Modifying Surfaces with the Primary and Secondary Faces of

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Modifying surfaces with the primary and secondary faces of cyclodextrins to achieve distinct anti-icing capability Qi Cheng, Shenglin Jin, Kai Liu, Han Xue, Bing Chen Huo, Xin Zhou, and Jianjun Wang Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.9b00284 • Publication Date (Web): 22 Mar 2019 Downloaded from http://pubs.acs.org on March 22, 2019

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Modifying surfaces with the primary and secondary faces of cyclodextrins to achieve distinct anti-icing capability Qi Chenga, Shenglin Jinb*, Kai Liub, Han Xueb, Bingchen Huod, Xin Zhoua* and Jianjun Wangb,c* a

School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100049 (P.R.

China). b

Key laboratory of Green Printing, Institute of Chemistry, Chinese Academy of Sciences, Beijing

100190 (P.R. China). c

School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences,

Beijing 100049 (P.R. China). d

School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049

(P.R. China). KEY WORDS. Heterogeneous ice nucleation, cyclodextrins, anti-icing surfaces

ACS Paragon Plus Environment

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ABSTRACT. Heterogenous ice nucleation (HIN) induced by organic materials is a long-lasting issue in wide-ranging fields from cryobiology to atmospheric physics, but efforts for controlling HIN are still restricted by incomplete understanding of its mechanism. In this work, distinct antiicing capabilities were achieved by experimentally investigating the HIN behavior on the surfaces modified with the primary face (PF) and secondary face (SF) of cyclodextrins (CDs) (i.e., α-1,4linked D- (+)-glucopyranose with two relatively flat and hydroxylated faces). To achieve this, CDs were firstly immobilized to the surfaces through selectively binding the PF and SF of CDs onto the solid surfaces, as such, either PF or SF is exposed to liquid water. Interestingly, HIN temperature and delay time assays indicate that HIN is depressed when the PF of CDs (which matches with the ice lattice) exposed to liquid water; while the HIN is facilitated when the SF of CDs (which mismatches with the ice lattice) exposed to the liquid water. This is deviated from commonly thought that surfaces with the template of ice lattice match facilitate the HIN. Instead, 1

H NMR studies show that the resonances of hydroxyl (OH) in the SF of CDs is the mostly

deshielded due to the formation of intramolecular hydrogen bonds, in the comparison to that of OH in the PF of CDs, which weakens the interaction between the OH groups on the SF and water molecules. Thus, the distinct anti-icing capabilities of the PF and SF of CDs can be achieved and established by the distinct interactions between OH groups on the two faces and water, which is of great potential for practical applications. The molecular level interactions between surfaces and water molecules may be a more appropriate criterion for forecasting materials’ HIN ability.


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INTRODUCTION

of cyclodextrins (CDs) as a function of ice

Ice nucleation is one of the ubiquitous phase transition on our planet, and critically influences in many fields from climate change1-6, cryobiology5,

7-9

to design and

fabrication of anti-icing surfaces.10-19 Ice

lattice match and surface-water interaction through selectively binding the PF and SF of CDs onto the solid surfaces. By which, the distinct anti-icing capabilities of the PF and SF of CDs were achieved.

nucleation often forms heterogeneously, and is

As known, the surfaces properties of ice

facilitated by the presence of foreign particles

lattice match on facilitating ice nucleation has

or on solid surfaces, that is, heterogeneous ice

been intensively discussed for more than half

nucleation (HIN). For instance: HIN in the

century,21-22 which is commonly thought as

majority of clouds is at the center of

one requisite property for good ice nucleation

precipitation formation, and thus alter the

agents,23 such as AgI24 and kaolinite25 (i.e. the

hydrological cycle and even the Earth’s

hydroxyl groups are arranged hexagonally).

climate.3-4 On the other hand, undesired

However, whether the ice lattice match is the

nucleation of ice on solid surfaces is inevitable

key of HIN is still under debate in many

and leads to serious economic, energy, and

current studies.5, 26-28 Molinero et al. claimed

safety issues.20 However, the rational design

that mismatch to ice lattice and fluctuation

and fabrication of anti-icing surfaces are often

both monotonously decreased the freezing

hindered by incomplete understanding of the

efficiency of monolayers of alcohols or acids

microscopic mechanism of HIN.13 In this

through

studying

article, we experimentally investigated the

surfaces

by

HIN behavior on the surfaces modified with

simulations.28 However, puzzles were cast on

the primary face (PF) and secondary face (SF)

the MD simulations of the ability of hexagonal

hydroxylated

molecular

dynamic

organic (MD)


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nuclei

hydrophilicity by Michaelides et al.26 He

Intensively studies have been made by

concluded that hexagonal surfaces with an ice

simulations and experiments, the exact roles of

lattice match can both inhibit and promote

ice lattice match and surface-water interaction

HIN, since an optimal interaction between

is

water and the surfaces exists for promoting ice

understanding of molecular level mechanisms

nucleation.26 Li et al. found that the HIN can

of HIN .29 This is also of great potential for

be enhanced as long as the motion of the water

designing and fabricating anti-icing materials

is restricted and structurally compatible with a

for practical applications.

regular unit of ice through simulating the HIN

in

highly

an

unconventional

fashion.5

surfaces to probe HIN as a function of the

desirable

in

deepening

the

To achieve this, cyclodextrins (CDs), the

27

within an atomically sharp, concave wedge.

Recently, by combining experiments and simulations, Michaelides et al. unraveled that the origins of ice nucleation on cholesterol crystals, which was determined by the ability of flexible hydrophilic surfaces forming unconventional ice-templating structures and nucleation sites offered by the diverse

cyclic oligosaccharides composed of α-1,4linked D- (+)-glucopyranose were chosen due to their diverse applications in pharmaceutical and as cryopreservative agents.30-32 It is vital important to understand the HIN behavior of the CDs to better design materials based on CDs in the practical applications such as cryobiology. CDs have a rigid truncated cone

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topography of the surfaces. Also, for the organic surfaces, the ice-like template may no longer necessary for aiding the ice nucleation. Instead,

the

flexibility and

density of

functional groups leads to the formation ice

shape with two relatively flat and hydroxylated faces. One is lined by the secondary hydroxyl (C2/C3-OH) groups (secondary face-SF), and the other is arranged by the primary hydroxyl (C6-OH) groups (primary face-PF)33 as shown


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in Figure 1A. As such, the interior of CDs is

1

hydrophobic, whereas the exterior of CDs is

interactions of the PF and SF of CDs with

hydrophilic. The CD made of six, seven and

water possibly leads to the distinct anti-icing

eight D-glucopyranose units is referred to α-

capabilities. That is, the molecular level

CD, β-CD and γ-CD, respectively (Figure

interaction between surfaces and water

1A).33

(d1)

molecules may be a more appropriate criterion

between the C6-OH in the PF of CDs are

for forecasting materials’ HIN ability. This is

within 4.4 - 4.5 Å (Figure 1A), which matches

consistent with the finding reported by

with ice oxygen atoms on the prismatic plane

Michaelides et.al that an optimal interaction

of ice.34-35 While, the distances (d2) between

strength for promoting ice nucleation between

the C2-OH and C3-OH in the SF of CDs (ca.

the surfaces and the water exists, which

2.8 - 3.4 Å)35 mismatches with the ice lattice

determines the ice nucleation.26

Interestingly,

the

distances

(Figure 1A).

H NMR studies imply the differences in

EXPERIMENT AND ANALYSIS

In this work, we immobilize the CDs through selectively binding the PF and SF of CDs onto the solid surfaces, as such, either PF and SF is exposed to liquid water. And then, the HIN temperature was measured on above prepared surfaces. Freezing temperature and delay time assays show that HIN is depressed when the PF (ice lattice match) of CDs exposed to liquid water. Whereas the SF (ice lattice mismatch) of CDs facilitates the HIN.

Selectively binding of PF and SF of CDs onto the solid surfaces. The C3-OH and C6OH on the SF and PF of CDs can be substituted by amine groups to obtain 3A-amino-3Adeoxy-α/β-cyclodextrin and

(α/β-CD-NH2-3A)

6A-amino-6A-deoxy-α/β-cyclodextrin

(α/β-CD-NH2-6A),36-37 respectively (details are given in the supporting information, SI, Figure

S1-S3).

The

methyldimethoxysilane

3-glycidoxypropyl (GOPTS)

surfaces


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were obtained using the method reported in the

indicated by the variations of the surface

literature38 (SI), were then used to graft CDs

roughness

by immersing the GOPTS surfaces into the 2.0

morphology (Figure S8) as well as the

(Figure

S8)

and

surface

mg mL-1 of α/β-CD-NH2-6/3A solution at 50 ℃ appearance of N1S peaks and the increasing of for 5.0 hours. Then the obtained surfaces were

N/C ratio in the XPS spectra after the

rinsed with ultrapure water (Milli-Q; 18.2 MΩ

modification (Figure S9, table S1 and Figure

cm-1) three times. When GOPTS surfaces were

1C).

immersed into the α/β-CD-NH2-3A solution, the surface with PF exposed (α/β-CD-PF) was obtained as shown in the left of Figure 1B (details in SI, Figure S4). In a similar manner, the surface with SF exposed (α/β-CD-SF) was obtained via immersing the obtained GOPTS surfaces into the α/β-CD-NH2-6A solution as shown in the right of Figure 1B (details in SI, Figure S5).

Relation between the grafting density and the immersion time. Selectively modified the surfaces

were

further

consolidated

by

monitoring the grafting process using quartz crystal

microbalance

with

dissipation

monitoring (QCM-D) (Q-Sense E3). The decreasing of frequency (F) and increasing of dissipation (D) in the process of grafting the CDs on the GOPTS surface indicate the

Verification of the surfaces modified with

changes of mass and viscoelasticity of the

the PF and SF of CDs. The atomic force

surface,39 respectively. The measurement of

microscopy (AFM) (SI, Figure S8) and X-ray

QCM-D can further confirm the successful

photoelectron spectroscopy (XPS) (Figure 1C)

grafting of the CDs on the substrates, and the

investigations

successful

grafting density reaches a saturation after 100

immobilization of the PF and SF of CDs (α/β-

minutes (mins) (Figure 1D). The change of

CD-NH2-6/3A) on the GOPTS surfaces, as

frequency ∆f is proportional to the mass40 of

confirm

the


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the grafted CDs on the GOPTS surface, thus,

mins as shown in the inset of Figure 1D. (After

according to the reaction kinetics, grafting

the grafting reaches saturation on the GOPTS

density of substrate is related to immersion

surfaces, i.e., t is larger than 100 mins, the

(grafting) time as follows:

linear relation is not valid anymore). This

𝐶(𝑡) ∝ ∆𝑓 (𝑡) = ∆𝑓0 (1 − 𝑒 −𝑘𝑡 )

verifies the reaction kinetics equation (1) is (1) applicable to our system.

Where C(t) is the grafting density on the substrates. ∆𝑓0 represents the change of

Attenuated

total

reflectance

Fourier

transform infrared spectroscopy (ATR-

frequency when the grafting saturation is FTIR) was used to further verify the reached on the substrates. k is the grafting rate successful grafting of the PF and SF of α-CDs constant, and t is the immersion time. on the GOPTS surfaces. As, illustrated the Figure 1D was obtained via measuring the

Figure 1E, the PF and SF share the same

frequency (F) change as a function of

absorbance in the range from 3,500 cm-1 to

immersion time. Through fitting the data

3,700 cm-1 due to the OH groups indicating the

obtained by QCM-D (Figure 1D) with the

successful grafting of α-CD on the GOPTS

equation (1). The Δ𝑓0 of -3.90, and k of 0.05

surfaces. Meanwhile, the intensity of the free

can be obtained for the β-CD-SF; similarly, the

OH absorbance at 3,600 cm-1 to 3,700 cm-1 of

Δ𝑓0 of -4.35, and k of 0.03 can be obtained for

the SF of α-CD is much weaker than that of the

the β-CD-PF. By using the obtained values of

PF of α-CD, which suggests that there are

Δ𝑓0 and k, the linear relation of ln (1-∆f / ∆f0 )

more free OH groups on the PF of α-CD. This

and t, i.e., ln (1- ∆f / ∆f0 ) = -kt, is verified

is consistent with the 1H NMR results, which

before the grafting saturation reached on the

will be in the Discussion section.

GOPTS surfaces, i.e., t is less than ca. 100


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Figure 1. Characterization of CDs modified surfaces. (A) Schematic illustration of CDs structure, and the SF and PF of α-CD on the prismatic face of hexagonal ice (Ih) shows the lattice positions of water oxygen atoms in ice (indicated by solid blue circles, the two faces of CD are represented with relative wide and narrow ends for distinguishing). (B) Schematic illustration of β-CD selectively tethered on GOPTS surfaces. The C and H atoms of CHn (n = 0, 1 and 2) are omitted


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for clarity, and rest of the atoms is colored as follows: Si, red; O, yellow; H of OH, blue. The green belt represents a complete belt formed by the intra-HB.33 (C) The XPS spectra of CDs modified surfaces in the comparison with that of GOPTS surface. (D) The immobilization of β-CD on GOPTS surfaces are identified by QCM-D via measuring the frequency (F) and dissipation (D) (SI, Figure S7B) changes during the immobilization, which verifies that CDs (β-CD-NH2-6/3A) were grafted on the GOPTS surface successfully. In the inset, ∆ f represents the change of frequency, ∆f0 represents the change of frequency when the grafting saturation is reached, and t is the immersion time. (E) The ATR-FTIR spectroscopy of α-CD-SF/PF on the GOPTS surfaces. The presence of absorbance at 3,500 cm-1 to 3,700 cm-1 due to the hydroxyl group indicating the success of grafting α-CD-SF/PF on the GOPTS surfaces. D2O was used for the grafting process.

The measurement of the HIN temperature.

droplets with each of 0.2 μL volume were

TH and delay time of ice nucleation on the CD

deposited atop of the CD modified surfaces to

modified surfaces were investigated in a

allow constant relative humidity of 100%, as

closed cell with a volume of 0.628 cm3

the volume of the sample cell is small enough

(diameter of 24.0 mm and height of 2.0 mm)

to allow the thermodynamic equilibria of water

as illustrated in SI Figure S6, using previously

droplet and water vapor. The sealed sample

reported homebuilt apparatus consisting of an

cell was then placed into the chamber of the

optical microscope (Nikon AZ100), a Linkam

cryostage and cooled at rates of 1.0, 2.0, 5.0

LinkPad

Scientific

and 10.0 ℃ min-1 until all the droplets are

The cell composed of

frozen. The freezing of droplets was observed

two cover glasses upheld by a rubber O-ring.42

through a microscope equipped with a high-

Inside the closed cell, nine Milli-Q water

speed CMOS camera system (Phantom V7.3).

cryostage

Instruments Ltd).38,

41

(Linkam


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To obtain the HIN delay time, the surface

cabinet to avoid possible contamination. The

temperature was fixed, and the time needed for

average values of TH and ice nucleation

the HIN to occur was recorded. The deposition

probability (Figure S11) were obtained based

of water droplets and fabrication of sealed cell

on independent ice nucleation events on ca.

were carried out in a class Ⅱ type A2 bio-safety

300 different

locations.

Figure 2. HIN on the PF (ice lattice match) and SF (ice lattice mismatch) of CDs. (A and B) Effects of the SF and PF of α/β-CDs on HIN. Insets show the TH of the fully covered α-CD-NH23/6A and β-CD-NH2-3/6A with various cooling rates, further suggesting that the SF of CDs facilitates the HIN and PF of CDs depresses the HIN. (C and D) TH with various immersion time (the change of frequency) of GOPTS surfaces in CD (β-CD-NH2-3/6A) solution, i.e., grafting densities or grafting mass.


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RESULTS AND DISCUSSION

α/β-CDs were exposed to water, the HIN was

Ice nucleation temperature on the PF and SF of α/β-CDs. When verifies that the GOPTS surfaces has been successfully modified with CDs (α/β-CD-NH2-6/3A), the investigation of HIN behavior of the PF and SF of CDs as a function of ice lattice match and surface-water interaction were then carried out. The TH on the α-CD-SF (ice lattice mismatch) and α-CDPF (ice lattice match) are ca.-23.2 ℃ and 26.2 ℃, respectively as shown in Figure 2A. Interestingly, the TH on the α-CD-SF (ice lattice mismatch) is significantly higher than that on the α-CD-PF (ice lattice match), i.e., αCD-PF (ice lattice match) suppresses the HIN. This finding is deviated from the usual thoughts of surface with template of ice lattice match promotes the HIN. This finding is further confirmed on the β-CD (β-CD-NH2-

suppressed, whereas the HIN was facilitated when the SF (ice lattice mismatch) of α/β-CDs were exposed to water. Insets of the Figure 2A-B show the TH on SF and PF of CDs at various cooling rate, which confirms that PF (ice lattice match) of CDs depresses the HIN. One may argue that the number of OH groups on the SF is twice of that on the PF of CDs, this might have effect on HIN. According to the calculation (SI), the density of OH groups on the same face (PF) of α-CD is nearly twice of that of γ-CD.33 While, the TH on α-CD-PF (26.2 ℃) and γ-CD-PF (-26.6 ℃) was barely changed as shown in Figure S10. Furthermore, the TH of SF of CDs is always higher than that of PF of β-CD during the grafting process (Figure 2C), which further verifies that PF (ice lattice match) of CDs depresses the HIN.

6/3A) modified surfaces, that is, the TH on the

Ice nucleation barriers on the PF and SF

β-CD-SF (ice lattice mismatch) (-22.1 ℃) is

α/β-CDs. To further evaluate and understand

critically higher than that on the β-CD-PF (ice

the distinct nucleation capabilities of PF and

lattice match) (-26.2 ℃) as shown in Figure 2B.

SF of CDs. TH with various immersion time of

As such, when the PF (ice lattice match) of

GOPTS surfaces in CD (β-CD-NH2-3/6A)


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solution,

i.e.,

grafting

densities,

was

systematically investigated.

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𝑎 𝑓(𝜃) of 1.5 × 104 and 0.8 × 104 can be obtained for the β-CD-PF (ice lattice match)

Usually, the ice nucleation temperature is determined by supposing the nucleation rate be approximately a constant while the ice nucleation occurs, thus based on the classic nucleation theory (CNT), after a long but simple derivative (see SI for details), there is,

and

β-CD-SF

(ice

lattice

mismatch),

respectively. The value of 𝑓(𝜃)on the β-CDPF (ice lattice match) is about twice of that on the β-CD-SF (ice lattice mismatch). That is, the nucleation barrier of β-CD-SF to ice is lower than that of β-CD-PF, thus, β-CD-SF nucleates more efficiently in the comparison to

∗ Δ𝐺Hete

𝑎 𝑓(𝜃) (∆𝑇)2

= 𝑐 + ln(1 − 𝑒 −𝑘𝑡 )

(2),

β-CD-PF. This is concordant with the

where ∆G*Hete is heterogeneous ice nucleation

experimental results that the TH on SF (ice

𝑘𝐵 𝑇

=

barrier on surfaces. kB is Boltzmann’s constant, T is the ice nucleation temperature. 𝑎 is determined by water rather than the surface

lattice mismatch) is ca. 4.0 ℃ higher than that on the PF (ice lattice match) of β-CD. In

addition,

as

grafting

density

is

and it is an approximate constant within the

proportional to the change of frequency37, the

small temperature range. 𝑓 (𝜃) is correlated

linear relation of 1/(∆T)2 and ln |∆f | with the

to the properties of the substrate, and θ is the contact angle of ice critical nucleus on the surface. ∆T is the supercooling temperature and ∆T = T - Tm, where Tm is the equilibrium melt temperature of ice. Through fitting the TH during grafting process (immersion time, t) with equation (2) (Figure 2C), the constant

1

slope 𝑎𝑓(𝜃) can be obtained. As illustrated in Figure 2D, obviously, the slope of the linear on β-CD-SF is larger than the that of β-CD-PF. Again, the ice nucleation barrier on the β-CDSF (ice lattice mismatch) is smaller than that on β-CD-PF (ice lattice match), or θSF (contact angle of ice nucleus on SF) is smaller than θPF ,


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i.e., β-CD-SF facilitates the ice nucleation more efficient.

Figure 3. The delay time measurement of water droplets on CDs surfaces is carried out by recording the time elapse for HIN to occur at a fixed temperature of -23.0 ℃ with cooling rate of 5.0 ℃ min-1 (scale bar, 1.0 mm). (A) The left images show the freezing process of supercooled droplets on the α-CD-PF (ice lattice match) and α-CD-SF (ice lattice mismatch), respectively. The freezing droplets were colored with red circle for the clarity. (B and C) The delay time on the SF (ice lattice mismatch) and PF (ice lattice match) of α/β-CDs.


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The waiting time for the ice nucleation to

lattice match) of α/β-CDs suppresses the HIN,

occur on the PF and SF of α/β-CDs. The

which is coincident with the results in previous

distinct anti-icing capabilities of the SF and PF

subsection.

of CDs were further evaluated by recoding the

The interaction of the PF and SF surfaces of

freezing delay time of water droplets on the

α/β-CDs with water. To further deepen the

CDs grafted surfaces at a fixed temperature of

molecular level mechanism of the PF (ice

-23.0 ℃. As shown in Figure 3A, there is only

lattice match) and SF (ice lattice mismatch) of

two out of nine water droplets nucleate before

α/β-CDs on HIN, 1H NMR was employed to

40 seconds on the PF (ice lattice match) of α-

study the chemical environment of OH groups

CD, while seven out of nine water droplets

on the PF and SF, respectively. As shown in

freeze on the SF (ice lattice mismatch) of α-

the Figure 4, the 1H NMR spectrum of the

CD within the same duration. Furthermore, the

resonances of OH groups of β-CD are

freezing delay time on the SF and PF of α/β-

expanded. The resonances at δ 5.71 - 5.69 ppm

CDs was quantitively evaluate as shown in

and δ 5.66 - 5.65 ppm can be assigned to C2-

Figure 3B and 3C, the time needed for the

OH and C3-OH groups (in the SF of β-CD),

nucleation of water droplets on the SF (ice

respectively, which is clearly separated from

lattice mismatch) of CDs (107 and 47 seconds)

the resonances of the free and more shielded

to occur was two order of magnitude lower

C6-OH groups (in the PF of β-CD) at δ 4.44 -

than that on the PF (ice lattice match) of α/β-

4.41 ppm. This clearly reveals that the

CDs (3105 and 4175 seconds), respectively.

chemical environment of C2/C3-OH of CDs is

This implies that the HIN barrier on the SF (ice

the mostly deshielded due to the formation of

lattice mismatch) is vital lower than that on the

intra-HBs between C2-OH and C3-OH.43 This

PF (ice lattice match) of CDs, i.e., the PF (ice

is also consistent with the ATR-FTIR results


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Figure 4. The schematic illustration of HIN on the PF (ice lattice match) and SF (ice lattice mismatch) surfaces of β-CD. The left image is a section of 1H NMR spectrum (400 MHz) of βCD at 25 ℃ in DMSO-d6.

that the peak of the absorbance of free OH on

Although the PF is with the template of ice

the SF of α-CDs is much weaker than that on

lattice match, a much lower and resonance of

the PF of α-CDs due to the formation of intra-

C6-OH on the PF (ice lattice match) of β-CD

HBs. As such, an intra-HB belt is formed on

indicates the more shielded and free OH

the SF (ice lattice mismatch), which weakens

groups. This implies that the interaction

the interaction between C2/C3-OH and water.

between the C6-OH on the PF of CDs and


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Page 16 of 20

water is stronger than that between the C2/C3-

HIN. The 1H NMR evaluation suggests that the

OH on the SF of CDs and water. The

interaction between water and SF is weakened

competition between ice lattice match and

due to the formation of intra-HB between C2-

surface-water interaction induces a net effect

OH and C3-OH in the SF (ice lattice mismatch)

that the PF is more likely to interact with water

of α/β-CDs.43 By contrast, the OH groups in

rather than ice in comparison with that of SF.

the PF of α/β-CDs can strongly interact with

Therefore, PF of CDs depresses the HIN. The

water, since a much lower and completely

interesting result indicates the lattice matching

separated chemical shift of the resonance of

with ice alone is probably not a good criterion

C6-OH in the PF (ice lattice match) indicative

to determine the ability of surface in HIN, and

of the more shield and free OH groups. This

the molecular level interaction between

implies that ice lattice match alone may not be

surfaces and water molecules may be a more

a good criterion for predicting the HIN ability,

appropriate predictor.

and the surface-water interaction at the molecular level may be a more appropriate

CONCLUSION

predictor for forecasting materials’ HIN ability. In summary, distinct anti-icing capabilities

This finding discovered in this article will

were achieved experimentally via modifying

certainly guide scientists to rational design and

surfaces with the PF and SF of CDs. Freezing

fabrication of CDs based materials in

temperature and delay time assays show that

regulating ice formation for diver applications

the PF of α/β-CDs with the distance between

such as cryopreservation.

OH groups matching with ice lattice (Figure 1A) depresses the HIN, while the SF of α/βCDs with the distance between OH groups mismatching with the ice lattice facilitates the

Corresponding Author Jianjun Wang, Email: [email protected] Xin Zhou, Email: [email protected]


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Langmuir

Shenglin Jin, Email: [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS We are grateful the National Key R&D Program

of

China

(2018YFA0208502),

Chinese National Nature Science Foundation (21733010,

51436004,

21503240

and

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Distinct anti-icing capability can be achieved through modifying surfaces with the primary and secondary faces of cyclodextrins. Icelattice match alone is not enough to determine materials’ HIN ability and the molecular level interaction needs to be considered.


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Modifying Surfaces with the Primary and Secondary Faces of

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