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Licensed Unlicensed Requires Authentication Published by De Gruyter May 16, 2023

Hollow microgels and their hybrids: classification, synthesis, characterization, properties and applications

  • Ahmad Hassan

    Ahmad Hassan is presently enrolled in M.Phil. Chemistry at School of Chemistry, University of the Punjab (PU), Lahore, Pakistan, under the supervision of Dr. Farooqi. He obtained his BS degree in Chemistry from the same institute in 2021. His area of research is polymer stabilized metal nanoparticles for catalysis.

    , Iqra Sajid

    Iqra Sajid is presently enrolled in M.Phil. Chemistry at School of Chemistry, University of the Punjab (PU), Lahore, Pakistan, under the supervision of Dr. Farooqi. She obtained her BS degree in Chemistry from the same institute in 2021. She completed her BS dissertation under the supervision of Dr. Farooqi. Her area of research is polymer microgels and their hybrids for environmental and catalytic applications.

    , Muhammad Akmal , Muniba Aslam , Prashun Ghosh Roy , Shuiqin Zhou

    Shuiqin Zhou received her BS (1988) and MS (1991) from Xiamen University, China, and her PhD (1996) from The Chinese University of Hong Kong. She received postdoctoral training at SUNY at Stony Brook and then worked at Union Carbide/The Dow Chemical Company as a senior chemist. She started her own research lab at The City University of New York at CSI in 2002 and is currently a professor of Chemistry at Department of Chemistry of College of Staten Island and Ph.D. Program in Chemistry, The City University of New York, 2800 Victory Boulevard, Staten Island, NY 10314, USA, working in field of gel-based nanomaterials for biosensing and smart drug delivery.

    , Ahmad Irfan , Muhammad Shahid , Robina Begum

    Robina Begum is an assistant professor at School of Chemistry, University of the Punjab, Lahore. She obtained her PhD degree in Chemistry from the same institute in 2019. She carried out a part of her research work in the laboratory of Prof. Jianliang Xiao at Department of Chemistry, University of Liverpool, UK as a split-site PhD scholar funded by Commonwealth Scholarship Commission, UK. Her research area is organic–inorganic hybrid materials for various applications.

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    and Zahoor H. Farooqi

    Zahoor H. Farooqi is an associate professor at School of Chemistry, University of the Punjab, Lahore, Pakistan. He worked as a research associate in CSI, CUNY, New York, USA, from January 2009 to March 2010. In 2018, Dr. Farooqi worked for five months as a honorary research fellow in Department of Chemistry, University of Liverpool, UK, and from November 2022 to January 2023 as a visiting academic staff member in Department of Chemical Engineering, Loughborough University, UK. His area of research is microgels loaded with inorganic nanoparticles for catalytic applications.

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Abstract

Hollow microgels and their hybrids have gained much attention in modern-day research because of their fascinating properties and potential applications. This article gives classification, preparation methods, properties and applications of hollow microgels and their hybrids in modern research. Some of the hollow microgels and their hybrids respond to change in specific environmental stimuli like pH, ionic strength and temperature of the medium. They are called smart polymer hollow microgels and smart hybrid microgels, respectively. This peculiar behaviour makes them a suitable candidate for their use in drug delivery, sensing, catalysis and many other fields. This review represents the current advancement along with future perspectives and suggestions for further research in this particular area.


Corresponding authors: Robina Begum and Zahoor H. Farooqi, School of Chemistry, University of the Punjab, New Campus, Lahore 54590, Pakistan, E-mail: , .

About the authors

Ahmad Hassan

Ahmad Hassan is presently enrolled in M.Phil. Chemistry at School of Chemistry, University of the Punjab (PU), Lahore, Pakistan, under the supervision of Dr. Farooqi. He obtained his BS degree in Chemistry from the same institute in 2021. His area of research is polymer stabilized metal nanoparticles for catalysis.

Iqra Sajid

Iqra Sajid is presently enrolled in M.Phil. Chemistry at School of Chemistry, University of the Punjab (PU), Lahore, Pakistan, under the supervision of Dr. Farooqi. She obtained her BS degree in Chemistry from the same institute in 2021. She completed her BS dissertation under the supervision of Dr. Farooqi. Her area of research is polymer microgels and their hybrids for environmental and catalytic applications.

Shuiqin Zhou

Shuiqin Zhou received her BS (1988) and MS (1991) from Xiamen University, China, and her PhD (1996) from The Chinese University of Hong Kong. She received postdoctoral training at SUNY at Stony Brook and then worked at Union Carbide/The Dow Chemical Company as a senior chemist. She started her own research lab at The City University of New York at CSI in 2002 and is currently a professor of Chemistry at Department of Chemistry of College of Staten Island and Ph.D. Program in Chemistry, The City University of New York, 2800 Victory Boulevard, Staten Island, NY 10314, USA, working in field of gel-based nanomaterials for biosensing and smart drug delivery.

Robina Begum

Robina Begum is an assistant professor at School of Chemistry, University of the Punjab, Lahore. She obtained her PhD degree in Chemistry from the same institute in 2019. She carried out a part of her research work in the laboratory of Prof. Jianliang Xiao at Department of Chemistry, University of Liverpool, UK as a split-site PhD scholar funded by Commonwealth Scholarship Commission, UK. Her research area is organic–inorganic hybrid materials for various applications.

Zahoor H. Farooqi

Zahoor H. Farooqi is an associate professor at School of Chemistry, University of the Punjab, Lahore, Pakistan. He worked as a research associate in CSI, CUNY, New York, USA, from January 2009 to March 2010. In 2018, Dr. Farooqi worked for five months as a honorary research fellow in Department of Chemistry, University of Liverpool, UK, and from November 2022 to January 2023 as a visiting academic staff member in Department of Chemical Engineering, Loughborough University, UK. His area of research is microgels loaded with inorganic nanoparticles for catalytic applications.

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: Z. H. Farooqi and R. Begum are grateful to PU, Lahore, Pakistan, for a research grant for the period of 2022–2023. S. Zhou acknowledges research support from the NIDDK-NIH under award no. R15DK127360-01A1. A. Irfan is grateful to King Khalid University for financial support (RGP1/36/43).

  3. Conflict of interest statement: The authors declare that they have no conflicts of interest regarding this article.

Abbreviations

4-AP

4-Aminophenol

4-NP

4-Nitrophenol

AA

acrylic acid

AFS

atom force spectroscopy

Ag NPs

silver nanoparticles

Ag

silver

AgNO3

silver nitrate

AIBA

2,2′-Azobis(2-methylpropionamidene) dihydrochloride

APBA

3-Aminophenylboronic acid

APMA

N-(3-Aminopropyl)methacrylamide

APS

ammonium persulphate

Au NPs

gold nanoparticles

Au

gold

BIS

N,N′-methylenebisacrylamide

BSA

bovine serum albumin

CTA

cetyltrimethylammonium

CTAB

cetyltrimethylammonium bromide

DEAP

2, 2-diethoxyacetophenone

D h

hydrodynamic diameter

DHEA

N,N’-(1,2-dihydroxyethylene) bisacrylamide

DLS

dynamic light scattering

DTT

dithiothrietol

DVB

divinylbenzene

EDC

N-(3-dimethylaminopropyl)-N′-ethyl-carbodiimide hydrochloride

EDX

energy-dispersive X-ray spectroscopy

EGDMA

ethylene glycol dimethacrylate

FESEM

field emission scanning electron microscopy

FITC

fluorescein isothiocyanate

FT-IR

fourier transmission-infrared spectroscopy

HA

hyaluronic acid

HAuCl4.3H2O

tetrachloroauric acid

HCl

hydrochloric acid

HEMA

hydroxyethylmethacrylate

HF

hydrofluoric acid

HsiM

hematite-silica microgel

HSPs

hollow silica particles

IA

itaconic acid

KBH4

potassium borohydride

KPS

potassium persulphate

LBL

layer by layer

LDH

lactate dehydrogenase

MAA

methacrylic acid

MMA

methylmethacrylate

N2

nitrogen

NaBH4

sodium borohydride

NADH

nicotineamide dinucleotide

NaIO4

sodium periodate

NaOH

sodium hydroxide

NIPAM

N-isopropylacrylamide

NMR

nuclear magnetic resonance

NPs

nanoparticles

PAA

poly-acrylic acid

Pb+2

lead ions

PBA

phenylboronic acid

PCS

photon correlation spectroscopy

Pd

palladium

PDMS

polydimethylsiloxane

PEG

polyethylene glycol

PGPR

polyglycerol polyricinoleate

PLL

poly-L-lysine hydrobromide

PMAA

poly(methacrylic acid)

PNB

poly(N-isopropylacrylamide-co-benzo-18-crown-6-acrylamide)

PNIPAM

poly(N-isopropylacrylamide)

PNIPMAM

poly(N-isopropylmethacrylamide)

PS

polystyrene

Pt

platinum

PVP

polyvinylpyrrolidone

R h

hydrodynamic radius

RHB

rhodamine B

RS

Raman spectroscopy

SANS

small angle neutron scattering spectroscopy

SEM

scanning electron microscopy

SiO2

silica

SLS

static light scattering

TEM

transmission electron microscopy

TGA

Thermogravimetric analysis

THF

tetrahydrofuran

THSMGs

thermo-responsive hollow microgels

TMSPMA

3-(trimethoxysilyl) propyl methacrylate

UV

ultraviolet

UV–vis

UV–visible spectroscopy

VPT

volume phase transition

VPTT

volume phase transition temperature

XPS

X-ray photoelectron spectroscopy

References

Ambreen, J., Al-harbi, F.F., Sakhawat, H., Ajmal, M., Naeem, H., Farooqi, Z.H., Batool, N., and Siddiq, M. (2022). Fabrication of poly (N-vinylcaprolactam-co-acrylic acid)-silver nanoparticles composite microgel with substantial potential of hydrogen peroxide sensing and catalyzing the reduction of water pollutants. J. Mol. Liq. 355: 118931, https://doi.org/10.1016/j.molliq.2022.118931.Search in Google Scholar

Anakhov, M.V., Gumerov, R.A., and Potemkin, I.I. (2022). Enhanced scavenging of a minor component from mixtures of two immiscible liquids by hollow polymer microgels. Mol. Syst. Des. Eng. 7: 285–293, https://doi.org/10.1039/d1me00152c.Search in Google Scholar

Arif, M., Shahid, M., Irfan, A., Wang, X., Noor, H., Farooqi, Z.H., and Begum, R. (2022a). Catalytic degradation of organic dyes using Au-poly (styrene@ N-isopropylmethacrylamide) hybrid microgels. Inorg. Chem. Commun. 144: 109870, https://doi.org/10.1016/j.inoche.2022.109870.Search in Google Scholar

Arif, M., Tahir, F., Fatima, U., Begum, R., Farooqi, Z.H., Shahid, M., Ahmad, T., Faizan, M., Naseem, K., and Ali, Z. (2022b). Catalytic degradation of methyl orange using bimetallic nanoparticles loaded into poly (N-isopropylmethacrylamide) microgels. Mater. Today Commun. 33: 104700, https://doi.org/10.1016/j.mtcomm.2022.104700.Search in Google Scholar

Begum, R., Naseem, K., and Farooqi, Z.H. (2016). A review of responsive hybrid microgels fabricated with silver nanoparticles: synthesis, classification, characterization and applications. J. Sol-Gel Sci. Technol. 77: 497–515, https://doi.org/10.1007/s10971-015-3896-9.Search in Google Scholar

Begum, R., Farooqi, Z.H., Ahmed, E., Naseem, K., Ashraf, S., Sharif, A., and Rehan, R. (2017). Catalytic reduction of 4-nitrophenol using silver nanoparticles-engineered poly (N-isopropylacrylamide-co-acrylamide) hybrid microgels. Appl. Organomet. Chem. 31: e3563, https://doi.org/10.1002/aoc.3563.Search in Google Scholar

Begum, R., Farooqi, Z.H., Ahmed, E., Sharif, A., Wu, W., and Irfan, A. (2019). Fundamentals and applications of acrylamide based microgels and their hybrids: a review. RSC Adv. 9: 13838–13854, https://doi.org/10.1039/c9ra00699k.Search in Google Scholar PubMed PubMed Central

Bergbreiter, D.E., Case, B.L., Liu, Y.S., and Caraway, J.W. (1998). Poly (N-isopropylacrylamide) soluble polymer supports in catalysis and synthesis. Macromolecules 31: 6053–6062, https://doi.org/10.1021/ma980836a.Search in Google Scholar

Berndt, I., Pedersen, J.S., and Richtering, W. (2006). Temperature-sensitive core–shell microgel particles with dense shell. Angew. Chem. 118: 1769–1773, https://doi.org/10.1002/anie.200503888.Search in Google Scholar PubMed

Brugnoni, M., Scotti, A., Rudov, A.A., Gelissen, A.P., Caumanns, T., Radulescu, A., Eckert, T., Pich, A., Potemkin, I.I., and Richtering, W. (2018). Swelling of a responsive network within different constraints in multi-thermosensitive microgels. Macromolecules 51: 2662–2671, https://doi.org/10.1021/acs.macromol.7b02722.Search in Google Scholar

Brugnoni, M., Fink, F., Scotti, A., and Richtering, W. (2020). Synthesis and structure of temperature-sensitive nanocapsules. Colloid Polym. Sci. 298: 1179–1185, https://doi.org/10.1007/s00396-020-04686-5.Search in Google Scholar

Chen, L., Kopeček, J., and Stewart, R.J. (2000). Responsive hybrid hydrogels with volume transitions modulated by a titin immunoglobulin module. Bioconjugate Chem. 11: 734–740, https://doi.org/10.1021/bc000046h.Search in Google Scholar PubMed

Chen, L., Chen, J., Zhang, X., and Xie, P. (2016). A review of reproductive toxicity of microcystins. J. Hazard. Mater. 301: 381–399, https://doi.org/10.1016/j.jhazmat.2015.08.041.Search in Google Scholar PubMed

Chen, Y., Chen, Y., Nan, J., Wang, C., and Chu, F. (2012). Hollow poly (N-isopropylacrylamide)-co-poly (acrylic acid) microgels with high loading capacity for drugs. J. Appl. Polym. Sci. 124: 4678–4685.10.1002/app.35515Search in Google Scholar

Cheng, C.J., Chu, L.Y., Ren, P.W., Zhang, J., and Hu, L. (2007). Preparation of monodisperse thermo-sensitive poly (N-isopropylacrylamide) hollow microcapsules. J. Colloid Interface Sci. 313: 383–388, https://doi.org/10.1016/j.jcis.2007.05.004.Search in Google Scholar PubMed

Choi, C.H., Jung, J.H., Kim, D.W., Chung, Y.M., and Lee, C.S. (2008). Novel one-pot route to monodisperse thermosensitive hollow microcapsules in a microfluidic system. Lab Chip 8: 1544–1551, https://doi.org/10.1039/b804839h.Search in Google Scholar PubMed

Contreras-Cáceres, R., Schellkopf, L., Fernández-López, C., Pastoriza-Santos, I., Pérez-Juste, J., and Stamm, M. (2015). Effect of the cross-linking density on the thermoresponsive behavior of hollow PNIPAM microgels. Langmuir 31: 1142–1149, https://doi.org/10.1021/la504176a.Search in Google Scholar PubMed

Deloney, M., Smart, K., Christiansen, B.A., and Panitch, A. (2020). Thermoresponsive, hollow, degradable core-shell nanoparticles for intra-articular delivery of anti-inflammatory peptide. J. Contr. Release 323: 47–58, https://doi.org/10.1016/j.jconrel.2020.04.007.Search in Google Scholar PubMed PubMed Central

Dinsmore, A., Hsu, M.F., Nikolaides, M., Marquez, M., Bausch, A., and Weitz, D. (2002). Colloidosomes: selectively permeable capsules composed of colloidal particles. Science 298: 1006–1009, https://doi.org/10.1126/science.1074868.Search in Google Scholar PubMed

Duan, H., Wang, D., Sobal, N.S., Giersig, M., Kurth, D.G., and Möhwald, H. (2005). Magnetic colloidosomes derived from nanoparticle interfacial self-assembly. Nano Lett. 5: 949–952, https://doi.org/10.1021/nl0505391.Search in Google Scholar PubMed

Dubbert, J., Honold, T., Pedersen, J.S., Radulescu, A., Drechsler, M., Karg, M., and Richtering, W. (2014). How hollow are thermoresponsive hollow nanogels? Macromolecules 47: 8700–8708, https://doi.org/10.1021/ma502056y.Search in Google Scholar

Dubbert, J., Nothdurft, K., Karg, M., and Richtering, W. (2015). Core–shell–shell and hollow double-shell microgels with advanced temperature responsiveness. Macromol. Rapid Commun. 36: 159–164, https://doi.org/10.1002/marc.201400495.Search in Google Scholar PubMed

Farooqi, Z.H., Khan, S.R., Begum, R., and Ijaz, A. (2016). Review on synthesis, properties, characterization, and applications of responsive microgels fabricated with gold nanostructures. Rev. Chem. Eng. 32: 49–69, https://doi.org/10.1515/revce-2015-0033.Search in Google Scholar

Farooqi, Z., Khan, S., and Begum, R. (2017). Temperature-responsive hybrid microgels for catalytic applications: a review. Mater. Sci. Technol. 33: 129–137, https://doi.org/10.1080/02670836.2016.1170396.Search in Google Scholar

Geisel, K., Rudov, A.A., Potemkin, I.I., and Richtering, W. (2015). Hollow and core–shell microgels at oil–water interfaces: spreading of soft particles reduces the compressibility of the monolayer. Langmuir 31: 13145–13154, https://doi.org/10.1021/acs.langmuir.5b03530.Search in Google Scholar PubMed

Guan, Y. and Zhang, Y. (2011). PNIPAM microgels for biomedical applications: from dispersed particles to 3D assemblies. Soft Matter 7: 6375–6384, https://doi.org/10.1039/c0sm01541e.Search in Google Scholar

Guerzoni, L.P., Bohl, J., Jans, A., Rose, J.C., Koehler, J., Kuehne, A.J., and De Laporte, L. (2017). Microfluidic fabrication of polyethylene glycol microgel capsules with tailored properties for the delivery of biomolecules. Biomater. Sci. 5: 1549–1557, https://doi.org/10.1039/c7bm00322f.Search in Google Scholar PubMed

Hajebi, S., Abdollahi, A., Roghani-Mamaqani, H., and Salami-Kalajahi, M. (2020). Temperature-responsive poly (N-isopropylacrylamide) nanogels: the role of hollow cavities and different shell cross-linking densities on doxorubicin loading and release. Langmuir 36: 2683–2694, https://doi.org/10.1021/acs.langmuir.9b03892.Search in Google Scholar PubMed

Hao, L.Y., Zhu, C.L., Jiang, W.Q., Chen, C.N., Hu, Y., and Chen, Z.Y. (2004). Sandwich Fe2O3@ SiO2@ PPy ellipsoidal spheres and four types of hollow capsules by hematite olivary particles. J. Mater. Chem. 14: 2929–2934, https://doi.org/10.1039/b404734f.Search in Google Scholar

Haraguchi, K. (2011). Stimuli-responsive nanocomposite gels. Colloid Polym. Sci. 289: 455–473, https://doi.org/10.1007/s00396-010-2373-9.Search in Google Scholar

He, X., Liu, Z., Fan, F., Qiang, S., Cheng, L., and Yang, W. (2015). Poly (ionic liquids) hollow nanospheres with PDMAEMA as joint support of highly dispersed gold nanoparticles for thermally adjustable catalysis. J. Nanopart. Res. 17: 1–10, https://doi.org/10.1007/s11051-015-2872-1.Search in Google Scholar

Heidari, S., Akhlaghi, M., Sadeghi, M., Kheirabadi, A.M., Beiki, D., Ardekani, A.E., Rouhollah, A., Saeidzadeh, P., and Soleyman, R. (2022). Development of 64Cu-DOX/DOX-loaded chitosan-BSA multilayered hollow microcapsules for selective lung drug delivery. J. Drug Delivery Sci. Technol. 73: 103477, https://doi.org/10.1016/j.jddst.2022.103477.Search in Google Scholar

Hu, Y., Wang, J., Li, C., Li, Z., Liang, R., Wang, Q., Wang, H., Zhu, J., and Yang, Y. (2015). Non-spherical hollow microgels with uniform sizes and tunable shapes from microfluidic-assisted approach. Sci. Adv. Mater. 7: 902–909, https://doi.org/10.1166/sam.2015.1907.Search in Google Scholar

Jans, A., Lölsberg, J., Omidinia-Anarkoli, A., Viermann, R., Möller, M., De Laporte, L., Wessling, M., and Kuehne, A.J.J.P. (2019). High-throughput production of micrometer sized double emulsions and microgel capsules in parallelized 3D printed microfluidic devices. Polymers 11: 1887, https://doi.org/10.3390/polym11111887.Search in Google Scholar PubMed PubMed Central

Karg, M. (2012). Multifunctional inorganic/organic hybrid microgels. Colloid Polym. Sci. 290: 673–688, https://doi.org/10.1007/s00396-012-2644-8.Search in Google Scholar

Karg, M. and Hellweg, T. (2009a). New “smart” poly (NIPAM) microgels and nanoparticle microgel hybrids: properties and advances in characterisation. Curr. Opin. Colloid Interface Sci. 14: 438–450, https://doi.org/10.1016/j.cocis.2009.08.002.Search in Google Scholar

Karg, M. and Hellweg, T. (2009b). Smart inorganic/organic hybrid microgels: synthesis and characterisation. J. Mater. Chem. 19: 8714–8727, https://doi.org/10.1039/b820292n.Search in Google Scholar

Kazemi-Andalib, F., Mohammadikish, M., Divsalar, A., and Sahebi, U. (2022). Hollow microcapsule with pH-sensitive chitosan/polymer shell for in vitro delivery of curcumin and gemcitabine. Eur. Polym. J. 162: 110887, https://doi.org/10.1016/j.eurpolymj.2021.110887.Search in Google Scholar

Keidel, R., Ghavami, A., Lugo, D.M., Lotze, G., Virtanen, O., Beumers, P., Pedersen, J.S., Bardow, A., Winkler, R.G., and Richtering, W. (2018). Time-resolved structural evolution during the collapse of responsive hydrogels: the microgel-to-particle transition. Sci. Adv. 4: eaao7086, https://doi.org/10.1126/sciadv.aao7086.Search in Google Scholar PubMed PubMed Central

Khan, Z., Singh, T., Hussain, J.I., and Hashmi, A.A. (2013). Au (III)–CTAB reduction by ascorbic acid: preparation and characterization of gold nanoparticles. Colloids Surf., B 104: 11–17, https://doi.org/10.1016/j.colsurfb.2012.11.017.Search in Google Scholar PubMed

Kozlovskaya, V., Higgins, W., Chen, J., and Kharlampieva, E. (2011). Shape switching of hollow layer-by-layer hydrogel microcontainers. Chem. Commun. 47: 8352–8354, https://doi.org/10.1039/c1cc12960k.Search in Google Scholar PubMed PubMed Central

Kwok, M.H., Li, Z., and Ngai, T. (2013). Controlling the synthesis and characterization of micrometer-sized PNIPAM microgels with tailored morphologies. Langmuir 29: 9581–9591, https://doi.org/10.1021/la402062t.Search in Google Scholar PubMed

Landrigan, P.J., Schecter, C., Lipton, J.M., Fahs, M.C., and Schwartz, J. (2002). Morbidity, mortality, and costs for lead poisoning, asthma, cancer and developmental disabilities. Environ. Health Perspec. 110: 721–728, https://doi.org/10.1289/ehp.02110721.Search in Google Scholar PubMed PubMed Central

Lapeyre, V., Ancla, C., Catargi, B., and Ravaine, V. (2008). Glucose-responsive microgels with a core–shell structure. J. Colloid Interface Sci. 327: 316–323, https://doi.org/10.1016/j.jcis.2008.08.039.Search in Google Scholar PubMed

Lapeyre, V., Renaudie, N., Dechezelles, J.F., Saadaoui, H., Ravaine, S., and Ravaine, V. (2009). Multiresponsive hybrid microgels and hollow capsules with a layered structure. Langmuir 25: 4659–4667, https://doi.org/10.1021/la9003438.Search in Google Scholar PubMed

Lawrence, D.B., Cai, T., Hu, Z., Marquez, M., and Dinsmore, A. (2007). Temperature-responsive semipermeable capsules composed of colloidal microgel spheres. Langmuir 23: 395–398, https://doi.org/10.1021/la062676z.Search in Google Scholar PubMed

Lee, H., Jeong, Y., and Park, T.G. (2007). Shell cross-linked hyaluronic acid/polylysine layer-by-layer polyelectrolyte microcapsules prepared by removal of reducible hyaluronic acid microgel cores. Biomacromolecules 8: 3705–3711, https://doi.org/10.1021/bm700854j.Search in Google Scholar PubMed

Li, G., Liu, G., Kang, E., Neoh, K., and Yang, X. (2008a). pH-responsive hollow polymeric microspheres and concentric hollow silica microspheres from silica− polymer core− shell microspheres. Langmuir 24: 9050–9055, https://doi.org/10.1021/la8010579.Search in Google Scholar PubMed

Li, G., Yang, X., Wang, B., Wang, J., and Yang, X. (2008b). Monodisperse temperature-responsive hollow polymer microspheres: synthesis, characterization and biological application. Polymer 49: 3436–3443, https://doi.org/10.1016/j.polymer.2008.06.004.Search in Google Scholar

Li, G., Shi, Q., Yuan, S., Neoh, K., Kang, E., and Yang, X. (2010). Alternating silica/polymer multilayer hybrid microspheres templates for double-shelled polymer and inorganic hollow microstructures. Chem. Mater. 22: 1309–1317, https://doi.org/10.1021/cm903501e.Search in Google Scholar

Li, Y., Zhang, S., Jiang, H., Guan, X., and Ngai, T. (2022). Multifunctional silica-modified hybrid microgels templated from inverse pickering emulsions. Langmuir 38: 6571–6578, https://doi.org/10.1021/acs.langmuir.2c00349.Search in Google Scholar PubMed

Lin, C., Fu, J., and Liu, S. (2019). Facile preparation of Au nanoparticle-embedded polydopamine hollow microcapsule and its catalytic activity for the reduction of methylene blue. J. Macromol. Sci., Part A 56: 1104–1113, https://doi.org/10.1080/10601325.2019.1658526.Search in Google Scholar

Lin, S., Wang, W., Ju, X.J., Xie, R., Liu, Z., Yu, H.R., Zhang, C., and Chu, L.Y. (2016). Ultrasensitive microchip based on smart microgel for real-time online detection of trace threat analytes. Proc. Natl. Acad. Sci. 113: 2023–2028, https://doi.org/10.1073/pnas.1518442113.Search in Google Scholar PubMed PubMed Central

Lin, T.W., Liu, C.J., and Lin, J.Y. (2013). Facile synthesis of MoS3/carbon nanotube nanocomposite with high catalytic activity toward hydrogen evolution reaction. Appl. Catal., B 134: 75–82, https://doi.org/10.1016/j.apcatb.2013.01.004.Search in Google Scholar

Lin, Y., Skaff, H., Böker, A., Dinsmore, A., Emrick, T., and Russell, T.P. (2003). Ultrathin cross-linked nanoparticle membranes. J. Am. Chem. Soc. 125: 12690–12691, https://doi.org/10.1021/ja036919a.Search in Google Scholar PubMed

Liu, G., Zhu, C., Xu, J., Xin, Y., Yang, T., Li, J., Shi, L., Guo, Z., and Liu, W. (2013). Thermo-responsive hollow silica microgels with controlled drug release properties. Colloids Surf., B 111: 7–14, https://doi.org/10.1016/j.colsurfb.2013.05.027.Search in Google Scholar PubMed

Liu, R., Milani, A.H., Freemont, T.J., and Saunders, B.R. (2011). Doubly crosslinked pH-responsive microgels prepared by particle inter-penetration: swelling and mechanical properties. Soft Matter 7: 4696–4704, https://doi.org/10.1039/c1sm05216k.Search in Google Scholar

Liu, X.Y., Yang, J.M., Zha, L.S., and Jiang, Z.J. (2014). Self-assembly of hollow PNIPAM microgels to form discontinuously hollow fibers. Chin. J. Polym. Sci. 32: 1544–1549, https://doi.org/10.1007/s10118-014-1508-8.Search in Google Scholar

Liu, Y., Deng, Y., Dong, H., Liu, K., and He, N. (2017). Progress on sensors based on nanomaterials for rapid detection of heavy metal ions. Sci. China: Chem. 60: 329–337, https://doi.org/10.1007/s11426-016-0253-2.Search in Google Scholar

Masoud, H. and Alexeev, A. (2012). Controlled release of nanoparticles and macromolecules from responsive microgel capsules. ACS Nano 6: 212–219, https://doi.org/10.1021/nn2043143.Search in Google Scholar PubMed

Mcmasters, J., Poh, S., Lin, J.B., and Panitch, A. (2017). Delivery of anti-inflammatory peptides from hollow PEGylated poly (NIPAM) nanoparticles reduces inflammation in an ex vivo osteoarthritis model. J. Contr. Release 258: 161–170, https://doi.org/10.1016/j.jconrel.2017.05.008.Search in Google Scholar PubMed PubMed Central

Moncho-Jorda, A., Germán-Bellod, A., Angioletti-Uberti, S., Adroher-Benítez, I., and Dzubiella, J. (2019). Nonequilibrium uptake kinetics of molecular cargo into hollow hydrogels tuned by electrosteric interactions. ACS Nano 13: 1603–1616, https://doi.org/10.1021/acsnano.8b07609.Search in Google Scholar PubMed

Nayak, S., Gan, D., Serpe, M.J., and Lyon, L.A. (2005). Hollow thermoresponsive microgels. Small 1: 416–421, https://doi.org/10.1002/smll.200400089.Search in Google Scholar PubMed

Nickel, A.C., Scotti, A., Houston, J.E., Ito, T., Crassous, J., Pedersen, J.S., and Richtering, W. (2019). Anisotropic hollow microgels that can adapt their size, shape, and softness. Nano Lett. 19: 8161–8170, https://doi.org/10.1021/acs.nanolett.9b03507.Search in Google Scholar PubMed

Nickel, A.C., Rudov, A.A., Potemkin, I.I., Crassous, J.J., and Richtering, W. (2022). Interfacial assembly of anisotropic core–shell and hollow microgels. Langmuir 38: 4351–4363, https://doi.org/10.1021/acs.langmuir.2c00093.Search in Google Scholar PubMed

Pelton, R. (2000). Temperature-sensitive aqueous microgels. Adv. Colloid Interface Sci. 85: 1–33, https://doi.org/10.1016/s0001-8686(99)00023-8.Search in Google Scholar PubMed

Pérez-Juste, J., Pastoriza-Santos, I., and Liz-Marzán, L.M. (2013). Multifunctionality in metal@microgel colloidal nanocomposites. J. Mater. Chem. A 1: 20–26, https://doi.org/10.1039/c2ta00112h.Search in Google Scholar

Pich, A., Bhattacharya, S., Lu, Y., Boyko, V., and Adler, H.J.P. (2004). Temperature-sensitive hybrid microgels with magnetic properties. Langmuir 20: 10706–10711, https://doi.org/10.1021/la040084f.Search in Google Scholar PubMed

Pich, A., Karak, A., Lu, Y., Ghosh, A.K., and Adler, H.J.P. (2006). Preparation of hybrid microgels functionalized by silver nanoparticles. Macromol. Rapid Commun. 27: 344–350, https://doi.org/10.1002/marc.200500761.Search in Google Scholar

Rodríguez-Fernández, J., Pérez-Juste, J., Mulvaney, P., and Liz-Marzán, L.M. (2005). Spatially-directed oxidation of gold nanoparticles by Au (III)− CTAB complexes. J. Phys. Chem. B 109: 14257–14261, https://doi.org/10.1021/jp052516g.Search in Google Scholar PubMed

Schmid, A., Dubbert, J., Rudov, A., Pedersen, J., Lindner, P., Karg, M., Potemkin, I., and Richtering, W. (2016). Multi-shell hollow nanogels with responsive shell permeability. Sci. Rep. 6: 1–13, https://doi.org/10.1038/srep22736.Search in Google Scholar PubMed PubMed Central

Schulte, M.F., Scotti, A., Gelissen, A.P., Richtering, W., and Mourran, A. (2018). Probing the internal heterogeneity of responsive microgels adsorbed to an interface by a sharp SFM tip: comparing core–shell and hollow microgels. Langmuir 34: 4150–4158, https://doi.org/10.1021/acs.langmuir.7b03811.Search in Google Scholar PubMed

Scotti, A., Brugnoni, M., Rudov, A., Houston, J., Potemkin, I., and Richtering, W. (2018). Hollow microgels squeezed in overcrowded environments. J. Chem. Phys. 148: 174903, https://doi.org/10.1063/1.5026100.Search in Google Scholar PubMed

Scotti, A., Denton, A.R., Brugnoni, M., Houston, J.E., Schweins, R., Potemkin, I.I., and Richtering, W. (2019). Deswelling of microgels in crowded suspensions depends on cross-link density and architecture. Macromolecules 52: 3995–4007, https://doi.org/10.1021/acs.macromol.9b00729.Search in Google Scholar

Scotti, A., Denton, A., Brugnoni, M., Schweins, R., and Richtering, W. (2021). Absence of crystals in the phase behavior of hollow microgels. Chem. Rev. 103: 022612, https://doi.org/10.1103/physreve.103.022612.Search in Google Scholar PubMed

Seiffert, S. and Weitz, D.A. (2010). Microfluidic fabrication of smart microgels from macromolecular precursors. Polymer 51: 5883–5889, https://doi.org/10.1016/j.polymer.2010.10.034.Search in Google Scholar

Shah, L.A., Sayed, M., Fayaz, M., Bibi, I., Nawaz, M., and Siddiq, M. (2017). Ag-loaded thermo-sensitive composite microgels for enhanced catalytic reduction of methylene blue. Nanotechnol. Environ. Eng. 2: 1–7, https://doi.org/10.1007/s41204-017-0026-7.Search in Google Scholar

Siltanen, C., Diakatou, M., Lowen, J., Haque, A., Rahimian, A., Stybayeva, G., and Revzin, A. (2017). One step fabrication of hydrogel microcapsules with hollow core for assembly and cultivation of hepatocyte spheroids. Acta Biomater. 50: 428–436, https://doi.org/10.1016/j.actbio.2017.01.010.Search in Google Scholar PubMed PubMed Central

Sun, Q. and Deng, Y. (2005). In situ synthesis of temperature-sensitive hollow microspheres via interfacial polymerization. J. Am. Chem. Soc. 127: 8274–8275, https://doi.org/10.1021/ja051487k.Search in Google Scholar PubMed

Tripathi, B.P., Dubey, N.C., and Stamm, M. (2014a). Hollow microgel based ultrathin thermoresponsive membranes for separation, synthesis, and catalytic applications. ACS Appl. Mater. Interfaces 6: 17702–17712, https://doi.org/10.1021/am504120c.Search in Google Scholar PubMed

Vialetto, J., Camerin, F., Grillo, F., Ramakrishna, S.N., Rovigatti, L., Zaccarelli, E., and Isa, L. (2021). Effect of internal architecture on the assembly of soft particles at fluid interfaces. ACS Nano 15: 13105–13117, https://doi.org/10.1021/acsnano.1c02486.Search in Google Scholar PubMed PubMed Central

Vialetto, J., Ramakrishna, S.N., and Isa, L. (2022). In situ imaging of the three-dimensional shape of soft responsive particles at fluid interfaces by atomic force microscopy. Sci. Adv. 8: eabq2019, https://doi.org/10.1126/sciadv.abq2019.Search in Google Scholar PubMed PubMed Central

Virtanen, O., Mourran, A., Pinard, P., and Richtering, W. (2016). Persulfate initiated ultra-low cross-linked poly (N-isopropylacrylamide) microgels possess an unusual inverted cross-linking structure. Soft Matter 12: 3919–3928, https://doi.org/10.1039/c6sm00140h.Search in Google Scholar PubMed

Wang, Q., Xu, Y., Xue, R., Fan, J., Yu, H., Guan, J., Wang, H., Li, M., Yu, W., Xie, Z., et al.. (2022). All-in-one theranostic platform based on hollow microcapsules for intragastric-targeting antiulcer drug delivery, CT imaging, and synergistically healing gastric ulcer. Small 18: 2104660, https://doi.org/10.1002/smll.202104660.Search in Google Scholar PubMed

Wang, W.T., Chen, R., Xu, J.H., Wang, Y.D., and Luo, G.S. (2014). One-step microfluidic approach for controllable production of gas-in-water-in-oil (G/W/O) double emulsions and hollow hydrogel microspheres. RSC Adv. 4: 16444–16448, https://doi.org/10.1039/c4ra01526f.Search in Google Scholar

Wang, Y., Liu, Z., Peng, H.Y., He, F., Zhang, L., Faraj, Y., Wang, W., Ju, X.J., Xie, R., and Chu, L.Y. (2018). A simple device based on smart hollow microgels for facile detection of trace lead (II) ions. ChemPhysChem 19: 2025–2036, https://doi.org/10.1002/cphc.201800138.Search in Google Scholar PubMed

Wypysek, S.K., Scotti, A., Alziyadi, M.O., Potemkin, I.I., Denton, A.R., and Richtering, W. (2020). Tailoring the cavity of hollow polyelectrolyte microgels. Macromol. Rapid Commun. 41: 1900422, https://doi.org/10.1002/marc.201900422.Search in Google Scholar PubMed

Wypysek, S.K., Centeno, S.P., Gronemann, T., Wöll, D. and Richtering, W. (2023). Hollow, pH-sensitive microgels as nanocontainers for the encapsulation of proteins. Macromol. Biosci.: 2200456, https://doi.org/10.1002/mabi.202200456.Search in Google Scholar PubMed

Xie, L., Chen, M., and Wu, L. (2009). Fabrication and properties of hollow poly (N-isopropylacrylamide)-Ag nanocomposite spheres. J. Polym. Sci., Part A: Polym. Chem. 47: 4919–4926, https://doi.org/10.1002/pola.23543.Search in Google Scholar

Xing, S., Guan, Y., and Zhang, Y. (2011a). Kinetics of glucose-induced swelling of P (NIPAM-AAPBA) microgels. Macromolecules 44: 4479–4486, https://doi.org/10.1021/ma200586w.Search in Google Scholar

Xing, Z., Wang, C., Yan, J., Zhang, L., Li, L., and Zha, L. (2011b). Dual stimuli responsive hollow nanogels with IPN structure for temperature controlling drug loading and pH triggering drug release. Soft Matter 7: 7992–7997, https://doi.org/10.1039/c1sm05925d.Search in Google Scholar

Yang, X., Chen, L., Huang, B., Bai, F., and Yang, X. (2009). Synthesis of pH-sensitive hollow polymer microspheres and their application as drug carriers. Polymer 50: 3556–3563, https://doi.org/10.1016/j.polymer.2009.06.027.Search in Google Scholar

Zha, L., Zhang, Y., Yang, W., and Fu, S. (2002). Monodisperse temperature-sensitive microcontainers. Adv. Mater. 14: 1090–1092, https://doi.org/10.1002/1521-4095(20020805)14:15<1090:aid-adma1090>3.0.co;2-6.10.1002/1521-4095(20020805)14:15<1090::AID-ADMA1090>3.0.CO;2-6Search in Google Scholar

Zhang, B., Sun, B., Li, X., Yu, Y., Tian, Y., Xu, X., and Jin, Z. (2015). Synthesis of pH-and ionic strength-responsive microgels and their interactions with lysozyme. Int. J. Biol. Macromol. 79: 392–397, https://doi.org/10.1016/j.ijbiomac.2015.05.011.Search in Google Scholar

Zhang, F. and Wang, C.C. (2008). Preparation of thermoresponsive core–shell polymeric microspheres and hollow PNIPAM microgels. Colloid Polym. Sci. 286: 889–895, https://doi.org/10.1007/s00396-008-1842-x.Search in Google Scholar

Zhang, H., Ju, X.J., Xie, R., Cheng, C.J., Ren, P.W., and Chu, L.Y. (2009). A microfluidic approach to fabricate monodisperse hollow or porous poly (HEMA–MMA) microspheres using single emulsions as templates. J. Colloid Interface Sci. 336: 235–243, https://doi.org/10.1016/j.jcis.2009.03.070.Search in Google Scholar

Zhang, Y., Guan, Y., and Zhou, S. (2005). Single component chitosan hydrogel microcapsule from a layer-by-layer approach. Biomacromolecules 6: 2365–2369, https://doi.org/10.1021/bm050058b.Search in Google Scholar

Zhang, Y., Guan, Y., and Zhou, S. (2007). Permeability control of glucose-sensitive nanoshells. Biomacromolecules 8: 3842–3847, https://doi.org/10.1021/bm700802p.Search in Google Scholar

Zhang, Z., Cheng, M., San Gabriel, M., Neto, Â.A.T., Da Silva Bernardes, J., Berry, R., and Tam, K.C. (2019). Polymeric hollow microcapsules (PHM) via cellulose nanocrystal stabilized Pickering emulsion polymerization. J. Colloid Interface Sci. 555: 489–497, https://doi.org/10.1016/j.jcis.2019.07.107.Search in Google Scholar

Zhou, S., Wu, B., Zhou, Q., Jian, Y., Le, X., Lu, H., Zhang, D., Zhang, J., Zhang, Z., and Chen, T. (2020). Ionic strength and thermal dual-responsive bilayer hollow spherical hydrogel actuator. Macromol. Rapid Commun. 41: 1900543, https://doi.org/10.1002/marc.201900543.Search in Google Scholar

Received: 2022-12-09
Accepted: 2023-04-03
Published Online: 2023-05-16
Published in Print: 2024-04-25

© 2023 Walter de Gruyter GmbH, Berlin/Boston

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