Extraction of Valuable Compounds from Orange Peel Waste for

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Extraction of valuable compounds from orange peel waste for advanced functionalization of cellulosic surfaces Mohamed Fawzy Rehan, Nayera Abdel-Wahed, Amr Farouk, and Manal El-Zawahry ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b04302 • Publication Date (Web): 26 Mar 2018 Downloaded from http://pubs.acs.org on March 27, 2018

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ACS Sustainable Chemistry & Engineering

Extraction of valuable compounds from orange peel waste for advanced functionalization of cellulosic surfaces Mohamed Rehan1*, Nayera A.M. Abdel-Wahed2, Amr Farouk3, Manal M.ElZawahry4 1

Department of Pretreatment and Finishing of Cellulosic based Textiles. Textile

Industries Research Division, National Research Centre, 33 Bohoth Street, Dokki, P.O. Box 12622, Giza 12522, Egypt. 2

Chemistry of Natural and Microbial Products Department, Pharmaceutical and Drug

Industries Research Division, National Research Centre, 33 Bohoth Street, Dokki, P.O. Box 12622, Giza 12522, Egypt. 3

Flavour and Aromatic Department, National Research Centre, 33 Bohoth Street,

Dokki, P.O. Box 12622, Giza 12522, Egypt. 4

Dyeing, Printing and Auxiliaries Department, Textile Industries Research, Division

National Research Centre, 33 Bohoth Street, Dokki, P.O. Box 12622, Giza 12522, Egypt. * Corresponding author. E-mail address: [email protected] (Dr/ Mohamed Rehan)

ABSTRACT The objective of this study is to explore; identify and evaluate the bio-active compound extracted from orange peels (OP) via ultrasonic method as potential ecofriendly agent for multifunctional cellulosic fabrics/fibers. The innovative strategy involved two approaches. (1) A closely prepared surface modification procedure for the production of multifunctional viscose fibers was successfully developed by an eco-friendly in-situ synthesis of Ag, ZnO and ZnO/Ag nanoparticles (NPs) using phenolic compounds extracted from OP. The treated viscose fibers are endowed with remarkable antimicrobial, antioxidant, UV protection as well as photo catalytic self-

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cleaning activity properties. (2) The micro-capsulation and application of limonene extracts from OP as insect-repellent agent for application in textile field. Based on the resultant promoting data, the OP extract can be considered as a promising cheap source that can be employed to develop multifunctional finishing textiles. Therefore, this study introduces novel simplified approach to design innovative cellulosic fabrics/fibers as viable materials for functional sportswear, medical and fashion clothing using active extracts from sustainable orange peels. KEYWORDS: Orange peels (OP), phenolic compound, Limonene, in-situ NPs, cellulosic fabrics/fibers, antimicrobial, antioxidant, Ultraviolet protection factor, selfcleaning and insect repellent.

INTRODUCTION Recently, the integration between green chemistry and nanotechnology has received a great attention among researchers 1. Green chemistry is the application of a set of principles to reduction either usage or generation of harmful substances throughout the production or application processes 2. Nanotechnology is a field of science that can be conducted at the nanoscale between 1-100 nm. Particularly, inorganic nanomaterial’s such as metals/metals oxides have received a great attention 3. Recently, the green approaches were used to prepare the nanoparticles and metal oxides of particular shape and size to improve their characteristics

4-5

. These

approaches devoid of toxic chemicals in the preparation protocols to avoid any harmful environmental impacts. Owing to the rich biodiversity of different plant parts and their potential secondary constituents, plants have gained attention in recent years as active media for metal oxides and preparation of nanoparticles

6-9

. Peels of some

vegetables and fruits that are generally thrown away considered as waste products.


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The peels of the citrus fruits contain various natural active compounds like, phenolic compound, flavonoid, natural color and essential oils

10

. These components having

biological activities like antioxidant, antimicrobial, anti-inflammatory and antiproliferative, this can be used for pharmacological, hygiene, biomedical or pharmaceutical purpose 11-13. Considering the importance of the biomedical properties of the natural bioactive compounds comes from the peels as agro-wastes, it has become a necessity to build up a standard towards an integrated approach to extract, purify, identification and characterize these active compounds and ultimately to value added products 14-16. The orange juice (OP) industry employs only the edible fractions of orange and a substantial quantity of peels are discarded as industrial agriculture wastes. OP is the by-products descending from industrial processing or consumption of fruits. It represents about 50 % of the fresh orange fruit weight, which results in an increasing interest to a number of natural products or compounds extraction 17. Such peels are reflected to be low-priced resources of priceless natural ingredients that can be industrialized into great value added products. The main phytoconstituent of flavonoid in OP are hesperetin, naringenin, apigenin, neohesperidin, hesperidin and naringin; and the major phenolic compounds include hydroxycinnamic acids (HCA), such as P-coumaric acid, caffeic acid and ferulic acid 18. Another important family of compound in OP is essential oil. The main phytoconstituent are D-limonene (90 %), citral, α-Pinene, citronella, n-decanal, n-dodecanal and linalyl acetate

19

. The

polyphenol extract from OP exhibit anti-oxidant, anti-carcinogenic, anti-microbial and anti-atherogenic properties agents owing to the existence of phenolic acid and flavonoids

13, 20-21

. Additionally, the employment of OP extract (reducing, stabilizing

or chelating agent) as a green or cleaner technology for the biosynthesis of noble metal NPs and metal oxides was studied

22-27

. Limonene as the main essential oil



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component of the orange peel can be used as mosquito repellent agent, antioxidant potential, anti-diabetic effect and other clinical applications

28-31

. There are different

methods used for extraction of natural products from OP such as Soxhlet extraction 32, steam distillation 33, cold pressing 34, conventional solvent extraction 35, high pressure extraction 36 and supercritical CO2 extraction 37. However, those methods reflect some disadvantages such as long extraction time, high temperature, incomplete extraction processing, and degradation of bioactive compounds. Recently, Recently, new extraction methods such application of microwave

38

or ultrasonic

39

have been

developed. These new methods provide cheap, low energy consumption, short time, simple and rapid extraction of active compounds. The use of metal oxide and nanoparticles on the fabric/fiber surfaces plays remarkable role on the performance and the appearances of the final product. Performance fabrics may have dual or multifunctionality like antimicrobial activity, UV protection function, self-cleaning and thermal stability properties and they are used to increase the fabric's versatility

40-45

.

There are different methods have been established for synthesis of metal oxides and nanoparticles. A polymer-NPs is prepared followed by spinning process 46, exo-situ 4754

and in-situ synthesis of NPs into the fibers surface were used 55-62. Lately, the using

of the plant parts as green obtainable and renewable sources for in-situ incorporation of NPs was prominently concerned more attentions by researchers 63-67. In the present study, we develop for the first time, to the best of our knowledge, an environmentfriendly green and cost effective process for advanced functionalization of cellulosic fabrics/fibers with bioactive compound extracted from OP as agro-waste product. This study has used different objective strategies for the exploitation of the bioactive compounds extracted from OP. (i) the ultrasonic extraction, characterization and identification of bioactive compound to evaluate the phytochemical composition of


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both phenolic and limonene compounds. (ii) In order to enhance cellulosic fabric/fiber functionalities by imparting anti-microbial, anti-oxidant, UV protection and photocatalytic self-cleaning properties, we have been developed a facile and ecofriendly method for the in-situ synthesis of Ag NPs, ZnO NPs and Ag/ZnO NPs on the viscose fibers using an aqueous phenolic compound extracted from OP as reducing, stabilizing and chelating agent. (iii) The limonene extracted from OP can be micro-encapsulated by spray drying and applied on the linen fabric surfaces by impregnation method to add insect repellent property to cellulosic fabrics.

EXPERMENTAL Materials and chemicals Orange fruits (Citrus sinensis) were obtained from local Egyptian market. The fully orange peels were collected immediately after the fruit was peeled. Viscose fibers (Lenzing Viscose®) were kindly supplied by Lenzing AG (Lenzing, Austria). Silver nitrate (99.5 %, from Panreac, Barcelona – Spain), zinc acetate (99.99% trace metals from Sigma-AldrichGermany) and ethanol was obtained from Sigma-Aldrich–Germany. All the chemicals and reagents were used without any further purification. The experimental strategies are demonstrated in flow chart 1.



Flow chart 1: The research strategy Extraction of different active components from orange peel After washing the fresh OP, they cut off into slight pieces. The extraction of bioactive compounds from wet OP was conducted using the ultrasound-assisted extraction technique. The aqueous phenolic compounds from wet fresh OP were extracted using ultrasonic bath operating at 38.50 kHz with maximum power level 500 W, liquor ratio 1:10 at 60 oC for different time periods ( 30, 60, 90 and 120 min). The extraction of limonene from OP was carried out using ethyl alcohol with water (80:20) as a solvent with a liquor ratio of 1:10 at 60 oC and power level 500 W for 60 min. After both extraction, the liquor extracted was filtered, cooled at room temperature and then concentrated by rotary evaporator to give crude active components (phenolic compounds and limonene).


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In-situ preparation of nanoparticles into viscose fibers matrix using phenolic compound extracted The in-situ synthesized Ag, ZnO and ZnO/Ag NPs incorporated viscose fibers via phenolic compound extract from OP was selected for this work. This is due to its ecofriendly route and their vital applications in biomedical field. In general, this was done by impersonation of viscose fibers into the mixing aqueous solution of both metallic precursor and the phenolic compound extract from OP at room temperature for 30 min followed by sonication in the ultrasonic bath. The Ag NPs were in-situ incorporation into the fiber surfaces by impersonation of the fibers into silver nitrate aqueous solution (300 ppm) and 10 ml of phenolic compound extracted as reducing and stabilizing agent for each 100 ml with liquor ratio of 1:50 at room temperature for 30 min after that, the solution was sonicated at 70 oC and power level 90 W for 60 min. For the in-situ synthesis of ZnO NPs, the viscose fibers were immersed into zinc acetate aqueous solution (0.1 M) and 10 ml of phenolic compound extracted for each 100 ml with liquor ratio of 1:50 at room temperature for 30 min. After that, the solution was sonicated at 80 oC and power level 500 W for 120 min. In the case of ZnO/Ag NPs in-situ incorporated viscose fibers, the fibers were immersed into zinc acetate aqueous solution (0.1 M), silver nitrate (300 ppm) and 20 ml of phenolic compound extracted for each 100 ml with liquor ratio of 1:50 at room temperature for 30 min. Finally, the solution was sonicated at 80 oC and power level 500 W for 120 min. After the treatment step, the fibers were picked up and washed by water then left to atmospheric dry for different investigation and characterization. Moreover, the absorbance of residual solution was measured by UV analysis.



Micro-capsulation of limonene The micro-capsulation process consists of two steps; Limonene extract emulsion formulation and then spray drying process 68. The emulsion contained 7.5g limonene extract, 15 g Arabic gum, 15 g maltodextrin and 1 g tween 80 were mixed well in 100 ml under magnetic stirred for 5 min. dissolution of the emulsion was carried out in a UP200S ultrasound homogenizer (IKA Hielscher GmbH, Berlin, Germany) at room temperature, 200 W and 24 KHz for 20 min to obtain a homogenous dispersion. Finally, the emulsion was subject to the spray drying process using Spray Dryer B290 (BÜCHI, Flawil, Switzerland) to form the micro-capsulation of limonene extract. Coating of linen fabrics with microcapsule of limonene Prior to linen fabrics impregnation process, the microcapsules were exhibited to an ultrasonic bath during 5 min, with a view to reduce the aggregation of the particles. The linen fabric is dipped in the ﬁnishing bath contain the ultrasonic-treated microcapsules with 1 % of Span-80 for 60 min, then dried for 10 min at 90 °C and fixation occurs at 120 °C during 3 min. Characterization and measurement

The UV absorption spectra are examined by using UV-Visible multi-channel spectrophotometer (V-630 UV/VIS, JASCO Instruments Ltd, Japan). The morphology of the fabric/fibers surfaces are investigated by using scanning electron microscopy (ZEISS, LEO 1530 Gemini) with an acceleration voltage up to 30 kV equipped with a LaB6 electron gun and a Philips-EDAX/DX4 energy-dispersive spectroscope (EDS). The FTIR spectroscopy (PerkinElmer Co., Ltd., MA, USA) are analyzed the fiber surfaces. OP was analyzed for moisture, ash, crude protein, crude fat, and crude fiber according to the standard methods of the Association of Analytical


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Communities

69-70

. The total phenolic content in the extract was determined by the

Folin-Ciocalteu method

71

. Identification of phenolic compounds was determined by

using direct analysis in real time DART mass spectrometry 72. The mass spectrometer used was a JMS-T100 LC (Accu-ToF) atmospheric pressure ionization time-of-flight mass spectrometer (Jeol, Tokyo, Japan) fitted with a DART ion source.

Evaluation of colorimetric properties The colorimetric properties of the modified fibers was evaluated using a Hunter Lab, Pro spectrophotometer (UltraScan, USA) 41. Evaluation of antimicrobial activities

The antimicrobial activity of the samples was tested against Escherichia coli as gramnegative bacteria, Bacillus subtilis and Staphylococcus aureus as gram-positive bacteria and Candida albican as fungi. The antibacterial activity was tested by means of liquid (turbidity evaluation) and solid medium (agar diffusion) antibacterial using nutrient broth medium. The antifungal activity of the treated viscose fibers was tested using sabouraud dextrose broth medium 16, 73.

Evaluation of antioxidant properties The antioxidant properties for active extracted compound and treated viscose fibers were measured by radical scavenging ability on 2, 2-diphenyl-2-picrylhydrazyl (DPPH) assay

74

and 2,2′-azino-bis(3 ethylbenzthiazoline-6-sulfonic acid (ABTS)

assay 75. Evaluation of UV protection UPF (Ultraviolet Protection Factor) is used to show the UV protecting performance of sun protection for textiles product. In this study, the evaluation of the UPF of the



fibers defined in AS/NZS 4399:1996 by using the UPF calculation system of a UV/Vis spectrophotometer is described ( AATCC Test Method 183:2010-UVA Transmittance). Evaluation of photocatalytic self-cleaning activities The self-cleaning activities by photocatalysis was estimated by degradation of methylene blue (MB) under UV irradiation (315 nm < λ < 380 nm) 42. Evaluation of insect repellent properties Repellent effect, knockdown effect and mortality resulting from tarsal contact with treated material were measured using standard World Health Organization (WHO) tests. The numbers of repellent and knockdown mosquitoes were recorded at fixed intervals (every 10, 30 and 60 min depending for repellent and knockdown rates). The mosquito mortality was observed after 1, 6 and 12 h (conducted in parallel with a control sample). Repellency, knockdown, and mortality rates were corrected using Abbott’s formula 76. Corrected repellency % = Percent observed repellency−Percent untreated repellency / 100 −Percent untreated repellency ×100 Corrected knockdown % = Percent observed knockdown−Percent untreated knockdown / 100 −Percent untreated knockdown ×100 Corrected mortality % = Percent observed mortality−Percent untreated mortality / 100 −Percent untreated mortality ×100

Results and discussion Characterization of extracted active component from wet orange peel OP contain many biologically active molecules such as phenolic compounds, carotenoids and essential oils (Limonene) which are natural compounds with desirable


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health benefits and nutraceutical properties. The proximate analysis in percentage (%) is performed to identify the average composition of OP as revealed in Table 1. Table 1: The proximate content (%) of the orange peel Parameters Moisture content Ash Fiber Protein Carbohydrate

% 49.9±0.75 1.13±0.02 14.8±1.06 1.8±1.05 32.3±1.7

The results in Table 1 indicate that the highest moisture content (49.9±0.75), which is an index of spoilage, may be due to the poor storage stability, the lowest ash content (1.13±0.02), moderate fiber content (14.8±1.06), low protein content (1.8±1.05), suggesting that the OP, could not be preferred choice for protein source and high carbohydrate (32.3±1.7). Phenolic compounds are main group of photochemical determined in OP which is soluble and diffused into the solvent depending on their chemical structure and changes greatly from simple to highly polymerized compounds. In this work we design more efficient, safety and eco-friendly environmental extraction process of phenolic compounds by using ultrasonic extraction and water as solvent which considered an ecological process. The effects of different extraction time were investigated to find the optimal time in the extraction process and the quantitative determination of total phenolic compounds in OP extract estimated according to the Folin-Ciocalteu colorimetric method. As presented in Table 2, the extraction yield of phenolic compound increased as the extraction time increased from 30 to 60 min, while above 60 min the yield slowly reaches a constant. It is worth noting that 60 min was chosen as the optimum time for phenolic compound extraction associated with



faint orange color with pH =5.5. The UV-Vis spectra (Figure 1) for the phenolic compounds was shown two peaks at 250 and 310 nm attributed to n → π* transitions of auxochrom and chromophor substituents including OH, COOH and C = O in the aromatic phenolic structure. Four strong peaks were noticed, at 390, 400, 425, and 450 nm, corresponding to a mixture of flavonoids 77-78. Table 2: Total phenolic content of orange peel extract Extract time (min)

Total phenolic content mg GA equivalent/g wet extract

30

40.7±1.07

60

56.8±2.1

90

57.4±1.09

120

58.1±1.2

1,4

Absorbance (a.u)

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

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1,2

1,0

0,8

0,6

0,4 200

250

300

350

400

450

500

550

600

Wavelength (nm) Figure 1: UV-Vis absorbance spectra for phenolic compound extraction


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The identification of phenolic compounds in the aqueous extract of OP was analyzed successfully using DART-MS (Figure 2, Table 3). The determination of OP components was identified by analyzing the extracted-ion chromatograms of the ion current at m/z values corresponding to [M - H]-and [M + H]+ ions of the studied compounds. The DART-MS analysis of orange peel extracts shown the existence of eight phenolic compounds including five phenolic acid and three flavonoids (Table 3 and Figure 3).

Figure 2: DART-MS spectrum of orange peel aqueous extract



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Table 3: The phenolic compounds identified by DART-MS. Compound

m/z

Types

1

P-coumaric acid

164

Hydroxycinnamic acid

2

Vanillic acid

168

Hydroxybenzoic acid

3

Gallic acid

172

Hydroxybenzoic acid

4

Caffeic acid

180


5

Ferulic acid

194


6

Catechin

290

Flavonoids

7

Sinensetin

373

Flavonoids

8

Nobiletin

403

Flavonoids


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O

OH

O OH OCH3

HO

OH Vanillic Acid

p-Coumaric Acid OH HO

OH

O

O H3CO

HO

OH

OH HO

HO HO

Ferolic Acid

O

Caffeic Acid

Gallic Acid OH HO

O

O O

O

O

OH O

OH OH

O

O

Sinensetin

Catechin O

O O

O

O

O O

O

Nobiletin

Figure 3: The chemical structures of the phenolic compounds Limonene is main essential oil component presents in OP was extracted by ultrasonic method using ethanol/water (80/20) as solvent for 60 min and the yield of Limonene obtained from orange peels is 0.602±1.09 %. Moreover, the physical characteristics of



Limonene were found pale-yellow liquid appearance, pH 3.4 with orange odor and specific gravity (0.86 g/ml). The UV-Vis spectra (Figure 4a) for the limonene OP extract shows the peaks obtained at 250 nm owing to π → π* transition, 300 nm owing to n → π* transition and 400 nm due to the presence of β- carotene. The FTIR spectra (Figure 4b) showed the bands at 3400 (OH – solvent), 2900 (C-H stretch, -CH3), 1600 (C-C stretch, C=CH2) 1450, 1400 (C-H bonding, -CH3), 1300 (C-H bonding of alkene substitution), 1000 (C-C stretch, alkene) and 960, 910 cm-1 (C-H bonding alkene CH2=CH-CH3), respectively. The UV and FTIR characteristic confirm the presence of cyclohexene ring, CH3 and H3C-C=CH2 groups 79.

0,6

Absorbance (a.u)

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

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a

0,5 0,4 0,3 0,2 0,1 0,0 200

250

300

350

400

450

500

Wavelength (nm)


550

600

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100

b

95

Transmittance %

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


90 85 80 75 70 65 4000

3500

3000

2500

2000

1500

1000

500

Wavenumbers cm-1 Figure 4: UV-Vis absorbance spectra (a) and FTIR (b) for limonene orange peels extract Characterization of treated cellulosic fiber/fabrics with orange peel extract In-situ incorporation of the nanoparticles on viscose fibers The appearance of the yellow/brown color in the solution and on the fabrics indicated that the formation of nanoparticles. Owing to their surface Plasmon resonance property (SPR), The UV-Vis spectroscopy is a way to characterize the formed Ag NPs

41, 57

, where the residual liquids after the treatment step were measured by UV–

Vis spectra, see Figure 5.



1,4

Viscose fibers/Ag NPs (a)

1,2

Absorbance (a.u)

1,0 0,8 0,6 0,4 0,2 0,0 -0,2 250

300

350

400

450

500

550

600

Wavelength (nm)

5

Viscose fibers/ZnO NPs Viscose fibers/ZnO/Ag NPs

(b)

Absorbance (a.u)

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

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4

3

2

1

0 300

350

400

450

500

550

600

650

700

Wavelength (nm) Figure 5: UV-Vis absorbance spectra for residual solution of Ag NPs after treatment of viscose fibers (a) and UV-visible spectra for residual solution of ZnO NPs and ZnO/Ag NPs after treatment of viscose fibers (b)


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Figure 5a shows an absorption peak between 430 and 480 nm that associated with SPR which indicated to Ag-NPs formation. Additionally, the Plasmon response of bulk silver is assured by the existence of shoulder peak at 330 nm 41. The absorption peaks are broad, which may be referred to the formation of aggregated Ag NPs. UV-Vis spectra were plotted to explore the effect of in-situ Ag NPs on the optical properties of ZnO NPs incorporated viscose fibers. Figure 5b shows the UV-Vis absorption spectra of the absorbance of the supernatant solutions. The ZnO NPs show optical absorption below 400 nm, which can be assigned to the band–band electron transition of ZnO NPs. This optical absorption improved in the spectra of ZnO/Ag NPs and the optical absorption above 400 nm is attributed to the Ag NPs, owing to their SPR. The band gap energy (Eg) of the samples were determined from the equation, Eg = hc / λ = 1239.8 / λ, where Eg is the band gab (eV) energy, h is Plank constant (4.135667×10-15 eV.s), c is the velocity of light (3×108 m/s) and λ is the wavelength at onset of absorption (nm) determined by the linear extrapolation of the steep part of the UV absorption toward the baseline 42. The spectra show λmax at 380 and 425 nm for ZnO and ZnO/Ag NPs respectively which corresponds to the band gap of 3.2 and 2.9 eV respectively. This value is in good agreement with the band gap of ZnO NPs 80, indicating the formation of ZnO NPs. In the present study, the NPs were prepared and incorporated on to the viscose fibers using bio in-situ method. The morphology of modified viscose fiber surfaces were observed using SEM. The SEM images of unmodified and modified fibers with different NPs are shown in Figure 6.



(a)

(b)

(c)


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(d)

(e)

(f)



(g)

Figure 6: SEM images and EDX of blank viscose fiber (a), Viscose fiber/Ag NPs (b, e), Viscose fiber/ZnO NPs (c, f) and Viscose fiber/ZnO/Ag NPs (d, g) respectively The SEM image of blank fiber (Figure 6a) shows clear and slick surface. Figure 6b demonstrates the SEM photographs of the Ag NPs grown viscose fibers by bio in-situ method. Compared with the blank, it is clear to see that the treated fibers were coated with a uniform and dispersed spherical Ag NPs particles. Figure 6c shows the morphology of ZnO NPs treated fibers. From this image, it is clear that there are many aggregated particles on the fiber surface, which is attributed to the cluster formation. The particles are uniform in shape and well dispersed. This aggregation of particles may be due to the high surface activity, and large specific surface area of the ZnO NPs, which lead them to agglomerate easily. The morphology of viscose fiber surface after in-situ ZnO/Ag NPs incorporated was investigated by SEM (Figure 6d). It shows that the viscose fiber surface is covered by dispersed of spherical Ag NPs particles and aggregated ZnO particles. EDX is another way applied to identify the formed NPs on the fiber surfaces; where there are signals appear at 3 KeV which confirmed the immobilization of Ag NPs onto viscose fibers

41

(Figure 6e). The presented signals of Zn and O atoms confirm

the successful in-situ deposition of ZnO incorporated viscose fibers and three peaks at


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0.9, 8.6 and 9.7 KeV relevant to ZnO appeared (Figure 6f). The EDX of ZnO/Ag NPs treated fiber (Figure 6g) showed that, the characteristic peaks of the Ag NPs appeared around 3 KeV and three peaks appeared at about 0.9, 8.6, and 9.7 keV and these correspond to ZnO NPs 81. These results confirm the existence of ZnO/Ag NPs on the viscose fiber surface. There are good matches between the SEM figures and EDX analysis and these results were likely confirmed that the different NPs were incorporated onto fiber surfaces.

The FTIR can be explaining the interaction between nanoparticles and fiber surfaces as shown in Figure 7.

Blank viscose fiber viscose fiber/Ag NPs

Normalized transmittance

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


(C=O)

(a)

(C-OH) (C-O)

4000

3500

3000

2500

2000

1500

Wavenumbers cm-1


1000

500



Blank viscose fiber Viscose fiber/ZnO NPs

4000

(Zn-O)

(b)

3500

3000

2500

2000

1500 -1

1000

500

Wavenumbers cm


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

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4000

Blank viscose fiber Viscose fiber/ZnO/Ag NPs

(Zn-O)

(C=O)

(c)

3500

3000

2500

2000

1500

1000

500

Wavenumbers cm-1 Figure 7: FTIR spectra of (a) viscose fiber/Ag NPs, (b) viscose fiber/ZnO NPs and (c) viscose fiber/ZnO/Ag NPs


Page 25 of 59 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


As shown in Figure 7a, the distinguishing peaks of blank fiber owing to cellulose matrix, appear at 3570 cm-1 (O–H stretching), 2900 cm-1 (C–H stretching), 1650 cm-1 (C=O stretching), 1520 cm-1 (C–H wagging), 1400 cm-1 (C–H bending), and 1300 cm1

(C–O stretching). The FTIR spectra of Ag NPs incorporated fibers (Figure 7a) show

the distinguishing bands of cellulose with boarding, slightly more intensive and blue shifted (higher wave numbers) with additional bands. The band at 1750 cm-1, which is attributed C=O quinone or quinoid of phenolic compound and at 1049 cm-1, may be due to C-OH of phenolic compound. An absorption band at 1360 cm−1 is owing to the existence of C-O-like phenol groups. The two weak bands at 800 cm−1 and 630 cm−1 are owing to the out-of-plane bending vibrations of –O-H and C-H groups of phenolic compound, respectively. Thus, the FTIR study reveals the multi-functionality of the aqueous phenolic compound extract of OP where reduction and stabilization occur concurrently 82.

The FTIR spectra of the ZnO in-situ incorporated viscose fibers have been noted (Figure 7b).The spectra show the typical bands of cellulose. The viscose fiber incorporated with ZnO NPs had a reduced intensity in these bands, which confirms the replacement of the oxygenated groups of the cellulose with the ZnO NPs. The additional stretching mode of the Zn-O band can be seen in the range from 460 cm-1 to 520 cm-1 and an extra sharp single band at 420 cm-1, which is ascribed to a Zn-O vibrational band. These bands were confirmed successfully in-situ synthesis of ZnO NPs on the viscose fiber surface. The FTIR spectra of ZnO/Ag NPs incorporated fibers (Figure 7c) revel that, the characteristic bands of cellulose with more intensive with additional bands at 1750 cm-1, which is attributed C=O quinone or quinoid of phenolic compound, 1049 cm-1, may be due to C-OH of phenolic compound, 460 cm1

to 520 cm-1,which is attributed stretching mode of the Zn-O and at 464 cm-1, which is



attributed to a Zn-O vibrational band. The result obtained from the FTIR confirms that, the in-situ synthesis of ZnO/Ag NPs on the viscose fiber surface was successes 83

.

The XRD patterns of unmodified and modified viscose fibers with NPs are shown in Figure 8.

Blankviscose fiber Viscose fiber/Ag NPs

500 450

Intensity (CPS)

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

Page 26 of 59

(a)

400 350 300 250 200 150 100 50

Ag

0 5

10

15

20

25

30

35

40

45

50

2-theta-scale


55

60

65

70

Page 27 of 59

450 Viscose fiber/ZnO NPs

Intensity (CPS)

400

(b)

350 300 250 200 150 100

ZnO

ZnO

ZnO ZnO

50 0 5

10

15

20

25

30

35

40

45

50

55

60

65

70

2-theta-scale

Viscose fiber/ZnO/Ag NPs

400

(c)

350

Intensity (CPS)

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


300 250 200 Ag

150 100

ZnO

ZnO

ZnO Ag ZnO

50

Ag

0 5

10

15

20

25

30

35

40

45

50

55

60

65

70

2-theta-scale Figure 8: XRD of (a) viscose fiber/Ag NPs, (b) viscose fiber/ZnO NPs and (c) viscose fiber/ZnO/Ag NPs



The presence of strong peaks at 2θ = 12.2°, 21.5° and 23.2°are associated to the crystalline structure of cellulose-II (Figure 8a). As the intensity of the peaks corresponding to cellulose was high in the blank viscose sample, the peaks corresponding to the Ag NPs incorporated viscose fiber could not be seen clearly. Only weak peaks at 2θ = 64.4° attributed to (220) planes of silver with face-centered. The low distinct diffraction peaks at 2θ= 32°, 36.2°, 42° and 51.2° were assigned to (100), (101), (102) and (110) related to structure of ZnO NPs (Figure 8b) were obtained in viscose fiber incorporated with in-situ ZnO NPs. The XRD patterns of viscose fiber in-situ incorporated with ZnO/Ag NPs are shown in Figure 8c. The strong peaks at 2θ = 12.2°, 21.5° and 23.2° are correlated to the crystalline structure of cellulose-II. Successful in-situ synthesis of ZnO/Ag NPs on the viscose fiber is proved by the appearance of the new peaks at 2θ = 32°, 36.2°, 42° and 51.2°related to structure of ZnO NPs and peaks at 2θ =38.3° (major), 44.6° and 64.4°, attributed to diffraction from the (111), (200) and (220) planes of silver with face-centered 81, 84.

Coating of linen fabrics with limonene microcapsules

In this case linen fabric was functionalized with limonene microcapsules to impart insect-repellent properties. The functionalization was carried out by limonene extract from OP following by spray drying process and then coating on the linen fabric. The morphology of microcapsules and treated linen fabric surfaces were observed using SEM (Figure 9).


Page 28 of 59

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(a)

(b)

(c)



(d)

(e)

(f)


Page 30 of 59

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Figure 9: SEM images of micro-capsulated powder (a, b), blank linen fabric (c, d) and treated fabric (e, f) The images of micro-capsulated powder (Figure 9a, b) show that the micro-capsules have different morphologies and the major shape was spherical with minimum aggregation. The SEM images depict that the blank linen fabric is characterized by uniformity and smooth surface (Figure 9c, d). Furthermore, it was noted that the treated linen fabric displays the present and adhesion of limonene microcapsules effectively on the surface of the fabric with uniformly distribution and no agglomeration was found.

In- situ nanoparticles immobilization into viscose fiber mechanism The identification of phenolic compounds in the aqueous extract of OP as shown above indicates that, it is a rich source of phenolic compound. All these phenolic compounds were display a powerful antioxidant properties and could play a main role in the bio-reduction of metal ions (M+) to metal nanoparticles (M0)

85

. The viscose

fibers have a negative zeta potential in neutral solution owing to hydroxyl or carboxyl groups in chemical matrix fibers. When the viscose materials were immersed into metal ions solution (M+ or M+2), the metal ions adsorbed and diffused into the viscose fiber surfaces owing to the electrostatic interaction between M+ ions and negatively charged alcoholate and/or carboxylate groups or by complex interaction between M+2 ions and hydroxyl groups in the cellulose chain. These attraction forces lower the mobility of M+ or M+2, promote the formation of metal nuclei and control their development 41, 55. When viscose fibers are soaked in silver nitrate solution, Ag+ will be firstly adsorbed onto the viscose fiber surfaces due to the heavy metal adsorption capacity and physical stability. Then the Ag+ will bind to cellulose matrix by electrostatic interaction of electron-rich oxygen atoms in hydroxyl and carboxylic



groups

Page 32 of 59

56-57

. Although, the phenolic compounds extracted from OP facilitate the

reduction Ag+ and stabilization of Ag+ to Ag NPs due to the electron donating ability of these phenolic compounds. The possible suggested mechanism for the reduction of Ag+ by phenolic acid compound is presented in Scheme 1. Multiple hydroxyl groups present in phenolic compound of OP may participate in the reduction reaction. The Ag+ ions can form intermediate complexes with hydroxyl (OH) groups present in phenolic acid and then reduced to Ag NPs by accepting an electron from a suitable electron donor leaving phenolic acid into its quinone or quinonoid form. Additionally, these compound produced by oxidation can be adsorbed on the surface of Ag NPs, accounting for their stabilization effect as shown as a band in the FTIR result (Figure 7a). The Ag NPs formed are likely to be anchored through association between Ag NPs and –COOand –OH groups of viscose fibers. The results obtained from FTIR were confirmed this suggested mechanism. OH R

O +

2Ag+

Ag

R

OH

O

Ag

-e

O

O 0 2Ag

-e +

R

Ag

R O

O

Scheme 1 Also, the phenolic compounds extracted from OP act as ligation agent. The aromatic O-H existing in phenolic structure ligate with Zn+2 create to form a stable Zn+2phenolate complexes compound able to undergo direct decomposition and


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consequently leads to the formation ZnO NPs

26, 86

. The possible reaction mechanism

is presented as schematic diagram in Scheme 2. OH HO

HO

+ Zn+2 +

O OH

OH HO

OH

HO

OH

OH

O

OH2

O

Zn+2

HO

O

OH O

O OH2

OH

HO

OH

OH

OH HO

O OH

2

+ ZnO + H2O

OH OH

Scheme 2 The main synthesis route of metal/metal oxide nanostructures composed of two major steps abbreviated in the preparation of metal oxide followed by reduction of the added metal ions. Here a one-step synthesis approach was exploited for in-situ synthesis of ZnO/Ag NPs on the viscose fiber matrix. Phenolic compounds extracted from OP can play dual significant roles in the in-situ synthesis process: it could act as ligating agent for the formation of ZnO NPs and reducing agent for the reduction of Ag+ to Ag NPs.

Colorimetric properties The coloration is a main factor in textile, which leverage the product demand and consumer predilection. The viscose fiber without and with in-situ generated Ag NPs are presented in Photo 1. From Photo 1, it is evident that the color of the viscose fiber was changed to yellow due to the incorporation of Ag NPs inside viscose fiber.



Page 34 of 59

Photo 1: photograph of (left) blank viscose fiber and (right) Ag NPs – viscose fibers To clarify the influence of Ag NPs incorporated viscose fibers on the color of the fiber, the color strength (K/S) and the CIE (L*, a*, b*) system were evaluated. The colorimetric data of pristine and treated viscose fiber with Ag NPs were provided in Table 4. Data of this table illustrated that the pristine viscose fibers have white color with low K/S value (0.80) high L* value (89.88 ± 0.11), negative a* value (-0.31 ± 0.04), and low b* values (2.44 ± 0.08). Moreover, the treated viscose fiber have significantly changed of K/S and (L*, a*, b*) system values compared to the pristine. The K/S value is significantly increased. The L* value is decreased with dramatically increased in a* and b* values. The color changes could be related to the in-situ incorporated of Ag NPs inside viscose fibers matrix.

Table 4: silver content and colorimetric data of treated fibers Samples Blank viscose fiber Viscose fiber/Ag NPs extracted

Silver content (mg/kg) 0.00

K/S 0.80

1269

6.33

L*

a*

b*

89.88 ± 0.11 60.60 ± 1.2

-0.31 ± 0.04 13.4 ± 2.2

2.44 ± 0.08 34.56 ± 1.7

Each value is the mean ± SD of triplicate measurements

Antimicrobial properties The major important factors in biomedical applications are the infection and microbial colonization. It is visualizing that the antimicrobial properties of the nanoparticles


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incorporated viscose fibers in question is an essential property and should be investigated. The antimicrobial properties of blank and nanoparticles incorporated viscose fibers against gram-negative bacteria namely; Escherichia coli, gram-positive bacteria namely; Staphylococcus aureus and Bacillus subtilis and fungi namely;

Candida albican, were evaluated by the qualitative method (inhibition zone) and the quantitative method (reduction %) by using the optical densities 546 nm. These pathogenic microorganisms are the most vital microbial reason for cross-infection in hospitals and at the same time they resist most of antibiotics. The inhibition zone and the reduction % of the antimicrobial reduction induced by different treated viscose fiber samples are demonstrated in Table (5) and (6) respectively.

Table 5: The inhibition zone of pathogenic microorganisms for treated samples Pathogenic microorganisms (inhibition zone nm) Gram positive bacteria samples

Gram negative bacteria

Fungi

Bacillus subtilis

Staphylococcus aureus

Escherichia coli

Candida albicans

Blank viscose fiber

-ve

-ve

-ve

-ve

Phenolic compound

-ve

-ve

-ve

-ve

Viscose fiber/Ag NPs

19

22

18

15

Viscos fiber/ZnO NPs

-ve

-ve

-ve

-ve


16

18

15

12



Page 36 of 59

Table 6: The reduction % of pathogenic microorganisms for treated samples Pathogenic microorganisms (Reduction %) Gram positive bacteria

Gram negative bacteria

Fungi

Bacillus subtilis Staphylococcus aureus

Escherichia coli

Candida albicans

samples

Blank viscose fiber

0

0

0

0

Phenolic compound

0

0

0

0


80

95

85

70

Viscose fiber/ZnO NPs

0

0

0

0


65

88

76

45

It is very obvious that, the blank and ZnO NPs in-situ incorporated viscose fibers does not possess antimicrobial activity, displaying the deficiency of an inhibition zone and the reduction % of pathogenic microorganisms. Also, the aqueous phenolic compound extract of OP did not show any antimicrobial action against the tested pathogens. As expected, the ZnO nanostructure has antimicrobial activity under UV light irradiation 87-88

. In contrast, the introducing and the in-situ incorporated Ag NPs into viscose

fiber matrix or in-situ doping with ZnO NPs have remarkably the antimicrobial activity for all pathogenic microorganisms. The different treatment showed significant differences in the size of inhibition zone and reduction %. The qualitative antimicrobial test of the viscose fibers/Ag NPs sample shows that, the inhibition zones against pathogenic microorganisms were much larger than the viscose


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fibers/ZnO/Ag NPs sample. The inhibition zones of this sample against

Staphylococcus aureus (22 nm) and Bacillus subtilis (19 nm) were much larger than those against Escherichia coli (18 nm) and against fungi; Candida albican (15 nm) suggesting that the Ag NPs has more effective antimicrobial activity against gram positive bacteria. Concerning the quantitative antimicrobial test results of the viscose fibers/Ag NPs sample show the same results were obtained by the qualitative method in which the viscose fibers/Ag NPs sample shows the excellent antibacterial activities against Staphylococcus aureus (95 %), Bacillus subtilis (80 %), Escherichia coli (85 %) and show very good antifungal activity against Candida albican (70 %). Overall, the tables of qualitative and quantitative antimicrobial methods revealed a number of findings as follow; (i) the Ag NPs modified viscose fibers sample display excellent antimicrobial resistance properties. (ii) The antibacterial efficacy of Ag NPs in-situ incorporated viscose fibers towards Staphylococcus aureus as gram-positive bacteria is higher than Escherichia coli as gram-negative and Bacillus subtilis as gram-positive bacteria indicating that the Staphylococcus aureus bacteria are generally more sensitive to Ag NPs modified samples than the other bacteria. This is notably due to differences in the cell wall structure of different types of pathogenic microorganisms. (iii) The introducing and presence of Ag NPs on the surface of the ZnO leads to significant improvement the antimicrobial activity of ZnO NPs in-situ incorporated viscose fibers. (v) The antimicrobial viscose fibers can be considered for medical applications such as surgical aprons, wound cleaning and dressing. Silver NPs have been showed a wide range activity against microorganisms. There are different mechanisms have been reported for the antimicrobial property of silver nanoparticles but the exact on is still understood: (1) adhesion of Ag NPs to the cell surface altering the membrane properties by decomposition of lipopolysaccharide



molecules and accumulation inside the membrane by forming pits and cause large increments in membrane permeability; (2) Ag NPs penetrate into the microorganism cell to result in DNA damage; (3) dissolution of Ag NPs releases antimicrobial Ag+ ions; (4) Ag NPs react with the –SH groups of enzymes leading to inhibition of the microbial proteins 89.

Antioxidant properties Active compounds like phenolic compound and limonene presented in OP extracted are natural antioxidants, which have a vital role in human health because of their free radical scavenging activity. The antioxidant activities were more significant for medical fabrics/fibers, because of trapping the free radial of oxygen species and prevent the cell deterioration and grow a new cell in the skin 90. Natural antioxidants, when practical topically as a cream or fabrics/fibers, may assistance protect the skin from diverse damages by decelerating the effect of free radical, which starts oxidation process that causes damage from oxygen that that may result in cell dysfunction. The antioxidant activity of the OP extracted and modified cellulosic fabrics/fibers by in-situ incorporated or coating methods was also examined by means of DPPH and ABTS assays, as shown in Table 7.


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Table 7: Antioxidant activity of different orange peel extracted and treated fiber samples Antioxidant activity (%)

Samples

DPPH assay

ABTS assay

Blank viscose fiber

0

2.13 ± 0.3

Blank linen fabric

0

2.03 ± 0.1

Phenolic compounds extracted

99± 0.3

99 ± 0.8

Limonene extracted Encapsulated limonene

99±0.1 58.2 ±0.8

99 ± 0.4 64.5±1.2


98 ± 1.06

98 ± 1.3


40.5 ±1.2

46.2 ±1.0


33.3 ±1.4

35.3 ±2.4

Linen fabric/encapsulated limonene

25.6 ±1.01

27.3 ±2.3

Each value is the mean ± SD of triplicate measurements

Table 7 reveals that; (i) although, cellulosic materials contain hydroxyl groups leading to weak antioxidant effect. However, the results we obtained displayed no antioxidant effect due to the low sensitivity of DPPH to detect such very low antioxidant effect of untreated cellulosic fabrics/fibers. On the other hand, the ABTS technique is highly sensitive to detect such low antioxidant effect

75

. This sensitive ability could be

attributed to the reaction mechanisms involved. (ii) The extracted OP as well as treated cellulosic fabrics/fibers have antioxidant activity. (iii) The highest activities were obtained with ABTS assay (iv) However, the highest scavenging activity was exhibited by phenolic compounds and limonene extracted samples respectively, whereas linen fabric/encapsulated limonene had the lowest scavenging activity. The antioxidative activity of natural compound chiefly owes to their redox property, which plays an imperative role in captivating and neutralizing free radicals. The major antioxidative orange peel phenolic compound can be divided into two general groups: phenolic acids (Gallic acid, Caffeic, Vanillic, p-Coumaric acidand Ferulic acid) and



Page 40 of 59

flavonoids (Nobiletin and Sinensetin). Phenolic acids usually act as antioxidants by trapping free radicals, while flavonoids can scavenge free radicals and chelate metals as well

91

. The antioxidant effect of limonene can be attributed to the synergistic

activities of multiform unsaturated structure of limonene

91-92

. (v) In-situ Ag NPs

incorporated viscose fibers has higher inhibitory activity as compared to the anther treated viscose fibers, which may be attributed to the higher polyphenol content in this sample. (vi) The moderate antioxidant activity of viscose fiber/ZnO NPs and viscose fiber/ZnO/Ag NPs may be attributed to the consumption of phenolic compound in chelating and reduction of Zn+2 and Ag+. (vii) The moderate and low antioxidant activity obtained by encapsulated limonene and encapsulated limonene coated linen fabrics respectively, may be attributed to loss of some limonene during the encapsulation process and/or during the application on the textile fabrics due to a low 93-95

resistance of the encapsulated limonene to heat or pressure

. Comparing to

previous results reported in literature, the antioxidant activity of the modified cellulosic fabrics/fibers by in-situ incorporated or coating methods is much higher than that reported in literature for cellulosic after incorporation of nanogold 96 and the same level for cotton fabric treated with natural product

97-99

. Therefore, all the

samples improved hygiene antioxidant property and the OP extracted as well as treated cellulosic fabrics/fibers can be considered for medical applications.

UV protection properties There are many diseases are linked to exposure of skin to solar ultraviolet light radiation likes freckles, sunburn and skin cancer. The solar UV light radiation contains three part; UV-A (400-315 nm), UV-B (315-290 nm) and UV-C (290-200 nm). The most of the UV-C and UV-B are filtered by the ozone layer. The main actual damage to human skin is UV-A. The much more attention has been paid on UV


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protective finishing of textile fabric/fibers goods by using metal oxides and NPs. The present study also confirmed that the metal oxides and NPs could significantly enhance the UV protective properties of cellulosic fibers. A simple, green chemical in-situ incorporated of Ag, ZnO and ZnO/Ag NPs into viscose fibers were suggested with a view to enhance the UV-protection property. Ultraviolet protection factor (UPF) can directly evaluate the UV-blocking activity of the viscose fibers. The UPF of blank and NPs in-situ treated viscose fibers was measured and represented in Table

8. Table 8: UV protection of treated fibers Samples

UPF

Blank viscose fiber

103


224


290 442


From this table, it can be noted that, the UPF values of the NPs treated fibers were higher than that of the blank fibers which indicate that the anti-UV property of viscose fibers is weak. It is notable that, the in-situ ZnO/Ag bi-component nanoparticles incorporated viscose fibers have the highest remarkable UV protection property in comparison with the viscose fibers treated with one component Ag NPs or ZnO nanostructure. The reasons for UV protection of metal oxides and Ag NPs incorporated cellulosic fibers could be due to the mechanism of the UV absorption property which is ascribed to the electronic structure of ZnO as semi-conductors. The UV absorption properties of ZnO are owing to its fundamental optical band gap energy, which is about 3.2 eV (381 nm) in our case. The ZnO particles can absorb light with the energy of hυ that matches or exceeds their band gap energy. The ZnO NPs have band gap energy in the UV range of the solar spectrum, and therefore ZnO



particles block UV radiation 100. The incorporated of Ag NPs into fibers matrix causes high UV absorption as a result of fiber color change to yellow/brown yellow and imparts a very efficient UV scattering because of the large refractive index of silver NPs

55

. Therefore, all treated viscose fiber samples have achieved excellent UV

protective property. These results suggested that the NPs incorporated viscose fibers were very effective at blocking out ultraviolet light and providing protection to human skin against harmful UV irradiation.

Photo catalytic self-cleaning properties One among the main applications of ZnO NPs is their catalytic action. Photo catalytic self-cleaning activity of in-situ treated viscose fibers was investigated by selecting the photo catalytic degradation of methylene blue (MB). The reduction potential of methylene blue (MB), E0red is 0.011 V (NHE), while the EeCB

of ZnO is 0.15 (NHE). On this ground, the MB is appropriate model for study the

photo catalytic activity and MB can be photo reduced in the presence of ZnO NPs 42. To evaluate the photo catalytic self-cleaning activity of the NPs incorporated viscose fibers, we measured the UV absorption changes of MB aqueous solution in the presence of treated viscose fibers under UV irradiation light for a range of given time. Figure 10 shows the spectral change of the methylene blue in the ZnO NPs incorporated viscose fibers (Figure 10a) and ZnO/Ag NPs incorporated viscose fibers (Figure 10b) under 8 h UV light illumination. A rapidly decrease in the absorbance at 665 nm occurs as the irradiation time increases as shown in Figures 10 due to the degradation of MB and a minor blue shift could be noted ascribed to the formation of the demethylated dyes

42

. The self-cleaning effectiveness was estimated by

subsequent the changes of MB concentration (C/C0) as a function of UV light


Page 42 of 59

Page 43 of 59

illumination time. Under UV light illumination, Figure 10c show that, the MB degradation in contact with blank viscose fibers stayed nearly at the same level under UV light illumination, which means that, it does not possess any photo-degradation ability. The incorporation of ZnO NPs and ZnO/Ag NPs onto viscose fiber surfaces caused noteworthy enhancement in photo-degradation of MB under UV light illumination. Figure 10c clearly shows that, Compared to the in-situ ZnO NPs incorporated viscose fibers, the in-situ depositions of the Ag NPs on ZnO NPs incorporated viscose fibers exhibited a significant increase in photo catalytic selfcleaning properties, which may be attributed to the beneficial effects of Ag NPs deposition on the photocatalytic activity of ZnO under UV light irradiation as discussed in the following mechanism.

1,8 1,6

Absorbance %

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


1,4 1,2 1,0


MB ref 2h 4h 6h 8h

(a)

0,8 0,6 0,4 0,2 0,0

-0,2 400

450

500

550

600

650

Wavelength (nm)


700

750

800


1,8

1,4

Absorbance %


MB ref 2h 4h 6h 8h (b)

1,6

1,2 1,0 0,8 0,6 0,4 0,2 0,0 -0,2 400

450

500

550

600

650

700

750

800

Wavelength (nm)

1,0 0,9 0,8

C/C0

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

Page 44 of 59

0,7 0,6 0,5

(c)

0,4

Blank Viscose fiber

0,3

Viscose fiber/ZnO NPs Viscose fiber/ZnO/ Ag NPs 0

2

4

6

8

Irradiation Time (h) Figure10: Spectral changes of methylene blue in the presence of ZnO NPs incorporated viscose fibers (a) ZnO/Ag NPs incorporated viscose fibers (b) and C/C0 changes of methylene blue after (c) 8 h irradiation


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The main process of MB degradation in the presence of metal oxides includes two steps. First one is the separation of electron-hole pairs in metal oxides then following by reduction–oxidation reaction. After ZnO NPs incorporated viscose fibers was irradiated by UV; the electron from the valence band of ZnO is promoted to the conduction band, creating pairs negative electrons (e-) and positive holes (h+). These active e-/h+ pairs can motivate the creation of reactive oxygen species, like as HO• and O2−•. These active species can play an imperative role in reduction–oxidation reaction of organic compound (MB) 52 . Therefore, the charge separation on ZnO surface is a crucial factor to affect the efficiency of MB photo degradation in ZnO under UV irradiation. Ag NPs can be enhancement the e- and h+ separation by acting as electron trap and the subsequent transfer of trapped electrons to the adsorbed oxygen acting as an electron acceptor and change the energy band structure of ZnO. This may be attributed to the electronic interaction occurring at the connection region between the Ag NPs and the ZnO NPs surface 42. This may cause the removal of electrons from ZnO into the vicinity of the Ag NPs resulting in the formation of the Schottky barriers leading to improve the charge separation as shown in Figure 11. Those electrons will be scavenged by oxygen molecules absorbed on the Ag NPs surface forming superoxide anion. Moreover, the holes at ZnO NPs surface can be oxidize the adsorbed H2O to produces hydroxyl radicals.



Page 46 of 59

Figure 11: the charge electron-hole separation in ZnO/Ag NPs under UV irradiation Insect repellent properties Many species of the insect are vectors of diseases. The blood sucking insects likes mosquitoes, flies, lice and bed bugs can torment humans and animals and can transmit dangerous disease. It is estimated that malaria causes over a million deaths mainly of African children every year. Insecticide-treated textile fabrics can provide effective levels of protection dangerous disease for individuals and the community. Recently, many of research work have been carried out on the incorporation of insect repellents on textiles and garments meant for outdoor activities. Insect repellent fabrics/fibers are normally prepared by two ways. The first one is the incorporation of the repellent agents on the fabric/fiber surfaces in its final form by fixation of repellent agents on the fabric/fiber surfaces by coating or encapsulation techniques

28, 76, 101-102

. The

second way is the incorporation of the repellent agents on fibers or yarn during the


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spinning step of the fibers

103

. The encapsulation technology was strong in increasing

the durability of the textile finishing processes

104-105

. The release mechanism of the

agents in the encapsulation technology occurs by diffusion through the capsule wall and/or rupture of the microcapsules

106

. Plant based bio-compounds are generally

safer to humans and fish with very low toxicity levels. Pesticide products containing based bio-compounds are employed for flea and tick control on pets, as an insecticide aerosol, an outdoor dog and cat repellent, a fly repellent tablecloth, a mosquito larvicide, and an insect repellent for use on humans

107-108

. Unfortunately, almost

methods used in insect repellent treated fabrics a large amount of water, energy and hazard toxic chemical materials. Thus, development of clean, non-toxic, environmentfriendly methods for the synthesis of insect repellent fabrics/fibers is needed. In this current approach, we attempt to use encapsulated limonene extracted from OP as a facile, green and cost effective approach for insect-repellent finishing process by coating linen fabrics with encapsulated limonene extracted. Table 9 shows bio-assay test result expressed as repellency percent, knock-down percent and mortality percent obtained with linen fabrics treated with encapsulated limonene extracted before and after washing. Table 9 reveals that the treated fabric exhibit toxic activity against mosquitoes. This is evidenced by the substantial values of repellency percent, knock down percent and mortality percent. Also, the values of repellency, knockdown and mortality increase by increasing the exposure time from 60 min to 12 h .The fabric sample showed lower initial knock-down and mortality activities against mosquitoes suggested that part of the mosquitoes would land directly on the fabric surface there by often getting knockdown and being exposed to high absorption of insecticide enough for quick killing action. Obviously, the coated fabrics display decreasing in insecticidal activity after five washing cycles. This result is appropriate particularly,



Page 48 of 59

by using these fabrics for bio-medical application which was potential in some cases where protection is necessary for several days or weeks with no need for washing such as disposable clothing. It must be stressed that the methodology illustrated to recognize this type of insect-repellent fabric is eco-friendly simple, inexpensive, reproducible technique and desirable aspect in green technology. Action mechanism of the limonene extract is not quite clear, may be due to the limonene interfere with octopaminergic nervous system which are absent in human and fishes, thereby giving it its safety and selectivity

109-110

. Furthermore the bioassay test results are presented

as corrected repellency, corrected knock down and corrected mortality. Table 10 shows the corrected toxicity of the treated fabric samples before and after washing.

Table 9: Insect repellent of treated samples Repellency % Samples Blank linen fabric Linen fabric encapsulated limonene Linen fabric encapsulated limonene after washing

Knock-down %

mortality %

10 min

30 min

60 min

10 min

30 min

60 min

1h

6h

12 h

13 57 30

6 83 62

2 95 76

0 23 14

0 67 43

7 82 60

0 0 0

0 44 20

8 79 57

Table 10: The corrected toxicity of treated samples Samples

Corrected repellency % 60 min

Corrected knock-down % 60 min

Corrected mortality % 12 h

Linen fabric encapsulated limonene Linen fabric encapsulated limonene after washing

95

80

77

76

63

59

CONCLUSIONS In this study, bioactive compounds extracted from orange peels (OP) residual e.g. or among these, total phenolic and limonene compounds was successfully designed using ultrasound. These bioactive compounds employed to enhance cellulosic


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fabric/fiber functionalization by imparting antimicrobial, antioxidant, UV protection and photo-catalytic self-cleaning properties as well as insect repellent properties. A simple green synthesizing of bio in-situ Ag, ZnO and Ag/ZnO NPs into viscose fibers via phenolic compounds extracted from OP was carried out as green simple one-pot method. Different characterization techniques, confirmed the success of the in-situ synthesis of Ag, ZnO and Ag/ZnO NPs into viscose fibers using the natural phenolic extract as a reducing, stabilizing and chelating agent. The antimicrobial properties of in-situ incorporated Ag NPs into cellulosic fabrics/fibers displayed a remarkable or excellent antimicrobial activities than Ag/ZnO NPs against four pathogenic microorganisms (two gram positive bacteria namely Staphylococcus aureus and Bacillus

subtilis, one gram negative bacteria namely Escherichia coli and fungi namely Candida albican. Also, the in situ Ag/ZnO NPs incorporated viscose fibers using OP extracts showed much higher UPF values than blank, Ag NPs and ZnO NPs viscose fibers which could be promising resource to be developed into a bio-absorber of ultraviolet rays. In addition to this, the in-situ deposition of Ag NPs on ZnO NPs incorporated viscose fibers increased the photocatalytic self-cleaning properties under UV irradiation than ZnO NPs alone. Therefore, all the samples improved hygiene antioxidant properties and the OP residual extracted as well as cellulosic fabrics/fibers can be considered for medical applications. Furthermore, the linen fabric was coated with limonene microcapsules using spray drying process. The limonene microcapsule was found to be distributed uniformly on the fabric surface to impart insect repellent properties which could reduce the cost and environmental effects. We envision that, this multifunctional cellulosic/ viscose fiber satisfies the market demand for natural "smart" products, and is also a promising practical material for application in the bio medical textile industry associated with a potential economic value.



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TABLE OF CONTENTS (TOC) GRAPHIC

In-situ synthesis of nanoparticles onto cellulose-based fibers using active extracts from sustainable orange peels toward multifunctional protective fibers


Extraction of Valuable Compounds from Orange Peel Waste for

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