A second-order scattering (SOS) method is presented for the characterization of aqueous particle suspensions undergoing aggregation. Scattering intensities are measured at 90° by a standard fluorimeter and referenced against dynamic light scattering (DLS) measurements to determine particle size increase in a metal-promoted aggregation process for 0.05 mg/mL aqueous poly-N-isopropylacrylamide (PNIPAm), MW ∼10 k g/mol. Particle size increases monotonically from 30 nm to 210 nm at temperature 308 K. A further validation of the SOS method was performed using monodisperse polystyrene reference particles sized at 52 nm, 101 nm, 151 nm, and 206 nm, which demonstrated the technique’s accuracy to within 6% and its versatility with respect to sample composition. The technique is ideal for monitoring colloidal stability and macromolecular assembly and it can be performed at lower concentrations than are typically used in DLS.
BuchholzB.A.BarronA.E.“The Use of Light Scattering for Precise Characterization of Polymers for DNA Sequencing by Capillary Electrophoresis”. Electrophoresis. 2001. 22(19): 4118–4128.
2.
BhattacharjeeS.“DLS and Zeta Potential - What They Are and What They Are Not?”. J. Controlled Release. 2016. 235(1): 337–351.
3.
KuznikW.LemanowiczM.KusA.GibasM.et al.“Temperature-Controlled Particle Size Distribution of Chalk Suspension Utilizing a Thermosensitive Polymer”. Powder Technol. 2010. 201(1): 1–6.
4.
ZhangY.FurykS.BergbreiterD.E.CremerP.S.“Specific Ion Effects on the Water Solubility of Macromolecules: PNIPAM and the Hofmeister Series”. J. Am. Chem. Soc. 2005. 127(41): 14505–14510.
QiaoJ.QiL.ShenY.ZhaoL.et al.“Thermal Responsive Fluorescent Block Copolymer for Intracellular Temperature Sensing”. J. Mater. Chem. 2012. 22(23): 11543–11549.
7.
MajiS.CesurB.ZhangZ.De GeestB.G.et al.“Poly(N-isopropylacrylamide) Coated Gold Nanoparticles as Colourimetric Temperature and Salt Sensors”. Polym. Chem. 2016. 7(9): 1705–1710.
8.
OsamboJ.SeitzW.R.KennedyD.P.PlanalpR.P.et al.“Fluorescent Ratiometric Indicators Based on Cu(II)-Induced Changes in Poly(NIPAM) Microparticle Volume”. Sensors. 2013. 13: 1341–1352.
9.
WanX.LiuT.LiuS.“Thermoresponsive Core Cross-Linked Micelles for Selective Ratiometric Fluorescent Detection of Hg2+ Ions”. Langmuir. 2011. 27(7): 4082–4090.
QuT.WangA.YuanJ.ShiJ.et al.“Preparation and Characterization of Thermo-Responsive Amphiphilic Triblock Copolymer and its Self-Assembled Micelle for Controlled Drug Release”. Colloids Surf. B. 2009. 72(1): 94–100.
12.
PhilippM.KyriakosK.SilviL.LohstrohW.et al.“From Molecular Dehydration to Excess Volumes of Phase-Separating PNIPAM Solutions”. J. Phys. Chem. B. 2014. 118(15): 4253–4260.
13.
AleksandrovaR.PhilippM.MüllerU.RiobóoR.J.et al.“Phase Instability and Molecular Kinetics Provoked by Repeated Crossing of the Demixing Transition of PNIPAM Solutions”. Langmuir. 2014. 30(39): 11792–11801.
LuY.YeX.ZhouK.ShiW.“A Comparative Study of Urea-Induced Aggregation of Collapsed Poly(N-isopropylacrylamide) and Poly(N, N-diethylacrylamide) Chains in Aqueous Solutions”. J. Phys. Chem. B. 2013. 117(24): 7481–7488.
16.
ChengH.ShenL.WuC.“LLS and FTIR Studies on the Hysteresis in Association and Dissociation of Poly(N-isopropylacrylamide) Chains in Water”. Macromolecules. 2003. 39(6): 2325–2329.
17.
BischofbergerI.TrappeV.“New Aspects in the Phase Behaviour of Poly-N-Isopropyl Acrylamide: Systematic Temperature Dependent Shrinking of PNIPAm Assemblies Well Beyond the LCST”. Sci. Rep. 2015. 5: 15520.
18.
GambinossiF.MylonS.E.FerriJ.K.“Aggregation Kinetics and Colloidal Stability of Functionalized Nanoparticles”. Adv. Colloid Interface Sci. 2015. 222: 332–349.
19.
WahiduzzamanM.DarA.HaqueM.A.IdreesD.et al.“Characterization of Folding Intermediates During Urea-Induced Denaturation of Human Carbonic Anhydrase II”. Int. J. Biol. Macromol. 2017. 95: 881–887.
20.
PaslayL.C.FalgoutL.SavinD.A.HeinhorstS.et al.“Kinetics and Control of Self-Assembly of ABH1 Hydrophobin from the Edible White Button Mushroom”. Biomacromolecules. 2013. 14(7): 2283–2293.
21.
YiX.GaoH.“Kinetics of Receptor-Mediated Endocytosis of Elastic Nanoparticles”. Nanoscale. 2017. 9(1): 454–463.
22.
RobertsC.J.“Protein Aggregation and its Impact on Product Quality”. Curr. Opin. Biotechnol. 2014. 30(1): 211–217.
23.
DuJ.YaoS.SeitzW.R.BencivengaN.E.et al.“A Ratiometric Fluorescent Metal Ion Indicator Based on Dansyl Labeled Poly(N-Isopropylacrylamide) Responds to a Quenching Metal Ion”. Analyst. 2011. 136(23): 5006–5011.
24.
J. Lakowicz. In: Principles of Fluorescence Spectroscopy. New York, NY: Springer Science+Business Media, 2006, 3rd edition. Chap. 3, p. 37.
25.
ChengR.LiL.OuS.BuY.et al.“Determination of Ag+ Ions by a Graphene Oxide Based Dual-Output Nanosensor with High Selectivity”. RSC Adv. 2016. 6(43): 36218–36222.
26.
LiJ.YangX.YangJ.LaiL.“Resonance Rayleigh Scattering and Resonance Nonlinear Scattering Methods for the Determination of Nicardipine Hydrochloride Using Eosin Y as a Probe”. RSC Adv. 2016. 6(31): 25887–25893.
27.
YuanY.FuS.XuQ.YangJ.et al.“The Fluorescence and Resonance Rayleigh Scattering Spectral Study and Analytical Application of Cerium(IV) and Cefoperazone System”. Spectrochim. Acta A Atom. Spectrosc. 2016. 162(1): 93–97.
28.
MandylaS.P.TsogasG.Z.VlessidisA.G.GiokasD.L.“Determination of Gold Nanoparticles in Environmental Water Samples by Second-Order Optical Scattering Using Dithiothreitol-Functionalized CdS Quantum Dots After Cloud Point Extraction”. J. Hazard. Mater. 2017. 323(Pt A): 67–74.
29.
GodderzL.J.PeakM.M.RodgersK.K.“Analysis of Biological Macromolecular Assemblies Using Static Light Scattering Methods”. Curr. Org. Chem. 2005. 9(9): 899–908.
30.
JamtingA.K.CullenJ.ColemanV.A.LawnM.et al.“Systematic Study of Bimodal Suspensions of Latex Nanoparticles Using Dynamic Light Scattering”. Adv. Powder Technol. 2011. 22(2): 290–293.
31.
KatoH.NakamuraA.OuchiN.KinugasaS.“Determination of Bimodal Size Distribution Using Dynamic Light Scattering Methods in the Submicrometer Size Range”. Mater. Express. 2016. 6(2): 175–182.
32.
HalperinA.KroegerM.WinnikF.M.“Poly(N-Isopropylacrylamide) Phase Diagrams: Fifty Years of Research”. Angew. Chem. Int. Ed. 2015. 54(51): 15342–15367.
PaceS.VasaniR.B.CuninF.VoelckerN.H.“Study of the Optical Properties of a Thermoresponsive Polymer Grafted onto Porous Silicon Scaffolds”. New J. Chem. 2013. 37(1): 228–235.
39.
LynchN.J.KilpatrickP.K.CarbonellR.G.“Aggregation of Ligand-Modified Liposomes by Specific Interactions with Proteins. II: Biotinylated Liposomes and Antibiotin Antibody”. Biotechnol. Bioeng. 1996. 50(2): 169–183.
ZhangC.LiuM.-S.HanB.XingX.-H.“Correcting for the Inner Filter Effect in Measurements of Fluorescent Proteins in High-Cell-Density Cultures”. Anal Biochem. 2009. 390(2): 197–202.
42.
D.A. Skoog. Principles of Instrumental Analysis. Belmont, CA: Brooks/Cole, 2007, 6th edition. Chap. 34, Pp. 950–962.
43.
IrvingH.M.WilliamsR.J.P.“Stability of Transition Metal Complexes”. J. Chem. Soc. 1953. 0: 3192–3210.
44.
ScottiA.LiuW.HyattJ.S.HermanE.S.et al.“The CONTIN Algorithm and its Application to Determine the Size Distribution of Microgel Suspensions”. J. Chem. Phys. 2015. 142(23): 234905.
45.
PeltonR.“Poly(N-isopropylacrylamide) (PNIPAM) is Never Hydrophobic”. J. Colloid Interface Sci. 2010. 348(2): 673–674.
Supplementary Material
Please find the following supplemental material available below.
For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.
For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.
