DOI: 10.5061/dryad.x3ffbg80q
title: Multi-responsive copolymer gated magnetic mesoporous composite and simultaneous controlling of stimuli to maximize release of encased guest molecules

description: This research is aimed at designing a multi-/dual-responsive copolymer
 gated mesoporous composite microcapsule that allows regulated and
 efficient release of active molecules. Temperature and pH are the two
 important physiological parameters. In this investigation, both these
 physiological parameters are simultaneously regulated to achieve high
 release of loaded cargo molecules. Here, mesoporous magnetic mFe3O4/mSiO2
 core-particles are modified with a copolymer gate via seeded radical
 copolymerization of 2-carboxyethyl acrylate (CEA) and
 N-isopropylacrylamide (NIPAM). The composite is referred as
 mFe3O4/mSiO2/P(NIPAM-CEA-MBA), where N,N'-methylenebisacrylamide
 (MBA) is a cross-linker. The composite surface is mesoporous with average
 pore diameter of around 3 nm and is highly paramagnetic (43.08 emu g-1).
 The copolymer gate showed both temperature- and pH-responsive phase
 transitions. Accordingly, the release of encased biomolecule and drugs
 utilizing lysozyme (LZ), vancomycin (VC) and clonazepam (CZ) is further
 executed through optimized simultaneous control of temperature and pH. The
 release efficiency of LZ, VC and CZ reached 98, 91 and 97 % and the
 release rate followed the first order kinetics. The synthesized composite
 up to 0.5 mg mL-1 is found suitable for therapeutic in-vivo application.
 The overall analyses suggest that the composite prepared can be safely
 used as microcapsule, a carrier-based release platform, for drug
 molecules.
description: # Multi-responsive copolymer gated magnetic mesoporous composite and
 simultaneous controlling of stimuli to maximize release of encased guest
 molecules Dataset DOI:
 [10.5061/dryad.x3ffbg80q](https://doi.org/10.5061/dryad.x3ffbg80q)
 Description of the data and file structure **File:
 Supplemental_Raw_Data-H._Ahmad.zip** The dataset contains
 characterizations related data of composite and intermediates obtained
 from Fourier Transform IR (FTIR) spectra, X-ray photoelectron spectroscopy
 (XPS) survey spectra, X-ray diffraction (XRD) patterns, magnetic moments
 measurements against applied field using a Micro Sense vibrating sample
 magnetometer (VSM), temperature and pH-dependent change in average
 hydrodynamic diameters by a NICOMP 380 particle sizer, zeta potential
 variation with pH using a Malvern zeta analyzer, and mass loss with
 temperature increment by a Thermogravimetry Analyzer (TGA). Loading and
 release behavior – loading of dyes, encapsulation, and release of
 biomolecules and drugs were assessed from absorbance values using a
 UV-visible spectrophotometer. Extended_Data \_Figure_3.x1sx Description:
 This file provides FTIR data used to follow step-by-step change in surface
 functionality of iron oxide nanoparticles during preparation of
 mFe3O4/mSiO2/P(NIPAM-CEA-MBA) composite. Variables • Wavenumber (cm⁻¹) –
 vibration frequency of bonds. • Transmittance (%) – amount of light
 passing through the sample. • Peak Height / Area (a.u.) – relative
 intensity of functional groups. Extended_Data \_Figure_4.x1sx Description:
 This file shows XPS survey spectral data used for confirming elemental
 compositions during the stepwise surface modification of iron oxide
 nanoparticles. Variables • Binding Energy (eV) – energy of photoelectrons
 emitted from the sample surface. • Intensity (a.u.) – relative XPS signal
 intensity (arbitrary units) of each element or chemical state. • Element /
 Peak Assignment – identifies the element and its chemical state for each
 coating step (Fe, O, Si, C, etc.). Extended_Data \_Figure_5.x1sx
 Description: This file provides data related to X-ray diffraction patterns
 of mFe3O4 particles, mFe3O4/mSiO2 core-particles and
 mFe3O4/mSiO2/P(NIPAM-CEA-MBA) composite. Variables • 2θ (degree) –
 diffraction angle in degrees (2θ). • Intensity (a.u.) – relative X-ray
 intensity (arbitrary units). • Crystallite Size (nm) – size of coherent
 diffracting domains calculated from peak broadening. • Crystallinity (%) –
 degree of crystallinity of the sample. Extended_Data \_Figure_6.x1sx
 Description: This file provides change in magnetization values with
 applied field measured by a Vibrating Sample Magnetometer (VSM) for mFe3O4
 particles, mFe3O4/mSiO2 core-particles and mFe3O4/mSiO2/P(NIPAM-CEA-MBA)
 composite. Variables • H (Oe) – applied magnetic field. • M (emu/g) –
 magnetization per gram of sample. Extended_Data \_Figure_7a.x1sx
 Description: This file depicts the relevant data describing the effect of
 temperature increase on the average hydrodynamic diameter of the
 mFe₃O₄/mSiO₂/P(NIPAM-CEA-MBA) composite at pH 8.0 and 10.0, indicating how
 particle size changes with temperature at different pH levels. Variables:
 • Temperature (°C) — The temperature at which the hydrodynamic diameter
 was measured. • Average Hydrodynamic Diameter (nm) — The effective size of
 the composite particles in solution. • pH (8.0 and 10.0) — The pH of the
 composite suspension adjusted before the measurement. Extended_Data
 \_Figure_7b.x1sx Description: This file shows data related to the change
 in zeta potential with pH for the mFe₃O₄/mSiO₂/P(NIPAM-CEA-MBA) composite.
 Variables • pH — The acidity or basicity of the solution during
 measurement. • Zeta Potential (mV) — The surface charge of the composite
 particles. Extended_Data \_Figure_8A.x1sx Description: This file gives
 change in loading amount on the mFe3O4/mSiO2/P(NIPAM-CEA-MBA) composite
 for cationic crystal violet (CV) dye against time (min). Variables • Time
 (min) Contact time between the CV dye solution and the composite material
 during the loading process. • Dye loading amount (mg g⁻¹) Amount of CV
 loaded per gram of composite, calculated from UV–visible absorbance
 measurements. • Temperature (°C) Experimental loading temperature (25° and
 40°C). • pH pH of the dye solution during loading (pH 5.0 and pH 10.0). •
 Initial dye concentration (0.02 mg mL⁻¹) • Solution volume (mL) Total
 volume of dye solution used in the loading experiment (100 mL).
 Extended_Data \_Figure_8B.x1sx Description: This file gives data of
 loading amount of anionic congo red (CR) on mFe3O4/mSiO2/P(NIPAM-CEA-MBA)
 composite against time (min) under different pH and temperature
 conditions. Variables • Time (min) Contact time between the CR dye
 solution and the composite during the loading process. • Dye loading
 amount (mg g⁻¹) Amount of CR dye loaded per gram of composite, calculated
 from UV–visible absorbance measurements. • Temperature (°C) Experimental
 loading temperature (25 °C and 40 °C). • pH pH of the dye solution during
 loading (pH 5.0 and pH 10.0). • Initial dye concentration (0.02 mg mL⁻¹).
 • Solution volume (mL) Total volume of dye solution used in the loading
 experiment (100 mL). File : Extended_Data \_Figure_9a.x1sx Description:
 The dataset contains data for the loading, encapsulation, and
 pH-temperature controlled release experiments of lysozyme (LZ) from
 mFe3O4/mSiO2/P(NIPAM-CEA-MBA) composite. These data are calculated from
 UV–visible spectrophotometric measurements. Variables • Time (min) –
 duration of loading or release. • Absorbance (a.u.) – UV–visible
 absorbance at 280 nm. • Lysozyme concentration (mg L⁻¹) – calculated from
 calibration curve. • Initial LZ amount (mg g⁻¹) – added per gram of
 composite. • Encapsulated lysozyme (mg g⁻¹) – retained in composite. •
 Released lysozyme (mg g⁻¹). • Encapsulation efficiency (%) – % of LZ
 encapsulated. • Cumulative release (%) – % of LZ released. Extended_Data
 \_Figure_9b.x1sx Description: The dataset gives the loading,
 encapsulation, and pH-temperature-controlled release experiments of
 vancomycin (VC) from mFe3O4/mSiO2/P(NIPAM-CEA-MBA) composite. These data
 are calculated from UV–visible spectrophotometric measurements. Variables
 • Time (min) – duration of loading or release. • Absorbance (a.u.) –
 UV–visible absorbance at 280 nm. • VC concentration (mg L⁻¹) – calculated
 from calibration curve. • Initial VC amount (mg g⁻¹) – added per gram of
 composite. • Encapsulated VC (mg g⁻¹) – retained in composite. • Released
 VC (mg g⁻¹) from composite. • Encapsulation efficiency (%) – % of VC
 encapsulated. • Cumulative release (%) – % of VC released. Extended_Data
 \_Figure_9c.x1sx Description: The dataset provides data for the loading,
 encapsulation, and pH-temperature-controlled release experiments of
 clonazepam (CZ) from mFe3O4/mSiO2/P(NIPAM-CEA-MBA) composite. These data
 are calculated from UV–visible spectrophotometric measurements. Variables
 • Time (min) – duration of the loading or release experiment. • Absorbance
 (a.u.) – UV–visible absorbance intensity of CZ measured at 261 nm. • CZ
 concentration (mg L⁻¹) – calculated from the calibration curve. • Initial
 CZ amount (mg g⁻¹) – added per gram of composite during loading. •
 Encapsulated CZ (mg g⁻¹) – amount retained within the composite after
 encapsulation. • Released clonazepam (mg g⁻¹) – amount released from the
 composite at a given time. • Encapsulation efficiency (%) – percentage
 encapsulated relative to the initial amount. • Cumulative release (%) –
 percentage released relative to the encapsulated amount. Extended_Data
 \_Figure_10a.x1sx Description: This file depicts the absorbance values
 obtained from supernatants of composite-RBC suspension during
 concentration-dependent (0.4, 0.5, 0.6, and 0.7 mg mL-1) hemolytic
 activity measurements of mFe3O4/mSiO2/P(NIPAM-CEA-MBA) composite.
 Variables • Composite concentration (mg mL-1) – variable concentrations
 used (0.4, 0.5, 0.6, 0.7 mg mL-1). • Absorbance of supernatant -
 absorbance value of supernatant from composite-RBC suspension at 540 nm •
 Positive and negative control – positive and negative control experiments
 in respective 1% aqueous TritonX-100 and 0.9% aqueous NaCl (physiological
 saline) solution • Hemolysis (%) – percentage of red blood cells lysed
 relative to the positive control, calculated from absorbance value using
 equation (2) Extended_Data \_Figure_10b.x1sx Description: This file
 provides the time-dependent hemolysis percentages of the composite at 0.5
 mg mL-1 concentration. Variables • Time (min) – incubation time during
 hemolysis testing (60, 90, 120 min). • Hemolysis (%) – percentage of red
 blood cell lysis observed at each time interval.
 Supplementary_Figure_S1a.x1sx Description: This file provides the
 calibration curve related absorbance data at 581 nm for crystal violet
 (CV) measured at pH 5.00. Variables • Concentration (mg mL⁻¹) –
 concentration (mg mL⁻¹) of CV in aqueous solution at pH 5.00. • Absorbance
 (581 nm) – UV–Vis absorbance intensity of CV measured at 581 nm
 (dimensionless). • Linear fit (y = 94.418x) – linear regression equation
 correlating absorbance with concentration. • R² – coefficient of
 determination indicating the goodness of fit of the calibration curve.
 Supplementary \_Figure_S1b.x1sx Description: This data presents
 calibration curve related absorbance values at 581 nm for different
 concentrations of crystal violet (CV) measured at pH 10.00. Variables •
 Concentration (mg mL⁻¹) – Concentration (mg mL⁻¹) of CV in aqueous
 solution at pH 10.00. • Absorbance (581 nm) – UV–Vis absorbance intensity
 of CV measured at 581 nm (dimensionless). • Linear fit (y = 58.874x) –
 Linear regression equation correlating absorbance with concentration. • R²
 – Coefficient of determination indicating the goodness of fit of the
 calibration curve. Supplementary_Figure_S2a.x1sx Description: This file
 gives calibration curve related experimental absorbance values at
 different concentrations of congo red (CR) recorded at pH 5.00 obtained at
 340 nm wavelength. Variables • Concentration (mg mL⁻¹) – Concentration (mg
 mL⁻¹) of CR in aqueous solution at pH 5.00. • Absorbance (340 nm) – UV–Vis
 absorbance intensity of CR measured at 340 nm (dimensionless). • Linear
 fit (y = 7.8863x) – Linear regression equation correlating absorbance with
 concentration. • R² – Coefficient of determination indicating the goodness
 of fit of the calibration curve. Supplementary \_Figure_S2b.x1sx
 Description: This file gives calibration curve related experimental
 absorbance values at different concentrations of congo red (CR) recorded
 at pH 10.00 obtained at 490 nm wavelength. Variables • Concentration (mg
 mL⁻¹) – Concentration (mg mL⁻¹) of CR in aqueous solution at pH 10.00. •
 Absorbance (490 nm) – UV–Vis absorbance intensity of CR measured at 490 nm
 (dimensionless). • Linear fit (y = 47.899x) – Linear regression equation
 correlating absorbance with concentration. • R² – Coefficient of
 determination indicating the goodness of fit of the calibration curve.
 Supplementary_Figure_S3a.x1sx Description: This file gives the UV–Vis
 calibration curve related absorbance data for variable concentrations of
 lysozyme (LZ) at pH 5.00 measured at 280 nm wavelength. Variables •
 Concentration (mg mL⁻¹) – Concentration (mg mL⁻¹) of LZ in aqueous
 solution at pH 5.00. • Absorbance (280 nm) – UV–Vis absorbance intensity
 of LZ measured at 280 nm (dimensionless). • Linear fit (y = 1.4315x) –
 Linear regression equation correlating absorbance with concentration. • R²
 – Coefficient of determination indicating the goodness of fit of the
 calibration curve. Supplementary \_Figure_S3b.x1sx: Description: This file
 gives the UV–Vis calibration curve related absorbance data for variable
 concentrations of lysozyme (LZ) at pH 10.7 measured at 280 nm wavelength.
 Variables • Concentration (mg mL⁻¹) – Concentration of LZ in aqueous
 solution at pH 10.7. • Absorbance (280 nm) – UV–Vis absorbance intensity
 of LZ measured at 280 nm (dimensionless). • Linear fit (y = 1.5201x) –
 Linear regression equation correlating absorbance with concentration. • R²
 – Coefficient of determination indicating the goodness of fit of the
 calibration curve. Supplementary \_Figure_S4a.x1sx Description: This file
 gives the UV–Vis calibration curve related absorbance data for variable
 concentrations of vancomycin (VC) at pH 5.00 measured at the wavelength of
 280 nm. Variables • Concentration (mg mL⁻¹) – Concentration (mg mL⁻¹) of
 VC in aqueous solution at pH 5.0. • Absorbance (280 nm) – UV–Vis
 absorbance intensity of VC measured at 280 nm (dimensionless). • Linear
 fit (y = 3.6764x) – Linear regression equation correlating absorbance with
 concentration. • R² – Coefficient of determination indicating the goodness
 of fit of the calibration curve. Supplementary \_Figure_S4b.x1sx
 Description: This file gives the UV–Vis calibration curve related
 absorbance data for variable concentrations of vancomycin (VC) at pH 8.2
 measured at the wavelength of 280 nm. Variables • Concentration (mg mL⁻¹)
 – Concentration of VC in aqueous solution at pH 8.2. • Absorbance (280 nm)
 – UV–Vis absorbance intensity of VC measured at 280 nm (dimensionless). •
 Linear fit (y = 3.9901x) – Linear regression equation correlating
 absorbance with concentration. • R² – Coefficient of determination
 indicating the goodness of fit of the calibration curve. Supplementary
 \_Figure_S5.x1sx Description: This file provides the UV–Vis absorbance
 values against different concentrations (mg mL⁻¹) of clonazepam (CZ) at pH
 10.00 measured at the wavelength of 261 nm. Variables • Concentration (mg
 mL⁻¹) – Concentration of CZ in aqueous solution at pH 10.00. • Absorbance
 (261 nm) – UV–Vis absorbance intensity of Clonazepam measured at 261 nm
 (dimensionless). • Linear fit (y =5.5958x) – Linear regression equation
 correlating absorbance with concentration. • R² – Coefficient of
 determination indicating the goodness of fit of the calibration curve.
 Supplementary \_Figure_S7a.x1sx Description: This file provides the pore
 size data of mFe3O4 particles, mFe3O4/mSiO2 core-particles and
 mFe3O4/mSiO2/P(NIPAM-CEA-MBA) composite, calculated using the BJH method.
 The differential pore volume (dV(log r)) is given as a function of pore
 diameter. Variables • Pore diameter (Å) – Average pore diameter of the
 mesoporous materials expressed in\ angstroms (Å). • dV(log r) (cm³ g⁻¹) –
 Differential pore volume per logarithmic pore radius interval, normalized
 by sample mass. Supplementary \_Figure_S7b.x1sx Description: This file
 provides the nitrogen adsorption–desorption isotherm values for mFe3O4
 particles, mFe3O4/mSiO2 core-particles and mFe3O4/mSiO2/P(NIPAM-CEA-MBA)
 composite measured as a function of relative pressure (P/P0). Variables •
 Relative pressure (P/P0) – Ratio of equilibrium pressure (P) to saturation
 vapor pressure (P0)\ of nitrogen (dimensionless). • Volume adsorbed (cc
 g⁻¹) – Volume of nitrogen (cc) adsorbed per gram of sample. Supplementary
 \_Figure_S8.x1sx Description: This file gives the experimental values of
 sample weight loss as a function of increasing temperature obtained from
 TG analyses for mFe3O4 particles, mFe3O4/mSiO2 core-particles and
 mFe3O4/mSiO2/P(NIPAM-CEA-MBA) composite. Variables • Temperature (°C) –
 the heating temperature of the sample. • Weight (%) – percentage of sample
 mass remaining during heating. ## Code/software Any program that will open
 a spreadsheet, such as Excel is recommended. ## Access information Other
 publicly accessible locations of the data: Not applicable * None Data was
 derived from the following sources: Not applicable * None