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Polimer karbohidrat 150 (2016) 201208

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Polimer Karbohidrat
Halaman Jurnal: w w w. e l s e v i e r. c o m / l o c a t e / c a r b p o l

Absorben Kitosan Magnetik yang Dapat Didaur Ulang dan Diregenerasi Untuk
Serapan Zat Warna
a,b
Weifeng Zhao , Xuelian Huang a , Yilin Wang a , Shudong Sun a
, Changsheng Zhao
a,

a
Sebuah perguruan Tinggi Polimer Ilmu dan Rekayasa, Negara Kunci Laboratorium Bahan Polimer Teknik Universitas Sichuan, 610.065 Chengdu, Cina
b
serat dan Polimer Teknologi, Sekolah Ilmu Kimia dan Teknik, Royal Institute of Technology (KTH), Teknikringen 56-58 SE-100 44, Stockholm, Swedia

Info artIkel a b s t r a

sejarah artikel:
Absorben polisakarida magnetik yang dapat didaur ulang dan dapat diregenerasi untuk penghilangan metilen blue (MB) telah
dibuat dari lapisan nanopartikel magnetic polietilen amin dengan citosan sulfonat dan selanjutnya diikat silang dengan
menerima 16 Maret 2016 Diterima di glutaraldehid. gaya dorong dari lapisan yaitu interaksi elektrostatik antara muatan positif PEI dan muatan negatif SCS. Spektra
direvisi bentuk 5 infra red, potensial zeta, analisa gravimetric termal dan difraksi sinar x menunjukan bahwa absorben polisakarida magnetik telah
berhasil dibuat. Penggabungan dari polisakarida dengan nanopartikel magnetik tidak mengubah nilai megnetiksasi satirasi dari
Mei 2016 Diterima 12 Mei 2016 Tersedia absorben permanen oleh getaran magnetometer sampel. Nanopartikel menunjukan kecepatan penghilangan MB (sekitar 30
secara menit untuk mencapai kesetimbangan). Secara khusus, kemampuan penghilangan MB setelah desorpsi menunjukan
kemampuan regenerasi yang sangat baik. Study ini memberikan pengetahuan baru dalam pemanfaatan polisakarida untuk
online 16 Mei 2016 memperbaiki masalah lingkungan dan menciptakan bahan magnetic canggih untuk berbagai aplikasi.
Kata kunci: 2016 Elsevier Ltd. All rights reserved.
magnetik chitosan penyerap didaur
ulang
regenerable Self-assembly Post-silang

1. Pendahuluan Baru-baru ini, nanopartikel magnetik Fe3O4 telah disintesis dengan


nanokomposit grafin oksida yang difungsionalisasi dengan PAA.
Saat ini, pencemaran air oleh zat warna dan ion logam berat kapasitas adsorpsi PAA/MGO lebih tinggi dibandingkan dengan
telah menjadi masalah serius bagi lingkungan. Di antaranya fungsionalisasi PAA dan kandungan gugus karboksil yang bermuatan
limbah dari industri (Wang et al., 2012). metilen blue (MB) adalah lebih tinggi dari pada MGO. Namun, polimer sintetik tidak dapat
salah satu pewarna beracun yang khas dengan efek berbahaya bagi terdegredasi dan menjadi polusi sekunder setelah penghilangan MB.
manusia (Wang, Ding et al., 2015). Adanya MB dalam sistem air Dengan demikian para ilmuan memfokuskan perhatian mereka
bahkan pada konsentrasi rendah 1 ppm dapat menghambat transisi terhadap pembuatan adsorben magnetic menggunakan polimer alami.
sinar matahari dan mempengaruhi proses fotosintesis dalam air Di antara polimer alami, polisakarida polimer yang bersifat,
(Guo & Wilson, 2012). Oleh karena itu, penghilangan MB perlu biodegradable, hidrofilik dan murah, sehingga biasa digunakan
diperhatikan sebelum dibuang ke lingkungan. Teknik pengolahan sebagai bahan adsorben untuk pengolahan air limbah (Lu et al.,
air limbah yang hemat biaya diperlukan untuk mengurangi 2015). Telah dilaporkan bahwa pektin (Rakhshaee & Panahandeh,
konsentrasi MB pada tingkat yang diperbolehkan. Di antara teknik 2011), karbon aktif / alginat (Ai, Li, & Li, 2011), GO / kalsium
ini, adsorbsi zat warna berdasarkan teknik pemisahan magnetik alginat (Lagu, Wu, Zhong, Lin, & Chen, 2015), selulosa / GO (Shi,
telah mendapatkan perhatian karena murah, efisiensi yang tinggi, Li, Zhong, & Xu, 2014), jerami jagung (Zhao, Xia, Yang, Wang, &
proses operasi yang mudah dan stabilitas mekanik yang baik Zhao, 2014), pati karboksimetil / poli (vinil alkohol) (Gong,
(Chen et al., 2014). Zhang, Cheng, & Zhou, 2015 ) dan -cyclodextrin (Badruddoza,
Banyak polimer termasuk polimer sintetis dan polimer alami Hazel, Hidajat, & Uddin, 2010;. Zhou et al, 2016) dapat digunakan
digunakan dengan bahan magnetik untuk penghilangan MB, untuk membuat absorben magnetik dalam penghilangan MB.
disebabkan jumlah sisi aktif yang besar dalam polimer. Asam Selain polisakarida, chitosan juga menarik banyak perhatian untuk
poliasiklik (PAA) merupakan polimer sintetik yang biasa penghilangan MB. Kitosan dilapisi nanopartikel silica mesopori
digunakan untuk penghilangan MB. nanopartikel PAA/Fe3O4 magnetic dengan kapasitas adsorpsi yang baik dan respon
Telah dikembangkan untuk absorpsi MB dari larutan encer (Mak & magnetic disintesis untuk menghilangkan zat warna metilen blue
Chen, 2004). (Li, Zhou, Nie, Sing, & Chen, 2015).

Corresponding author.

E-mail addresses: zhaoscukth@163.com (W. Zhao), huangxlscu@163.com


(X. Huang), 525642600@qq.com (Y. Wang), sunshudong@scu.edu.cn (S. Sun),
zhaochsh70@163.com, zhaochsh70@scu.edu.cn (C. Zhao).

http://dx.doi.org/10.1016/j.carbpol.2016.05.037
0144-8617/ 2016 Elsevier Ltd. All rights reserved
W. Zhao
W. Zhao
et al.et/ al.
Carbohydrate
/ Carbohydrate
Polymers
Polymers
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(2016)
(2016)
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Zeng et al. (2015) absorben magnetic disintesis dari citosan, Fe3O4 yang 2.3. S u l f o n a s i k i t o s a n
disisipkan campuran mikrosfer untuk penghilangan MB. untuk memanfaatkan 10 g CS dilarutkan dalam asam asetat/DMF (w/w 1/10) pada suhu 60o C
sifat GO yang menjanjikan, bioadsorbent komposit magnetic yang dibuat dari selama beberapa jam. larutan tersebut didinginkan dibawah suhu 0o C.
chitosan magnetic dan GO disiapkan sebagai absorbent magnetic untuk kemudian ditambahkan HSO3Cl/DMF (v/v 1/2 ) selama 1 jam dibawah kondisi
penghilanganMB (Fan et al, 2012). Untuk memperoleh adsorben stabil, gas nitrogen. Reaksi berlangsung dalam suhu 0o C selama 10 jam. CS yang
ethylenediaminetetraacetic dianhydride-dimodifikasi dengan kompleks chitosan tersulfonasi diekstraksi dengan dietil eter, kemudian dimurnikan dengan etanol.
magnetik dibuat menggunakan glutaraldehid sebagai agen ikat silang untuk produk kemudian dikeringkan dalam oven vacumm pada suhu 50o C selama 48
penghilangan MB (Xia et al, 2013). Dengan menggunakan strategi yang sama, jam.
dapat dihipotesiskan bahwa pembentukan dimulai dari muatan negatif 2.4. K a r a k t e r i s a s i S C S
polisakarida dan muatan positif nanopartikel megnetik yang selanjutnya diikuti
spektrometer FTIR (Nicolet 560, America) digunakan untuk
dengan ikatan silang yang dapat menghasilkan partikel magnetic yang dapat
memperoleh pembentukan spectra FTIR dari modifikasi SCS. 1H
didaur ulang dan diregenerasi untuk penghilangan MB. data NMR diperoleh dari spectrometer BRUKER (400 MHz). berat
Tujuan dari percobaan ini yaitu untuk membuat absorben magnetic yang molekul dan distribusi berat molekul diukur dengan kromatografi
gel (HLC-8320GPC, Japan). Analisis unsur dilakukan
dapat didaur ulang dan dapat diregenerasi untuk penghilangan MB dengan
menggunakan CARLO Erba 1106 analyzer unsur karbon (Italy),
lapisan nanopartikel polietilenemin magnetic (PEI@MNP) dengan citosan hidrogen, nitrogen dan sulfur dengan gas murni (He, pada laju alir
sulfonat (SCS) dan selanjutnya diikat silang dengan glutaraldehid. SCS 100 mLmin-1) pada suhu 100o C menggunakan sampel padat.
disintesis terlebih dahulu oleh sulfonat dari CS dengan HSO3Cl. Reaksi
solvothermal digunakan untuk menghasilkan PEI@MNP. Setelah pembentukan 2.5. Pembentukan dan ikatan silang dari SCS pada
nanopartikel magnetik.
SCS menjadi PEI@MNP dengan interaksi elektrostatik, kemudian SCS di
silangkan dengan glutaraldehid. sebagai konsekuensinya, SCS distabilkan 20 mL PEI@MNPs (1 mg/mL) ditambahkan tetes demi tetes ke dalam 10
menjadi nanopartikel magnetik sehingga bahan magnet hybrid ini bisa mL larutan SCS. pembentukan dilakukan dengan pengadukan selama 1 jam.
PEI @ MNP / SCS diperoleh dari pencucian dengan 20 mL air DI selama 3-5
diregenerasi dan didaur ulang selama pengujian air limbah. Spectra Infra red,
kali untuk menghilangkan SCS yang berlebih. untuk ikatan silang dari SCS
resonansi magnetic nuklir, GPC, dan analisis unsur lainnya digunakan untuk pada nanopartikel magnetik, 1 ml dari 50 % larutan glutaraldehida ditambahkan
karakterisasi SCS. Selain itu, IR, potensial Zeta, analisis gravimetric termal dan ke PEI@MNP / SCS, ikatan silang dilakukan pada suhu 70o C selama 3 jam,
yaitu sebagai PEI@MNP/SCSCL. untuk membandingkan efek dari selain
difraksi X-ray juga digunakan untuk melihat terbentuknya ikatan silang SCS
produk asam pada ikatan silang dari SCS, 100 mL asam asetat ditambahkan
pada nanopartikel magnetic. Proses magnetisasi partikel magnetik ditunjukkan pada saat reaksi silang PEI@MNP/SCS, dan dinamakan sebagai
dengan getaran pada sampel magnetometer. adsorpsi, desorpsi dan readsorpsi PEI@MNP/SCSCLA. pembentukan PEI@MNP/SCSCLA digambarkan dalam
skema 1.
nanopartikel magnetik bagi MB juga diteliti.

2.6. K a r a k t e r i s a s i n a n o p a r t i k e l m a g n e t i k
2. Percobaan
Analisis ATR-FTIR menggunakan instrument nicolet 560, dilengkapi
2.1. Bahan dengan single-bouncing diturunkan Total sel refleksi, adetector, dan satu kristal
Chitosan dengan tingkat deasetilasi 95% dan viskositas 100- ZnSe. Semua spektra IR diperoleh dengan resolusi 4 cm-1 dalam jarak 4000-600
200 mpa s dibeli dari Aladin Inc. FeCl3.6H2O 99%, polyetilenemin cm-1. Sebelum analisis termal, semua sampel dikeringkan lebih dulu di 30C
(PEI), dietilen glikol (DEG), asam asetil, asam klorosulfonik, etanol, selama 24 jam di bawah vakum. TGA dari spesimen menggunakan TG209F1
NAOH, dan larutan garam. N.N Dimetilformamida (DMF) disuling (Netzsch Co, Jerman), dan sampel dipanaskan dari 30o C sampai 700o C pada laju
dalam keadaan vakum sebelum digunakan. Air deionisasi (DI) 10o C min-1, dengan kondisi nitrogen. Pengukuran XRD dilakukan menggunakan
digunakan pada saat penelitian. Empyrean difraksi sinar-X (B.V. analitis, Netherland) dengan menggunakan Cuk
radiasi (= 0,154 ). Saat ini, Tegangan operasi masing-masing berada pada 40
2.2. Persiapan untuk polietileneimin magnetic (PEI) kV dan 35 mA. Kisaran 2 adalah 10-70 dalam tahapan 0.03 dengan hitungan
Nanopartikel (PEI@MNPs) waktu 0,2 s. Potensi zeta nanopartikel magnetik ditentukan oleh hamburan cahaya
dinamis (DLS) (ZETA-Sizer, MALVERN Nano-ZS90). Suhunya 25 C dan sudut
PEI@MNPS disintesis dengan modivikasi reaksi solvothermal. Pertama hamburannya adalah 90. Larutan nanopartikel diencerkan 0,1 mg / mL sebelum
0,8 g NaOH ditambahkan kedalam 20 mL DEG pada suhu 120o C selama 1 jam pengujian. Gambar TEM diambil menggunakan Tecnai G2 F20 S-TWIN (FEI,
dibawah kondisi N2, dan didinginkan hingga suhu 70o C untuk menghasilkan Amerika) mikroskop elektron transmisi dengan filamen tungsten pada tegangan
larutan NaOH/DEG. Kemudian, 1 g PEI dan 1 g FeCl3.6H2O didispersi pada percepatan 200 kV. Sifat magnetik dari nanopartikel diukur dari getaran sampel
40 mL DEG, dan dipanaskan pada suhu 220o C dibawah kondisi nitrogen dan magnetometer (VSM) pada suhu kamar dengan density sebesar -10 sampai 10 kG.
diaduk secara konstan. Setelah itu, 5 mL larutan NaOH/DEG dimasukan
kedalam campuran panas. Campuran yang dihasilkan disimpan pada suhu 220o 2.7. Adsorpsi
C selama 1 jam. Kemudian dibiarkan dingin pada suhu kamar. dengan bantuan Penghilangan warna dilakukan dengan menggunakan metil biru (MB)
magnet, produk kotor dicuci dengan air DI beberapa kali untuk menghilangkan sebagai pewarna standar~ 10 mg nanopartikel magnetik terpecah menjadi 4 mL
pelarut dan bahan kimia yang tidak bereaksi, kemudian disimpan dalam larutan 100 Mol / L MB dengan pengadukan secara terus menerus.
garam.
Scheme 1. Illustrating synthesis of magnetic particles.
Setelah kesetimbangan tercapai, pewarna terserap hibrida magnetis dipisahkan 3.1. Preparation and characterization of sulfonated chitosan (SCS)
menggunakan magnet dan konsentrasi kesetimbangan dari pewarna kemudian
ditentukan menggunakan spektrofotometer UV-vis pada = 631 nm. Jumlah The IR of SCS is shown in Fig. 1A. The SCS exhib-
adsorpsi dihitung menggunakan perbedaan konsentrasi MB dalam larutan ited a strong characteristic amide carbonyl stretching band at

sebelum dan sesudah adsorpsi. approximately1631 cm 1 , which was slightly shifted from
that
Q e = (Cb Cf )V/m
(1648 cm 1 ) of neat chitosan (Chang & Huang, 2012). The broad

absorption band at about 30003500 cm 1 was contributed by the
Qe adalah kesetimbangan konsentrasi MB pada adsorben (mg g- stretching vibrations of NH2 and OH groups. The signicant
1); Cb dan C tarif konsentrasi MB sebelum dan sesudah band characteristic
of the sulfonamide group ( N SO3 ) appeared
adsorpsi, masing-masing; V adalah volume (mL) larutan MB; around
1
1204 cm 1 . The intensity of the peaks in the 9601100
dan m adalah berat (g) dari nanopartikel magnetik. Percobaan cm
penghilangan warna diulang tiga kali untuk mendapatkan data region ( C O C vibrations from the sugar units) remained con-
yang akurat. stant since there was almost no change for the C O C bonds
during the reaction (Zhao, Glavas, Odelius, Edlund, & Albertsson,
3. Results and discussion 2014a; Zhao, Glavas, Odelius, Edlund, & Albertsson, 2014b). The
1
H NMR (DMSO-d6 ) spectrum of SCS is shown in Fig. 1B. A peak
Fe3 O4 nanoparticles have been paid considerable attention due at 2.16 ppm was assigned to the methyl hydrogen (s, HNCOCH3 ),
to their alluring properties and a wide range of potential applica- and the peaks at 3.05.0 ppm were attributed to the hydrogen of
tions such as bio-separation (Deng et al., 2005; Wang, Bao, Wang, pyranose ring (m, C1C6) (Xue, Zhao, Nie, Sun & Zhao, 2013). The
Zhang, & Li, 2006), magnetic resonance imaging (Gelbrich, molecular weight and molecular weight distribution were 22.6
Reinartz, kDa and 3.5, respectively. The degree of substitution (DS) of
& Schmidt, 2010; Kania et al., 2015; Wang, Niu et al., 2015; Zhu sulfonic group was determined by elemental analysis, and with a
et al., 2013), drug delivery (Yu, Park, Jeong, Moon, & Jon, 2010; number

Zhu et al., 2013), catalysis (Mojtahedi, Abaee, & Eghtedari, 2008) of 0.92. That is to say, there is approximately one-SO3 functional
and environmental remediation (Li, Liu, Wu, Kim, & Fortner, group in one sugar unit. The high DS of chitosan ensures the pos-
2014). For environmental concern, the current Fe3 O4 -based sibility of self-assembly with positively charged PEI, also the high
polymers are much concentrated on their removal ability of dyes removal capacity of methylene blue.
and/or heavy metals. The magnetic Fe3 O4 nanoparticles aid to
separate the adsor- bent from the wastewater after use. 3.2. Preparation and characterization of magnetic nanoparticles
However, the regeneration and stability of magnetic materials
have not gained enough attrac- tion. Therefore, we propose an
PEI@MNP was synthesized by a solvothermal reaction. Subse-
approach combining self-assembly and post-cross-linking
quently, PEI@MNP was immersed into an SCS solution to form
towards magnetic materials to function- alize and stabilize the
self-assembly clusters. The driving force for self-assembly is the
functional polymers onto magnetic Fe3 O4 nanoparticles.
electrostatic interaction between the positively charged PEI and the
Sulfonated chitosan (SCS) was rstly synthesized by a negatively charged SCS. The structure of the magnetic nanoparti-
sulfonation of CS with HSO3 Cl. A solvothermal reaction was cles was characterized by FTIR (Fig. 2A). All of the samples showed
applied to produce PEI@MNP. After a self-assembly of SCS onto
a broad hydroxyl band at 3400 cm 1 and a characteristic peak
PEI@MNP by electrostatic interaction, the SCS was subsequently 1
of Fe3 O4 at 587 cm . The peak around 1630 cm 1 for all of the
cross-linked by glutaraldehyde. As a consequence, the functional samples was assigned to the stretching vibration of NH in PEI.
SCS was stabilized onto the magnetic nanoparticles so that these After self-assembly of SCS onto PEI@MNP, the strong character-
magnetic hybrid materials could be regenerated and recycled
istic amide carbonyl stretching band at approximately1631 cm 1
dur- ing wastewater treatments. was overlapped with the stretching vibration of NH in PEI.
The PEI@MNP/SCS, PEI@MNP/SCSCL and PEI@MNP/SCSCLA exhib-

ited a shifted band of the sulfonamide group at 1236 cm 1 . After
the cross-linking of SCS by glutaraldehyde (Fig. 2A (c)), the band
Fig. 1. FTIR (A) and 1 H NMR (B) of SCS.

Fig. 2. IR (A) and zeta potential (B) of PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and PEI@MNP/SCSCLA (c) nanoparticles.

around 1016 cm1 enhanced, which was resulted from the newly the electrostatic expulsion of the negative charges in PEI@MNP/SCS
formed C O C groups. Interestingly, the intensity of this band and PEI@MNP/SCSCL magnetic nanoparticles prevented the aggre-
decreased after the addition of acetic acid during cross-linking, as gation of the clusters. Besides the zeta potential, the sizes of the
shown in Fig. 2A (d). Acetic acid is a commonly used catalyst for magnetic nanoparticles also affected their stability in water. Parti-
cross-linking of polysaccharide (Zhao, Li, Guo, & Ma, 2015). The cle sizes and size distribution of these magnetic nanoparticles
cross-linking of SCS was enhanced by glutaraldehyde. As a subse- were also investigated by transmission electron microscopy
quence, more aldehyde groups were cross-linked with SCS, and (TEM). As shown in Fig. 3B, the PEI@MNP nanoparticles exhibited
the amount of free aldehyde groups thus decreased. spherical structure with the mean sizes of about 10 nm. Although
Additionally, DLS measurement was also applied to follow the there was no signicant difference in the size after the assembly
formation of the PEI@MNP/SCSCLA nanoparticles. Zeta potentials of SCS with magnetic nanoparticles, it could be observed that the
number of free PEI@MNP decreased and the cluster
of PEI@MNP, PEI@MNP/SCS, PEI@MNP/SCSCL and PEI@MNP/SCSCLA
nanoparticles markedly increased, suggesting that the SCS
nanoparticles are shown in Fig. 2B. The zeta potential value of
molecules were successfully assembled onto the PEI@MNP. It
PEI@MNP was +0.5 mV. The zeta potential value decreased to
was noteworthy that the clear boarder of PEI@MNP nanoparticles
25.1 mV when the PEI@MNP was self-assembly with SCS. This
could not be observed after the cross-linking of SCS (Fig. 3B (c)).
result indicated that the prepared SCS was a highly negatively
The situation also occurred when acetic acid was added during the
charged polymer. The decrease in zeta potential from +0.5 mV to
cross-linking reaction.
25.1 mV also revealed that the SCS has been successfully coated
As shown in Fig. 4A, the X-ray diffraction patterns of PEI@MNP,
onto the surface of PEI@MNP. The zeta potential of PEI@MNP/SCSCL
PEI@MNP/SCS, PEI@MNP/SCSCL and PEI@MNP/SCSCLA nanoparti-
increased up to 16.9 mV. The more polymer chains of SCS were
cles are also investigated. All the samples displayed the diffraction
cross-linked, the more negative charges were covered. As the
result, peaks similar to that of naked Fe3 O4 . The peaks at 29.55 , 35.13 ,

the cross-linking of SCS beneted the increase of zeta potential, 43.22 , 53.81 , 57.20 and 62.84 corresponded to the cubic phase
and the value further increased when the catalyst of acetic acid of Fe3 O4 (220), (311), (400), (422), (511) and (440), respectively,
was added during the cross-linking reaction. which indicated that all of the magnetic nanoparticles still had
The zeta potentials of the magnetic nanoparticles are strongly cubic crystal structures as the neat Fe3 O4 nanoparticles (Wan et
associated with their stability. Fig. 3A shows the pictures of al.,
PEI@MNP, PEI@MNP/SCS and PEI@MNP/SCSCL magnetic nanopar- 2016). TGA measurement was carried out to determine the per-
ticles suspended in de-ionized water (1 mg/mL). After 60 min, cent weight loss of the magnetite complexes, which manifested
the PEI@MNP nanoparticles aggregated at the bottom of the vial, the amount of SCS assembly on the surfaces of nanoparticles. All
while the PEI@MNP/SCS and PEI@MNP/SCSCL magnetic nanoparti- of the magnetic nanoparticles lost 68% (w/w) of their weights,
cor-
cles were well dispersed in aqueous solution. The reason was that
responding to the evaporation of bound water below 200 C
(Zhao,
Nugroho et al., 2015; Zhao, Odelius, Edlund, Zhao, & Albertsson,
Fig. 3. The stability of PEI@MNP (a), PEI@MNP/SCS (b) and PEI@MNP/SCSCL (c) nanoparticles (A). TEM photos of PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and
PEI@MNP/SCSCLA (d) nanoparticles (B).

Fig. 4. XRD (A) and TGA (B) curves of PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and PEI@MNP/SCSCLA (d) nanoparticles.
2015). The TGA curves of PEI@MNP and PEI@MNP/SCS
showed 200 and 200 G are shown in the inserted image of Fig. 5. All of
weight losses of about 90.2% and 93.1% at 400 C, respectively,
composite nanoparticles exhibited an extremely small hysteresis
indicating that the amount of SCS assembled on the surface of
loop and very low coercivity (about 130 G). These ndings were
PEI@MNP was 2.9%. It was noticed that the thermal stability
the typically characteristic of superparamagnetic particles. The
of PEI@MNP/SCSCL decreased compared to that of PEI@MNP/SCS
satura- tion magnetizations were 68.0, 64.1, 52.4 and 56.9 emu/g
above 200 C, which was due to the low degradation tempera- for the PEI@MNP, PEI@MNP/SCS, PEI@MNP/SCSCL and
ture of pendant glutaraldehyde. As we hypothesized, the thermal
PEI@MNP/SCSCLA nanoparticles, respectively. In comparison to the
stability of the PEI@MNP/SCSCL was enhanced after the addition
naked PEI@MNP, the saturation magnetization of PEI@MNP/SCS
of acetic acid, as shown in the TGA curve of PEI@MNP/SCSCLA
decreased due to the covers of SCS on the surfaces of the
(d).
nanoparticles, which reduced the magnetic moment. The similar
trend was also found in the PEI@MNP/SCSCL and
3.3. Reserved high magnetization of nanoparticles PEI@MNP/SCSCLA . When acetic acid was added during the
cross-linking, the situation became complicated. The VSM
The magnetizations of PEI@MNP, PEI@MNP/SCS, PEI@MNP/ results suggested that the synthetic PEI@MNP, PEI@MNP/SCS,
SCSCL and PEI@MNP/SCSCLA nanoparticles are measured using a PEI@MNP/SCSCL and PEI@MNP/SCSCLA nanoparticles had the
vibrating sample magnetometer (VSM) at 298 K, as shown in Fig. poten- tial to be separated by the magnetic bar when they were
5. No remanence was observed from the magnetization curves at using as adsorbents in wastewater.
low magnetic eld. The remanence of the four samples was zero
and the coercivity was almost negligible in the case of the
absence of the external magnetic eld. The coercivity (Hc) is the 3.4. Recycle and regeneration of magnetic nanoparticles for dye
magnetic- eld strength necessary to demagnetize a magnetic removal
material that is fully magnetized. The magnetic hysteresis loops of
the composite nanoparticles could reect their coercivities. The The removal percentage (%) versus time (min) of the magnetic
enlarged mag- netic hysteresis loops of the nanoparticles in the nanoparticles is conducted, and the results are as shown in Fig.
range between 6A. The magnetic nanoparticles containing SCS exhibited high
removal ability (over 50%) of MB, while the naked PEI@MNP only
adsorbed
Fig. 5. VSM photos of PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and PEI@MNP/SCSCLA (d) nanoparticles.

Fig. 6. The removal percentage (%) of MB versus time (min) for PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and PEI@MNP/SCSCLA (d) nanoparticles (A). Adsorption,
desorption and re-adsorption of MB curves (B) and photos (C) by PEI@MNP (a), PEI@MNP/SCS (b), PEI@MNP/SCSCL (c) and PEI@MNP/SCSCLA (d) nanoparticles.

about 15% of MB. To evaluate the recyclability and regeneration of re-adsorption experiments. All of the adsorbents containing SCS
the magnetic adsorbents, adsorption, desorption and re- exhibited a high ability to desorb and re-adsorb MB. However, the
adsorption experiments are conducted and the results are un-cross-linked PEI@MNP/SCS showed the reduced ability to re-
shown in Fig. 5B and C. As shown in Fig. 6B, the removal adsorb the dye MB. The adsorption, desorption and re-adsorption
ability of MB by the PEI@MNP was kept at a low level during of MB were more visualized in Fig. 6C.
adsorption, desorption and
Scheme 2. The illustration of adsorption and desorption of PEI@MNP/SCS and PEI@MNP/SCSCL .
The adsorption process of MB is illustrated in Scheme 2. For Chen, R., Wang, W., Zhao, X., Zhang, Y., Wu, S., & Li, F. (2014). Rapid hydrothermal
the rst time of MB adsorption, both uncross-linked and cross- synthesis of magnetic Cox Ni1 -xFe2 O4 nanoparticles and their application on
linked SCS magnetic nanoparticles have the ability to adsorb MB removal of congo red. Chemical Engineering Journal, 242, 226233.
Deng, H., Li, X. L., Peng, Q., Wang, X., Chen, J. P., & Li, Y. D. (2005). Monodisperse
due to the interaction between the active sites of adsorbent and magnetic single-crystal ferrite microspheres. Angewandte Chemie International
the cationic group of MB. However, some uncross-linked SCS poly- Edition, 44(18), 27822785.
mers are lost during the desorption of MB. In the re-adsorption of Fan, L., Luo, C., Sun, M., Li, X., Lu, F., & Qiu, H. (2012). Preparation of novel magnetic
MB, the PEI@MNP/SCS has fewer amount of functional SCS, there- chitosan/graphene oxide composite as effective adsorbents toward methylene
blue. Bioresource Technology, 114, 703706.
fore it shows decreased removal ability of MB. Compared with Gelbrich, T., Reinartz, M., & Schmidt, A. M. (2010). Active ester functional single
PEI@MNP/SCSCL , the PEI@MNP/SCSCLA has higher removal ability core magnetic nanostructures as a versatile immobilization matrix for effective
of MB during re-adsorption process. The reason is that the bioseparation and catalysis. Biomacromolecules, 11(3), 635642.
Gong, G., Zhang, F., Cheng, Z., & Zhou, L. (2015). Facile fabrication of magnetic
trapped acetic acid in the cluster might be removed during the
carboxymethyl starch/poly(vinyl alcohol) composite gel for methylene blue
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4. Conclusion Kania, G., Kwolek, U., Nakai, K., Yusa, S.-i., Bednar, J., Wojcik, T., et al. (2015). Stable
polymersomes based on ionic-zwitterionic block copolymers modied with
Herein, we report an efcient method for creating recyclable superparamagnetic iron oxide nanoparticles for biomedical applications.
Journal of Materials Chemistry B, 3(27), 55235531.
and regenerable magnetic adsorbent for MB removal. The mate- Li, W., Liu, D., Wu, J., Kim, C., & Fortner, J. D. (2014). Aqueous aggregation and
rials containing SCS showed high negatively charged surfaces. In surface deposition processes of engineered superparamagnetic iron oxide
addition, due to the presence of Fe3 O4 nanoparticles, the nanoparticles for environmental applications. Environmental Science &
Technology, 48(20), 1189211900.
nanomate- rial exhibited magnetic properties. The cross-linked
Li, Y., Zhou, Y., Nie, W., Song, L., & Chen, P. (2015). Highly efcient methylene blue
PEI@MNP/SCS product was used as an effective adsorbent for the dyes removal from aqueous systems by chitosan coated magnetic mesoporous
removal of MB in a short duration. Furthermore, beneting from silica nanoparticles. Journal of Porous Materials, 22(5), 13831392.
their high satu- ration magnetization (over 52 emu/g), the Lu, T., Xiang, T., Huang, X.-L., Li, C., Zhao, W.-F., Zhang, Q., et al. (2015).
Post-crosslinking towards stimuli-responsive sodium alginate beads for the
obtained polysaccharide adsorbent could be easily separated from
removal of dye and heavy metals. Carbohydrate Polymers, 133,
the solution by a magnet. The magnetic polysaccharide absorbent 587595.
could be regenerated and reused for MB removal. Based on the Mak, S. Y., & Chen, D. H. (2004). Fast adsorption of methylene blue on polyacrylic
experimental results, the pro- posed route can pave a way to acid-bound iron oxide magnetic nanoparticles. Dyes and Pigments, 61(1),
9398.
recycle absorbents to provide large amounts of highly valuable
Mojtahedi, M. M., Abaee, M. S., & Eghtedari, M. (2008). Superparamagnetic iron
polysaccharide materials in the future. oxide as an efcient and recoverable catalyst for rapid and selective
trimethylsilyl protection of hydroxyl groups. Applied Organometallic Chemistry,
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Acknowledgements Rakhshaee, R., & Panahandeh, M. (2011). Stabilization of a magnetic
nano-adsorbent by extracted pectin to remove methylene blue from aqueous
This work was nancially sponsored by the National Natural solution: a comparative studying between two kinds of cross-likened pectin.
Journal of Hazardous Materials, 189(12), 158166.
Science Foundation of China (Nos. 51433007 and 51503125), and
Shi, H., Li, W., Zhong, L., & Xu, C. (2014). Methylene blue adsorption from aqueous
China Postdoctoral Science Foundation (No. 2015 M580791). We solution by magnetic cellulose/graphene oxide composite: equilibrium,
appreciate Miss Ying Liu for the preparation of Fe3 O4 kinetics, and thermodynamics. Industrial & Engineering Chemistry Research,
53(3), 11081118.
nanoparticles. Song, N., Wu, X.-L., Zhong, S., Lin, H., & Chen, J.-R. (2015). Biocompatible
G-Fe3 O4 /CA nanocomposites for the removal of methylene blue. Journal of
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