Supporting Information

Tree Gum-Graphene Oxide Nanocomposite Films as

Gas Barriers

Abhilash Venkateshaiah§, Jun Young Cheong‡, Christoph Habel¦, Stanislaw Wacławek§, Tomáš

Lederer§, Miroslav Cernik§, Il-Doo Kim‡, Vinod V.T Padil§*, Seema Agarwal∥*

§
Department of Nanomaterials in Natural Sciences, Institute for Nanomaterials, Advanced

Technologies and Innovation (CXI), Technical University of Liberec (TUL), Studentská 1402/2,

Liberec 1, Czech Republic, 461 17

‡
Department of Materials Science and Engineering, Korea Advanced Institute of Science and

Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon 34141, Republic of Korea

¦
Department of chemistry, University of Bayreuth, Universitätsstraße 30, 95447, Bayreuth,

Germany
∥
Macromolecular Chemistry II, University of Bayreuth, Universittsstraße 30, 95447 Bayreuth,

Germany.

*Correspondence Email: vinod.padil@tul.cz (Dr. V. V. T Padil);

agarwal@uni-bayreuth.de (Prof. Seema Agarwal)

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Gums-GO films characterization

SEM and TEM analysis

Film surface morphologies were observed with a scanning electron microscope (SEM, Zeiss LEO
1530), operating at an acceleration voltage of 3 kV employing an Everhart-Thornley secondary
electron detector. Prior imaging, all of the samples were fractured with mechanical force in liquid
nitrogen, vacuum-dried overnight at 50 °C and the samples were sputter-coated (Sputter Coater
208HR) with a thin platinum layer of 2.0 nm. Transmission electron microscopy (TEM) analysis
of instrument (LEO 922, Zeiss, Germany) with an accelerating voltage of 200 kV and the sample
was prepared by using a microtome equipped with a diamond knife under nitrogen conditions.

X-ray diffraction (XRD) analysis

X-ray diffraction (XRD) patterns were recorded on an Empyrean diffractometer (PANalytical

B.V.; the Netherlands, Bragg-Brentano geometry) using Cu Kα radiation (λ=1.54187Å).

ATR-FTIR (Attenuated total reflection-Fourier transform infrared) spectroscopy

ATR-FTIR (Nicolet IZ10, Thermo Scientific, USA) was used to characterize the native gums (GA,
GK and KG), GO, GO/GA, GO/GK, GO/KG films. The spectrometer was equipped with a multi-
reflection, variable angle, and horizontal ATR accessory.

Raman Spectroscopy

WITec alpha 300 RA+ imaging system equipped with a UHTS 300 spectrometer was used.

Thermogravimetric analysis (TGA)

The thermal stability of samples (~5 mg) was studied using a thermogravimetric analyzer (TGA-
4000, PerkinElmer, USA) under nitrogen atmosphere with a flow rate of 50 ml/min. A heating rate
of 10ºC/min was employed.

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Mechanical Properties

Zwick/Roell BT1-FR 0.5TND14 tensile tester was used with a 200 N KAF-TC load sensor and a
strain rate of 25 mm min−1 (preload of 0.02 N mm−1 at 21 °C). Dog bone shaped (length 30 mm
and width 2 mm) samples were stamped using a Ray-Ran cutting machine.

Oxygen transmission rate

Oxygen transmission rates were determined on a Mocon OX-TRAN 2/21 M10x instrument with a
lower detection limit of 0.0005 cm3 m−2 day−1 bar−1. A mixture of 95% nitrogen and 5% hydrogen
was used as carrier gas and pure oxygen (>99.95%, Linde Sauerstoff 3.5) as permeant gas. The
measurements were conducted at 23 °C and relative humidity of 65%, applying the ISO 14663-2
standards.

Water Vapor Transmission

The water vapor transmission rates (WVTR) were determined at 23°C and a relative humidity of
65% on a HiBarSens HBS 2.0 HT (Sempa Systems GmbH, Dresden, Germany). The lower
detection limit is 1×10-6 g m-2 day-1.

Moisture content

A typical to procedure to determine moisture content includes drying 3cm × 3cm films at 100 ᵒC
for 24h. The MC of the films was calculated measuring the change in weight of the sample before
and after drying and is expressed as percentage weight loss. The MC is calculated using the
following equation:

𝑊𝑊0 − 𝑊𝑊𝑑𝑑
𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀𝑀 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 (%) = × 100
𝑊𝑊0

Where W0 corresponds to the initial weight of the sample and Wd corresponds to the weight of the
dried sample.

Biodegradation Test

Samples of GO/Gum films (in duplicates) were tested for biodegradation under aerobic conditions.
The testing methodology is based on the European standard method based on ISO 14851:1999.

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Tested materials was characterized on the content of oxidizable organics (chemical oxygen
demand – total amount of oxygen for total oxidation of organic matter present in the tested
material) – specific COD. Activated sludge from WWTP Liberec in concentration of 4.3 g/L was
used as an inoculum. Approx. 2 g of tested material was added to 95 ml of biological medium
(reference on ISO 14851:1999) and 5 ml of Activated Sludge. The mixture was dosed into 250 ml
respiration cell and respiration test was immediately started. The testing period was 28 days. Only
activated sludge (without any organic substrate) with the same concentration was used as a control
(blank). The Micro-Oxymax respirometer (Columbus Instruments International, USA) was used
for the measurements with paramagnetic oxygen sensor. Biochemical oxygen demand (BOD) was
measured during the test and ratio of total measured BOD to COD (based on accurate weight of
the samples and determined specific COD) was calculated as an expression of degree of
biodegradation according to the following equation. Modification of the standard formula - COD
value used instead of TOD; TOD cannot be accurately calculated (complex chemical structure
with inorganic and organic carbon).

𝑩𝑩𝑩𝑩𝑩𝑩𝑺𝑺
𝑫𝑫𝒕𝒕 = × 𝟏𝟏𝟏𝟏𝟏𝟏 [%]
𝑪𝑪𝑪𝑪𝑪𝑪

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Figure S1 (a) UV-Vis spectra of GO showing a typical peak at 230 nm. (b) Raman spectra of
GO with peaks corresponding to D band (1341 cm-1) and G band (1582 cm-1). (c) FTIR spectra
of GO with peaks at 3380 cm-1 (-OH Stretching), 1724 cm-1 and 1619 cm-1 (C=O stretching of
carboxylic and/or carbonyl moiety functional groups), 1222 cm-1 and 1041 cm-1 (C-O stretching
of epoxy and alkoxy groups). (d) TGA profile of GO. (e) XRD spectra of GO. (f) SEM image of
GO with wrinkled surface of graphene sheet and wormlike structure randomly aggregated.

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Figure S2. Brittle gum films of (a) Gum Arabic, (b) Gum Karaya, (c) Gum Kondagogu.

Figure S3. SEM images of (a) GA, (b) GK, and (c) KG (scale 100μm)

Figure S4. TEM images of GO at different magnifications (a) 0.5μm (b) 50nm

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Figure S5. Representative biological oxygen demand of the nanocomposite films

Table S1. Summary of composition of different films.

Gum GO
Sample name concentration concentration

(g/L) (g/L)

GA/GO 0.5% 10 5

GA/GO 1% 10 10

GK/GO 0.5% 10 5

GK/GO 1% 10 10

KG/GO 0.5% 10 5

KG/GO 1% 10 10

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 Table S2. Summary of mechanical properties of different films.

Young’s Tensile Strength Elongation at

Sample name
modulus (GPa) (MPa) break (%)

GA/GO 0.5% 0.49 19 9

GA/GO 1% 0.82 28 4

GK/GO 0.5% 0.46 22 13

GK/GO 1% 0.60 24 12

KG/GO 0.5% 0.36 15 13

KG/GO 1% 0.46 18 14

Table S3. Moisture content of different films

Sample Moisture content (%)a

GA-GO 0.5% 22.1±0.8

GA-GO 1% 21.3±0.6

GK-GO 0.5% 17.6±0.9

GK-GO 1% 16.0±0.5

KG-GO 0.5% 18.0±1.0

KG-GO 1% 16.6 ±0.5

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Table S4. Biodegradation analysis of nanocomposite films (BOD = biological oxygen demand;
COD = chemical oxygen demand; duration of test = 28 days)

BOD COD
Material Dt28 ∅Dt28 [%]
[mg/L] [mg/L]

GA-GO 620 2197 0.282 28.2

GK-GO 560 1957 0.286 28.6

KG-GO 585 2062 0.284 28.4

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