectively. For example,
AzoMA (250.0 mg, 0.63 mol), CPADB (3.26 mg, 0.012 mmol), ACVA (0.656 mg,
0.004 mmol) and dried tetrahydrofuran (1.5 mL) were added into a 5 mL
ampoule bottle. The reaction tube was flame-sealed under an argon
atmosphere after deoxygenated with three freeze thaw cycles. Then the
polymerization was carried out at 70 \textsuperscript{o}C for 9 h.
Polymers of other molecular weights were obtained by changing the molar
ratio of monomers and RAFT reagents.

\textbf{Synthesis of D-glucose pentamethyl esters (D-Glu) and L-glucose
pentamethyl esters (L-Glu)}

The glucose (4.10 g, 22.51 mmol) was first dissolved in acetic acid (100
mL) and acetic anhydride (400 mL), then 1.5 mL of concentrated sulfuric
acid was added to the reaction flask, and the reaction was carried out
in ice bath for 2 hours. After the reaction was completed, 200 mL of DCM
was added to dilute the mixture, and then the mixture was washed
successively with ice water (3 \selectlanguage{ngerman}× 300 mL), saturated
Na\textsubscript{2}CO\textsubscript{3} solution, and saturated brine
until the aqueous solution was neutral. The organic phase was dried over
anhydrous sodium sulfate, and then DCM was removed under reduced
pressure to obtain D-Glu. L-Glu was also synthesized with the same
procedure.\textsuperscript{27}

\textbf{Preparation of CABu/PMMAzo composite films}

Firstly, 2.0 mg of \textbf{PMMAzo-1} (\emph{M} \textsubscript{n} = 4600)
and 4.0 mg of CABu were co-dissolved in 200 \selectlanguage{greek}μ\selectlanguage{english}L THF solvent. Then, 100 \selectlanguage{greek}μ\selectlanguage{english}L
of the mixture was spin-coated on a clean quartz plate at a low-speed of
600 rpm for 10 s and a high-speed of 1900 rpm for 20 s. The composite
film was annealed at 80 \textsuperscript{o}C for 10 min. The other
composite films were prepared by changing \emph{M} \textsubscript{n}
of\textbf{PMMAzo} polymers, the mass ratio of CABu to \textbf{PMMAzo-1}
, solvents, and the chiral biosources.

Supporting Information

The supporting information for this article is available on the WWW
under https://doi.org/10.1002/cjoc.2021xxxxx.

Acknowledgement

The authors are grateful for the financial support from the National
Nature Science Foundation of China (92056111 and 21971180), China
Postdoctoral Science Foundation (2022M722312), Key Laboratory of
Polymeric Material Design and Synthesis for Biomedical Function, the
Priority Academic Program Development (PAPD) of Jiangsu Higher Education
Institutions and the Program of Innovative Research Team of Soochow
University.

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\begin{longtable}[]{@{}l@{}}
\toprule
Manuscript received: XXXX, 2022 Manuscript revised: XXXX, 2022
Manuscript accepted: XXXX, 2022 Accepted manuscript online: XXXX, 2022
Version of record online: XXXX, 2022\tabularnewline
\bottomrule
\end{longtable}

The Authors\selectlanguage{english}
\begin{longtable}[]{@{}lll@{}}
\toprule
& After acceptance, please insert a group photo of the authors taken
recently. &\tabularnewline
& \textbf{Left to Right:} Authors Names &\tabularnewline
\bottomrule
\end{longtable}

\textbf{Entry for the Table of Contents}\selectlanguage{english}
\begin{longtable}[]{@{}l@{}}
\toprule
\textbf{Chiroptical Generation, Switching, and Long-Term Memory in
Supramolecular Azobenzene-Pendant Polymer: Regulation by Cellulose
Peralkyl Esters, D-/L-Glucose Permethyl Esters, Solvents, UV Light
Irradiation, and Thermal Annealing Process} Shiyuan Yi, Laibing Wang,
Xiaoxiao Cheng,* Michiya Fujiki,* Wei Zhang* \emph{Chin. J. Chem.}
\textbf{2022}, \emph{40}, XXX---XXX. \textbf{DOI:
10.1002/cjoc.202200XXX}\tabularnewline
The chirality transfer from a natural chiral biosource to achiral
azobenzene polymers is developed based on the simple and efficient
spin-coated film. The annealing treatment, the content of chiral inducer
and the molecular weight of the Azo polymer are key to the induction of
supramolecular chirality by cellulose derivatives. The corresponding
chirality-inducing mechanism was demonstrated to arise from the
aggregation chirality induced by the C-H/O=C and C-H/\selectlanguage{greek}π \selectlanguage{english}interactions
between the glucose repeating units and the PMMAzo polymer
side-chains.\tabularnewline
\bottomrule
\end{longtable}

\selectlanguage{english}
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\end{document}

