Host guest chemistry with water-soluble gold nanoparticle supraspheres

Transcription

1 In the format provided by the authors and unedited. SUPPLEMENTARY INFORMATION DOI: /NNANO Host guest chemistry with water-soluble gold nanoparticle supraspheres Authors: Yizhan Wang, Offer Zeiri, Manoj Raula, Benjamin Le Ouay, Francesco Stellacci and Ira A. Weinstock* These authors contributed equally to this work. Corresponding authors: * NATURE NANOTECHNOLOGY Macmillan Publishers Limited, part of Springer Nature. All rights reserved.

2 Materials and methods Supplementary Fig. 1. DLS analysis of the titration of 1-capped 4-nm Au NPs with hex-sh. Supplementary Fig. 2. Additional cryo-tem images of 1 capped colloidal supraspheres. Supplementary Fig. 3. Determination of 1 on colloidal suprasphere surfaces based on HSR titration. Supplementary Fig. 4. Cryo-TEM image of 1 electrostatically bound to the surfaces of suprasphere nuclei. Supplementary Fig. 5. Additional cryo-tem images of 1 bound to the surfaces of suprasphere nuclei. Supplementary Fig. 6. Characterization of SR + and SR -capped colloidal supraspheres. Supplementary Fig. 7. Characterization of PEG-S and 50% PEG-S-50% hex-s-capped supraspheres. Supplementary Fig. 8. UV-vis spectra and TEM imaging of dis-assembled supraspheres. Supplementary Fig. 9. Phase transfer of PEG-S-capped colloidal supraspheres. Supplementary Fig. 10. UV-vis spectra of bisphenol A uptake by PEG-S-capped supraspheres. Supplementary Fig. 11. DLS analysis of PEG-S-capped supraspheres after the uptake of bisphenol A. Supplementary Fig H NMR spectrum of hex-s-capped 4-nm Au NPs in CD 2 Cl 2. Supplementary Fig H NMR spectrum of bisphenol A released upon dissolution of PEG-Scapped suprasphere hosts in CD 2 Cl 2. Supplementary Fig. 14. Emission spectra of azulene uptake by PEG-S-capped supraspheres. Supplementary Fig. 15. Emission spectra of azulene uptake by SR -capped supraspheres. Supplementary Fig H NMR spectra of TNT released from 50% PEG-S-50% hex-scapped supraspheres. Supplementary Fig H NMR spectrum of RDX released from 50% PEG-S-50% hex-scapped supraspheres. Supplementary Fig H NMR spectrum of Alachlor released from 50% PEG-S-50% hex-scapped supraspheres. Supplementary Fig H NMR spectra of p-dcb released from 50% PEG-S-50% hex-scapped supraspheres. Supplementary Fig H NMR spectra of p-xylene released from 50% PEG-S-50% hex-scapped supraspheres. Supplementary Fig H NMR spectrum of bisphenol A and TNT released upon dissolution of 50% PEG-S-50% hex-s-capped suprasphere hosts in CD 2 Cl 2. Supplementary Fig H NMR spectra showing the selective uptake of bisphenol A after reacting a mixture of bisphenol A and TNT with 100% PEG-S capped suprasphere hosts, and subsequent release in CD 2 Cl 2. 2

3 Supplementary Fig. 23. SAXS analysis of PEG-S-capped 200-nm diameter supraspheres. Supplementary Fig. 24. Calculation of the volume of a tetrahedral hole, and the height of the pores in its triangular faces. Supplementary Fig. 25. Protection of cis-azobenzene guests from light-induced isomerization via encapsulation within suprasphere hosts. Quantitation methods and calculations used to obtain the values in Table 1 References Materials and methods Materials. HAuCl 4, trisodium citrate, C 6 H 5 Na 3 O 7 2H 2 O, NaBH 4, and 11-mercaptoundecanoic acid (HS(CH 2 ) 10 COOH) were purchased from Sigma-Aldrich. HS(CH 2 ) 10 COO (HSR ) was prepared by dissolving 11-mercaptoundecanoic acid in 2 equivalents of NaOH solution to give its Na + salt. Mercapto-poly(ethyleneglycol)-methylether, PEG-SH, MW: 2015 Da) was purchased from Iris Biotech. Bisphenol A, p-dichlorobenzene, p-xylene and azulene were obtained from Alfa Aesar and used as received. α-k 9 AlW 11 O 39 (K 9 1), and N,N,N-trimethyl(11- mercaptoundecyl)ammonium chloride (HS(CH 2 ) 11 N(CH 3 ) 3 Cl, HSR + Cl ) were prepared according to the published methods 1. 1-Hexanethiol (hex-sh, from Acros Organics) was distilled and kept in the dark under nitrogen before use. All solutions were prepared using highly purified water (Millipore Direct-Q), added salts were of the highest purity available, and all glassware used for the synthesis and storage of gold-nanoparticle (Au NP) solutions was pretreated with fresh aqua regia (3:1 v/v ratio of HCl to HNO 3 ) and rinsed thoroughly with purified water. All Au NP solutions were stored at ambient temperature in the dark. Instrumentation. UV-vis spectra were obtained using a Hewlett-Packard 8453 diode array spectrophotometer. Dynamic light scattering (DLS) data were collected at 25 C on an ALV- CGS-8F instrument (ALV-GmbH, Germany). 1 H NMR spectra were recorded on a Bruker Advance 400 MHz spectrometer. Dry TEM measurements were performed on a FEI Tecnai 12 G2 electron microscope, working under an acceleration voltage of 120 kv. SEM measurements were conducted with a JEOL (Tokyo, Japan) model JSM-7400F scanning electron microscope. Cryogenic transmission electron microscopy (cryo-tem). Samples were prepared using a fully automated vitrification device (Leica, EM GP). First, 4 μl of the sample solution was placed by pipet onto a glow discharged Cu grid covered with a lacey-carbon film, held inside a 100%-humidity chamber. The grid was mechanically blotted, and immediately plunged into liquid ethane (mp: K) cooled by liquid nitrogen (77.2 K). Samples were prepared with variable holding times (up to 1 sec), after blotting and before plunging, to ensure that sampling did not affect the results. Images were captured on the FEI Tecnai 12 G2 instrument (120 kv) using a Gatan slow-scan camera. Image brightness and contrast were adjusted using DigitalMicrograph. Reactions of colloidal supraspheres with HSR. Titration of colloidal supraspheres by aqueous solutions of HSR, to determine the thiol concentration needed for complete displacement of 1, was done using a published method 1. Stabilization of fully formed colloidal supraspheres by 3

4 HSR was achieved by adding the desired volume of freshly prepared 1.5 mm HSR to a solution of colloidal supraspheres (the necessary HSR concentration was determined by titration), manually stirring the solution (shaken gently by hand) for ca. 30 s, then aging for 12 h. Reactions of colloidal supraspheres with HSR + and PEG-SH. Stabilization of colloidal supraspheres by the cationic alkanethiol HS(CH 2 ) 11 N(CH 3 ) + 3 (HSR + ) and neutral PEG-SH (Mw = 2015 Da), was performed by adding the thiol (1.5 mm solution) to solutions of colloidal suprasphere or their nuclei (smaller aggregates), and manually shaking the sample for ca. 30 s, then aging for 12 h. The amount of thiols added (required for full displacement of 1) was predetermined by titrating the same solution using HSR. Phase transfer of PEG-S capped colloidal supraspheres. 2 ml of as prepared PEG-S-capped 200 nm diameter supraspheres in water was stirred in a two-phase system that included a layer of CH 2 Cl 2 (2 ml). After stirring for 1 hour at room temperature, transfer of the Au NPs into the organic phase was indicated by color, UV-vis spectra, DLS and TEM Normalized intensity ,000 10,000 R H (nm) Supplementary Fig. 1. Suprasphere growth. DLS data for samples of 1-capped 4-nm Au NPs (blue curve), after reaction with 1-hexanethiol (hex-sh) with absorbance of 0.11 (red), 0.16 (green) and 0.23 (purple) at 750 nm. a b Supplementary Fig. 2. Additional images of colloidal supraspheres. The two particles are 65 nm for a and 90 nm for b in diameter. Scale bar = 10 nm. 4

5 Abs a 0.8 b 0.2 c MUA (μm) Abs MUA (μm) Abs MUA (μm) Supplementary Fig. 3. POM ions on the outer surfaces of the supraspheres. UV-vis spectroscopy and the SPR maximum (near 535 nm), were used to quantify the displacement of 1 from the surfaces of freshly prepared supraspheres by titration with the water-soluble thiol, HS(CH 2 ) 10 COO (HSR ). Titration results for: (a) 1-protected Au NPs, (b) a solution of 156-nm diameter colloidal supraspheres (based on DLS), (c) individual NPs or small nuclei present in the colloidal suprasphere solution after centrifugation for 10 minutes at 6000 RPM was used to remove the colloidal supraspheres. Endpoint HSR concentrations are (a) (b) 4.93 (c) 3.89 μm (in case equal to the HSR concentrations needed to completely displace 1 from the particles 2 ). Therefore, after subtracting the 3.89 µm value (attributed to unreacted 1-protected particles) from each of the endpoints in plots a and b, we find the ratio between the amount of HSR added to the colloidal suprasphere, to that added to the 1-protected NPs, (equal to the ratio between the amount of 1 located on Au-NP surfaces of the colloidal supraspheres, to the amount of 1 on the original solution of individual 1-protected NPs), is equal to 1.04 / 30.03, or 3.46%. The small difference between the calculated value (see below) and the experimental result is strong evidence for the presence of 1 at the colloidal suprasphere surfaces. Theoretical determination of 1 on colloidal suprasphere surfaces: A colloidal suprasphere with an average radius of 78 nm has a surface area of nm 2 (eq. 1) and a volume of nm 3 (eq. 2). S.A. = 4πr 2 (eq. 1) V. = 4/3πr 3 (eq. 2) From these equations, a 1-protected 4 nm Au NP (r = approximately 3.75 nm) has a surface area of nm 2 (eq. 1), and a hex-s protected 4 nm Au NP (r = approximately 3 nm) has a volume nm 3 (eq. 2). Working under the assumptions that (1) a colloidal suprasphere is composed of hex-s protected particles in its interior and hex-s-1 mixed shell Janus-like particles on its surface (with the 1 domain in contact with the aqueous environment), (2) colloidal supraspheres have an approximately closest packed structure (74% of the volume is occupied by the particles), we calculate that an average 78-nm radius colloidal suprasphere is comprised of 13,006 NPs (protected by hex-s), and has 865 NPs at the colloidal suprasphere surface (Janus particles, 5

6 covered with 40%-60% molecules of 1, 60%-40% hex-s). Correspondingly, the amount of 1 on the Janus-like particles is equal to the amount of 1 on 346 to nm particles with complete monolayers of 1. Hence, the amount of 1 present at the surface of the supraparticles is equal that needed to completely cover 346 to 519 of the NPs, or % of the HSR used in panel A. The titration in panel B gave a definitive endpoint of 3.46%, corresponding to domains of 1 on 52% of the surfaces of the outermost ( Janus -like) Au NPs of the supraspherical assemblies. Supplementary Fig. 4. Use of cryo-tem imaging to confirm the presence of hydrophilic domains of 1 at the suprasphere-water interface. Due to occurrence of Fresnel fringes, it is difficult to image thin (1-nm thick) monolayers of 1 on very large, highly electron dense supraspheres (see additional comments immediately below). Hence, cryo-tem evidence for exchangeable domains of 1 was obtained by reacting a solution of smaller (ca. 50-nm diameter) clusters with HS(CH 2 ) 11 N(CH 3 ) 3 + (HSR + ), a relatively long (1.5 nm) alkanethiol with cationic endgroups. These bind to the gold surface through sulfur, while their opposite, positively charged ends form strong electrostatic associations with highly negatively charged molecules of 1. The cryo-tem image of this assembly, shown above, features a shell of 1 anions (in two-dimensional projection), displaced by insertion of HSR + to a distance of 1.5 nm from the perimeter of a relatively small cluster of hydrophobically assembled Au NPs 1. Scale bar = 10 nm. Additional comments: In TEM imaging, Fresnel fringes are often visible as thin white regions at the perimeters of electron dense materials such as gold. This is particularly challenging in twodimensional projections of thin (ca. 1 nm) monolayers of relatively less electron dense tungsten oxide clusters at the surfaces of large gold NPs or their aggregates. To observe molecules of 1 at the suprasphere-water interface, the effects of Fresnel fringes were minimized by using relatively smaller gold-np aggregates. 6

7 Supplementary Fig. 5. Additional cryo-tem images of colloidal suprasphere nuclei after insertion of the cationic thiol, HSR +. Scale bar = 20 nm. Abs. 1 a λ (nm) Normalized intensity c d 1 b R H (nm) Supplementary Fig. 6. Characterization of supraspheres with anionic and cationic alkanethiolate-derived ligand shells. a. UV-vis spectra for colloidal supraspheres protected by 1 (black), SR (HS(CH2)10CO 2, blue), 2 and SR + (HS(CH2)11N(CH3) 3 +, red). Other than the decrease in absorbance at ca. 530 nm due to replacement of 1 by SR almost no change is observed. The cationic SR + ligands insert between gold surfaces and 1, resulting in much less change in the SPR absorbance 1. b. DLS results for colloidal suprasphere protected by 1 (black), SR (blue) and SR + (red). The small differences between the samples are within the statistical error of the method. c. TEM image of a dried sample of SR -capped colloidal suprasphere. d. TEM image of a dried sample of SR + -capped colloidal suprasphere. Scale bar = 20 nm. 7

8 a Abs. b λ (nm) R H (nm) Normalized intensity Supplementary Fig. 7. Characterization of supraspheres with PEG-S ligand shells. a. UVvis spectra for supraspheres capped by 1 (black), neutral PEG-S (red) and 50% PEG-S-50% hex-s (blue). Other than a small decrease in absorbance at ca. 530 nm due to replacement of 1 by the thiolate ligands, almost no change is observed. b. DLS results for colloidal suprasphere protected by 1 (black), PEG-S (red), and 50% PEG-S-50% hex-s (blue). The small increase observed for the thiolate-protected samples is due to the larger size of the PEG-S protecting ligands. a 1.2 b 0.8 Abs λ (nm) Supplementary Fig. 8. Phase transfer of PEG-S-capped supraspheres. a. UV-vis spectra of the remaining water solution (black line) after phase transfer of PEG-S-capped colloidal supraspheres from 2 ml of water into 2 ml of CH 2 Cl 2, and the disassembled nanoparticles (dried from the CH 2 Cl 2 phase) redissolved in 2 ml toluene (red line). b. Large-field dry TEM image of disassembled PEG-S-capped colloidal supraspheres after their dissolution in CH 2 Cl 2. 8

9 1. Spin down 2. Isolate assembly H 2 O 3. Disassemble CD 2 Cl 2 in CD 2 Cl 2 Supplementary Fig. 9. Photographs showing the disassembly of PEG-S-capped colloidal supraspheres in CD 2 Cl 2. A 1.5 ml, 30 pm solution of PEG-S-capped supraspheres (left photograph) was spun down (10 min at rpm) and the resultant pellet (20 µl) was dissolved in 1.5 ml CD 2 Cl 2 (right photograph). Abs µl 1 µl 2 µl 5 µl 10 µl 20 µl Control λ (nm) Supplementary Fig. 10. Uptake of bisphenol A. UV-vis spectra of aqueous bisphenol A solutions (1.5 ml, initially 0.85 mm) after reaction for 24 hours at room temperature by increasing concentrations of PEG-S-capped supraspheres. Experiments were performed by mixing 1.5 ml of bisphenol A solution (0.193 mg/ml, 0.85 mm) with X µl of PEG-Ssupraspheres (4.6E-9 M), and completed with 20-X µl of H 2 O. (X = 0, 1, 2, 5, 10, 20). The uptake was performed for 24 h in glass vials at room temperature without stirring, followed by centrifugation to completely remove the supraparticle hosts (13,500 rpm, 10 min). A portion (0.7 ml) of the supernatant was collected and diluted with 0.7 ml water, then used for UV measurement. The control curve (red curve) refers to a control experiment used to verify that bisphenol A was hosted inside the supraspheres, rather than adsorbed within their PEG-S ligand shells. This was carried out using PEG-S-capped 24-nm diameter Au NPs. Twenty µl of the PEG-S-capped 9

10 24 nm gold nanoparticle solution, containing the same PEG-S-covered surface area as that present in the 30 pm solution of PEG-S-capped supraspheres, was reacted for 24 hours with a 0.85 mm aqueous solution of bisphenol A. After isolation of the PEG-S-capped 24-nm Au NPs, no decrease in the concentration of bisphenol A was seen in the supernatant solution (red-colored control curve). Upon dissolution of the pellet in CD 2 Cl 2, no bisphenol A was detected by 1 H NMR spectroscopy. These observations definitively ruled out adsorption of bisphenol A within the PEG-S ligand shells intensity R H (nm) Supplementary Fig. 11. DLS results for PEG-S stabilized supraspheres in water before (black) and after (red) the uptake of bisphenol A. Supplementary Fig H NMR spectrum of hex-s-capped 4 nm-au NPs in CD 2 Cl 2. 10

11 Supplementary Fig H NMR spectrum of isolated (spun-down) PEG-S-capped supraspheres containing bisphenol A guests after dissolution in 0.5 ml CD 2 Cl 2. The signal for CDHCl 2 at 5.37 ppm in the significantly expanded spectrum includes signals due to spin-spin coupling between 13 C and 1 H (178 Hz). The broad signal at ca ppm is due to the CH 2 groups of the PEG-S ligands, and the signal at ca ppm is from residual H 2 O. The signals at ca and 1.31 ppm arise, respectively, from the methyl and methylene groups of the hexanethiolate ligands. The signals arising from the methyl groups of bisphenol A (1.65 ppm) are obscured by the signal from residual H 2 O at 1.64 ppm. a Intensity Stock 0 µl 25 µl 50 µl 75 µl 100 µl b Int. at 746 nm λ (nm) Volume of PEG-S-capped assemblies (μl) Supplementary Fig. 14. Uptake of azulene. a. Emission spectra of azulene solutions after uptake by PEG-S-capped supraspheres. b. The fluorescence intensity at 746 nm decreases linearly with the amount of supraspheres added. The slope corresponds to 3.0 µg of azulene per 100 µl of supraspheres. Experiments were performed by mixing 1 ml of azulene solution (20 µg/ml) with X (< 100) µl of PEG-S-capped supraspheres (92 pm), and completed with (100-X) µl of H 2 O. Solutions were preprared with X = 100, 50, 25, 10, and 0. The uptake was performed in glass vials. Solutions were reacted for 24 h, then centrifugated ( rpm, 10 min, 20 C), completely removing the supraspheres. The supernatant solutions were used for fluorescence measurements. Due to the adsorption of azulene on the walls of the eppendorfs, large uncertainties were observed when using very small volumes of suprasphere (i.e., near 0 µl in b). 11

12 a Intensity Stock 0 µl 10 µl 25 µl 50 µl 75 µl 100 µl b Int. at 746 nm Wavelength (nm) Supplementary Fig. 15. Uptake of azulene. a. Emission spectra of azulene solution after adsorbed by different amount of mercaptoundecanoate- (SR )-capped supraspheres. b. The fluorescence intensity decreases at 746 nm with the amount of SR -capped supraspheres added. The slope corresponds to 3.2 µg of azulene per 100 µl of supraspheres. Experiments were performed by mixing 1 ml of azulene solution (15 µg/ml) with X (< 100) µl of SR -capped supraspheres (92 pm), and completed with (100-X) µl of H 2 O, where X = 100, 50, 25, 10, 0. The uptake was performed in glass vials. Solution reacted for 24 h, and were then centrifugated ( rpm, 10 min, 20 C), completely removing the supraspheres from solution. The supernatant solutions were used for fluorescence measurements Volume of SR -capped assemblies (μl) Supplementary Fig. 16. NMR quantification of released TNT. 1 H NMR spectra of: a. isolated pelletized 50% PEG-S-50% hex-s-capped supraspheres containing TNT molecules after disassembly in 0.5 ml CD 2 Cl 2 ; b. control experiment without supraspheres. 12

13 Supplementary Fig. 17. NMR quantification of released RDX. 1 H NMR spectrum of isolated pelletized 50% PEG-S-50% hex-s-capped supraspheres containing RDX molecules after disassembly in 0.5 ml CD 2 Cl 2. Supplementary Fig. 18. NMR quantification of released alachlor. 1 H NMR spectrum of isolated pelletized 50% PEG-S-50% hex-s-capped supraspheres containing Alachlor molecules after disassembly in 0.5 ml CD 2 Cl 2. 13

14 Supplementary Fig. 19. NMR quantification of released para-dichlorobenzene. 1 H NMR spectra of a. isolated pelletized 50% PEG-S-50% hex-s-capped supraspheres containing p-dcb molecules after disassembly in 0.5 ml CD 2 Cl 2 ; b. control experiment without supraspheres. Supplementary Fig. 20. NMR quantification of released para-xylene. 1 H NMR spectra of isolated pelletized a. 50% PEG-S-50% hex-s and b. PEG-S-capped supraspheres containing p- xylene molecules after disassembly in 0.5 ml CDCl 3. 14

15 Supplementary Fig. 21. NMR quantification of mixture of released TNT and bisphenol A. 1 H NMR spectrum of isolated pelletized 50% PEG-S-50% hex-s-capped supraspheres containing bisphenol A and TNT molecules after disassembly in 0.5 ml CD 2 Cl 2. NO 2 OH NO 2 O 2 N NO 2 O 2 N NO 2 OH PEG-S c 1:1 PEG-S : hex-s b no assembly a Supplementary Fig. 22. Chemoselective uptake of bisphenol A. 1 H NMR spectra showing the selective uptake of bisphenol A. a. the initial aqueous mixture of bisphenol A (0.5 mm) and TNT (0.5 mm) after extraction into CD 2 Cl 2 ; b. the same aqueous mixture of bisphenol A and TNT after reaction with 50% PEG-S-50% hex-s-capped supraspheres, and subsequent release into CD 2 Cl 2 ; c. the same aqueous mixture of bisphenol A and TNT after reaction with 100% PEG-S capped suprasphere, and subsequent release into CD 2 Cl 2. 15

16 Intensity q (A -1 ) Supplementary Fig. 23. Small-angle X-ray scattering (SAXS) results for a PEG-S-capped colloidal suprasphere solution. While the exact phase structure could not be obtained, the data reveal a repeating unit of 6.0 ± 0.1 nm (D = 2π(1/q); maximum at q = ± Å -1, the uncertainty is due to noise and was estimated by using different smoothing methods). The result is a good fit for the distance between the centers of neighboring 4-nm diameter gold cores, each with a monolayer shell of 1-hexanethiolate ligands. Supplementary Fig. 24. Diagrams used to calculate volumes of tetrahedral and octahedral holes, and the diameters of pores in their faces. a. Tetrahedral hole (Td) formed by four equal spheres (radius = R) in close packed structure; b. the regular tetrahedron with Td hole inside formed by four centers of the spheres; c. small fraction from one of the four spheres inside of the regular tetrahedron of b.; d. one face from the regular tetrahedron of b.; e. enlargement of the pore on a regular tetrahedron surface. 16

17 Void-space volumes (based on an idealized close-packed structure): Step 1. A 100-nm radius suprasphere contains 27,400 hex-s-protected Au NPs, each with a radius (Au core + thiolate shell) of ca. 3 nm. Although the suprasphere is not an infinite lattice, the large number of Au NPs in each suprasphere makes it possible to approximate the numbers of O h and T d holes by reference to the N O h holes and 2N T d holes in infinite closest-packed lattices. Hence, for 27,400 Au NPs, there are ca. 27,400 O h holes and ca. 54,800 T d holes. Finally, with these approximations, the total combined volume, V, of the O h + T d holes is equal to the fraction of void space (0.26) of a closest-packed lattice. This void-space volume is: 27,400 * V Oh + 54,800 * V Td = 4/3 * π * (100 nm) 3 *0.26 = 1.1E6 nm 3 (eq. 3) Step 2. A Td hole is formed by four touching equal spheres (radius = R = 3 nm), the sphere centers of which can form a regular tetrahedron with edge length of 2*R (Supplementary Fig. 24, panel a). The volume of the regular tetrahedron is: V regular tetrahedron = V Td hole + 4 * V F = 1/12 * (2 * R) 3 * 2 (eq. 4) where V F is the volume of the small fraction from one of the four spheres inside of the regular tetrahedron (Supplementary Fig. 24, panel b). The volume:volume ratios of V F to volume of sphere is equal to the area:area ratios of the spherical triangle area (S F, Supplementary Fig. 24, panel c) to the sphere surface area: V F / V sphere = S F / S sphere (eq. 5) The spherical triangle's area is: S F = (A + B + C - π)*r² (eq. 6) where R is the radius of the sphere and A, B, and C are spherical angles measured in radians (A = B = C, Supplementary Fig. 24, panel c). According to spherical trigonometry, the spherical angle A can be calculated from the formula: cos a = cos b * cos c + sin b * sin c * cos A (eq. 7) where a, b, and c are the subtending angles (a = b = c = π / 3, Supplementary Fig. 24 c). Step 3. Based on eqs. 3-7, the volumes of each Oh and Td hole are: V Oh hole = nm 3, and V Td hole = nm 3. The height of the pores in triangular faces of tetrahedral or octahedral holes (based on an idealized close-packed structure): The radius (r) of the inscribed circle of the pore in Supplementary Fig 24 d) is equal to: r = R/cos30 o R 0.155*R = 0.155*3 nm = nm. 17

18 So, T 1 T 2 = T 1 C 2 +C 2 T 2 = R*tan30 o + r nm. The height of largest regular triangle inside of the pore on one face of the tetrahedron or octahedron is equal to: A 1 T 2 = A 1 C 2 +C 2 T 2 = r/sin30 o + r nm. trans- azobenzene cis-azobenzene d c b a Supplementary Fig H NMR spectra showing how encapsulation within 50% PEG-S-50% hex-s capped supraspheres protects cis-azobenzene guests from light-induced isomerization. The basis for this is that the gold-nanoparticles renders the host assemblies opaque, and thus able to protect light-sensitive guests from photo-degradation. In a preliminary experiment, the rapid visible-light-induced isomerization of cis- to trans-azobenzene was prevented upon uptake by the suprasphere hosts: a. the starting material of cis-azobenzene in CD 2 Cl 2 containing 5% trans-isomer; b. after irradiating the cis-azobenzene aqueous solution (0.6 mm) with room light for 2 hours, and subsequent extraction by CD 2 Cl 2. The mole ratio of trans to cis-isomers is 70:30; c. after the uptake of cis-azobenzene with 50% PEG-S-50% hex-s capped supraspheres, and subsequent release in CD 2 Cl 2. The mole ratio of trans to cis-isomers is 20:80 (this partial isomerization occurred during the five-hours allowed for complete uptake); d. after the uptake of cis-azobenzene with 50% PEG-S-50% hex-s capped supraspheres, and irradiating with room light for 2 hours and subsequent release into CD 2 Cl 2. The mole ratio of trans to cis-isomers is 25:75. Hence, once encapsulated within the suprasphere, two hours of exposure to visible light resulted in a change of from 80 to75% cis, while in the absence of the supraspheres, a change of from 95% to 30% cis was observed. (Most of the 5% isomerization of the encapsulated substrate, i.e., from 80 to 75% cis, probably occurred during work-up and NMR analysis.) 18

19 Quantitation method for Table 1: The initial concentration of HAuCl 4 is 5E-4 M. The 4-nm Au NPs are comprised of ca Au atoms. The concentration of 1 protected Au NPs is 5E-4 M / 1977 / 2 = 1.26E-7 M (diluted 2 times after adding 1 solutions). The concentration of 100-nm radius PEG-S-capped supraspheres in aqueous solution is 1.26E-7 M / 27,400 = 4.6E-12 M (colloidal supraspheres with an average radius of 100 nm are comprised of ca 2.74E4 NPs). After centrifugation, the concentration of 100-nm radius PEG-S-capped supraspheres in the pellet is 1.26E-7 M / 27,400 * 1000 = 4.6E-9 M (concentrated by a factor of 1000 via centrifugation, from 10 ml to 0.01 ml). van der Waals volumes of each guest 3 : 1) Bisphenol A (C 15 H 16 O 2 ): V vdw = all atom contributions 5.92N B 14.7R A 3.8R NA (N B is the number of bonds N B =N-1+R A +R NA, R A is the number of aromatic rings, and R NA is the number of nonaromatic rings, V vdw (H) = 7.24 Å 3,V vdw (C) = Å 3, V vdw (O) = Å 3 ) = 15* * * * *2 = Å 3 2) Azulene (C 10 H 8 ): V vdw = all atom contributions 5.92N B 14.7R A 3.8R NA (N B is the number of bonds N B =N-1+R A +R NA, R A is the number of aromatic rings, and R NA is the number of nonaromatic rings, V vdw (H) = 7.24 Å 3,V vdw (C) = Å 3 ) = 10* * * *2 = Å 3 3) TNT (C 7 H 5 N 3 O 6 ): V vdw = all atom contributions 5.92N B 14.7R A 3.8R NA (N B is the number of bonds N B =N-1+R A +R NA, R A is the number of aromatic rings, and R NA is the number of nonaromatic rings, V vdw (C) = Å 3, V vdw (H) = 7.24 Å 3, V vdw (N) = 15.6 Å 3, V vdw (O) = Å 3 ) = 7* * * * * *1 = Å 3 4) RDX (C 3 H 6 N 6 O 6 ): V vdw = all atom contributions 5.92N B 14.7R A 3.8R NA (N B is the number of bonds N B =N-1+R A +R NA, R A is the number of aromatic rings, and R NA is the number of nonaromatic rings, V vdw (C) = Å 3, V vdw (H) = 7.24 Å 3, V vdw (N) = 15.6 Å 3, V vdw (O) = Å 3 ) = 3* * * * *21 3.8*1 = Å 3 5) Alachlor (C 14 H 20 ClNO 2 ): V vdw = all atom contributions 5.92N B 14.7R A 3.8R NA (N B is the number of bonds N B =N-1+R A +R NA, R A is the number of aromatic rings, and R NA is the number of nonaromatic rings, V vdw (H) = 7.24 Å 3,V vdw (C) = Å 3, V vdw (O) = Å 3, V vdw (Cl) = Å 3, V vdw (N) = 15.6 Å 3 ) = 14* * * * * * *1 = Å 3 19

20 6) p-dcb (C 6 H 4 Cl 2 ): V vdw = all atom contributions 5.92N B 14.7R A 3.8R NA (N B is the number of bonds N B =N-1+R A +R NA, R A is the number of aromatic rings, and R NA is the number of nonaromatic rings, V vdw (H) = 7.24 Å 3,V vdw (C) = Å 3, V vdw (Cl) = Å 3 ) = 6* * * * *1 = Å 3 7) p-xylene (C 8 H 10 ): V vdw = all atom contributions 5.92N B 14.7R A 3.8R NA (N B is the number of bonds N B =N-1+R A +R NA, R A is the number of aromatic rings, and R NA is the number of nonaromatic rings, V vdw (H) = 7.24 Å 3,V vdw (C) = Å 3 ) = 8* * * *1 = Å 3 Calculation details for each substrate in Table 1: Bisphenol A: Based on the UV-vis absorbance decrease at 278 nm after isolating the PEG-S-cappedsupraspheres from the aqueous solution, the amount of bisphenol A encapsulated by PEG-Scapped supraspheres can be obtained. According to Supplmentary Fig. 10, when mixing 1.5 ml bisphenol A solution (0.85 mm) with 20 µl 100-nm radius PEG-S-capped supraspheres (4.6 x 10-9 M) for 24 hours at room temperature, the total UV-vis absorbance decrease at 278 nm is 0.40 ± (The supernatant was diluted by a factor of 2; the UV-vis absorbance decreased from 1.32 to 1.12; the indicated uncertainty is based on different experiments, ΔA = 0.06). The extinction coefficient of bisphenol A in water solution is ԑ = 3 x 10 3 cm -1 M -1. So, the decrease in the concentration of bisphenol A after uptake by PEG-S-capped supraspheres is 0.40 ± 0.06 / (3 x 10 3 cm -1 M -1 x 1 cm cell length) = (0.13 ± 0.02) mm. Therefore, the total amount of bisphenol A hosted by the PEG-S-capped supraspheres is (0.13 ± 0.02) mm x 1.52 ml. The mole-to-mole ratio between encapsulated bisphenol A and PEG-S-capped supraspheres is (0.13 ± 0.02) mm x 1.52 ml / (4.6 x 10-9 M x 20 x 10-6 L) = (2.1 ± 0.3) x 10 6, which is equal to numbers of molecules of bisphenol A per 100-nm radius PEG-S-capped suprasphere. The volume of a 100- nm radius PEG-S-suprasphere is 4/3 x π x (100 nm) 3 = 4.2 x 10 6 x 1 x dm 3. So the concentration of bisphenol A in a 100-nm radius PEG-S-suprasphere is (2.1 ± 0.3) x 10 6 / (6.02 x ) mol / (4.2 x 10 6 x 1 x ) dm 3 = (0.8 ± 0.1) M. The van der Waal (vdw) volume of one bisphenol A molecule is nm 3. So, the total vdw volume of bisphenol A in one 100-nm radius PEG-S-capped-suprasphere is (2.1 ± 0.3) x 10 6 x nm 3. The void-space volume of a 100-nm radius PEG-S-suprasphere is equal to 4/3 x π x (100 nm) 3 x 0.26 = 1.1 x 10 6 nm 3. Assuming all the bisphenol A is in the void space of the suprasphere, the occupancy of the void space in the suprasphere by bisphenol A is (2.1 ± 0.3) x 10 6 x nm 3 / (1.1 x 10 6 nm 3 ) = (43 ± 6)%. Azulene: According to Supplementary Fig. 14, (3.0 ± 0.2) x 10-6 g azulene is hosted by 100 µl supraspheres (conc. = 9.2 x M). So, numbers of bisphenol A per 100-nm radius PEG-Ssuprasphere is (3.0 ± 0.2) x 10-6 g / g/mol / (9.2 x M x 100 x 10-6 L) = (2.5 ± 0.2) x The volume of a 100-nm radius PEG-S-capped-suprasphere is 4/3 x π x (100 nm) 3 = 4.2 x 10 6 x 1 x dm 3. Therefore, the concentration of azulene in a 100-nm radius PEG-Ssuprasphere is (2.5 ± 0.2) x 10 6 / (6.02 x ) mol / (4.2 x 10 6 x 1 x dm 3 ) = (0.9 ± 0.1) M. 20

21 The vdw volume of one azulene molecule is nm 3. Thus, the total vdw volume of azulene in one 100-nm radius PEG-S-capped-suprasphere is (2.5 ± 0.2) x 10 6 x nm 3. The void-space volume of a 100-nm radius PEG-S-suprasphere is equal to 4/3 x π x (100 nm) 3 x 0.26 = 1.1 x 10 6 nm 3. Assuming all the azulene is in the void space of the suprasphere, then the occupancy of the void space in the suprasphere by azulene is (2.5 ± 0.2) x 10 6 x nm 3 / (1.1 x 10 6 nm 3 ) = (28 ± 2)%. p-xylene, TNT, RDX, p-dcb, and Alachlor, the quantitation methods were the same; details for TNT are provided here in full detail as a representative example: TNT: Based on the 1 H NMR spectrum in Supplementary Fig. 16, the integrated peak area ratio of protons from the methyl group of TNT at 2.74 ppm, to protons from the methyl group of the thiolate ligand at 0.92 ppm in CD 2 Cl 2, after phase transfer, is 0.40 ± 0.1 (this 25% uncertainty is based on the signal to noise ratio of the 1 H NMR signals of the TNT guest in CD 2 Cl 2 ). Hence, the mole-to-mole ratio of TNT / thiolate ligand in a 100-nm radius 50% PEG-S 50% hex-ssuprasphere is 0.40 ± 0.1. The footprint of a hexanethiolate ligand is ca Å 2. Assuming the gold NPs inside the suprasphere are fully covered by the hexanethiolate ligands, the number of hexanethiolate ligands on each 4 nm-au NP is 4 x π x (20 Å) 2 / 21.3 Å 2 = 236. Each 100-nm radius suprasphere has 27,400 gold NPs. So, the number of TNT molecules per 100-nm radius 50% PEG-S 50% hex-s-suprasphere is 236 x 27,400 x (0.4 ± 0.1) = (2.6 ± 0.6) x10 6, which gives (2.6 ± 0.6) x 10 6 / 6.02 x ) mol TNT per 100-nm radius 50% PEG-S 50% hex-ssuprasphere. The volume of a 100-nm radius 50% PEG-S 50% hex-s-suprasphere is 4/3 x π x (100 nm) 3 = 4.2 x 10 6 x 1 x dm 3. Therefore, the concentration of TNT in a 100-nm radius 50% PEG-S 50% hex-s-suprasphere is (2.6 ± 0.6) x 10 6 / (6.02 x ) mol / (4.2 x 10 6 x 1 x dm 3 ) = (1.0 ± 0.2) M. The vdw volume of one TNT molecule is nm 3. So, the total vdw volume of TNT in one 100-nm radius 50% PEG-S 50% hex-s-capped-suprasphere is (2.6 ± 0.6) x 10 6 x nm 3. The void-space volume of a 100-nm radius 50% PEG-S 50% hex-s-cappedsuprasphere is equal to 4/3 x π x (100 nm) 3 x 0.26 = 1.1 x 10 6 nm 3. Assuming all the TNT is in the void space of the suprasphere, the occupancy of the void space by TNT is (2.6 ± 0.6) x 10 6 x nm 3 / (1.1 x 10 6 nm 3 ) = (42 ± 10)%. RDX: Based on the 1 H NMR data in Supplementary Fig. 17, the integrated peak-area ratio of the methylene group form RDX at 5.98 ppm / methyl group from the thiolate ligand at 0.87 ppm in CD 2 Cl 2 after phase transfer is 0.8 ± 0.2. The mole ratio of RDX/thiolate ligand in a 100-nm radius 50% PEG-S 50% hex-s-capped-suprasphere is 0.4 ± 0.1. Numbers of RDX per 100-nm radius 50% PEG-S 50% hex-s-suprasphere are 236*27400*(0.4 ± 0.1) = (2.6 ± 0.6) x The concentration of RDX in a 100-nm radius 50% PEG-S 50% hex-s-capped-suprasphere: (2.6 ± 0.6) x 10 6 / (6.02 x ) mol / (4.2 x 10 6 x 1 x dm 3 ) = (1.0 ± 0.2) M. Occupancy of the void space by RDX, based on its vdw volume: (2.6 ± 0.6) x 10 6 x nm 3 / (1.1 x 10 6 nm 3 ) = (38 ± 9)%. Alachlor: 21

22 Based on 1 H NMR data in Supplementary Fig. 18, the integrated peak area ratio of methyl group form Alachlor at 3.49 ppm to methyl group from thiolate ligand at 0.92 ppm in CD 2 Cl 2 after phase transfer is 0.2 ± The mole ratio of p-dcb /thiolate ligand in a 100-nm radius 50% PEG-S 50% hex-s-capped-suprasphere is 0.2 ± Numbers of molecules of Alachlor per 100-nm radius 50% PEG-S 50% hex-s-capped-suprasphere: 236*27400*(0.2 ± 0.05) = (1.3 ± 0.3) x The concentration of Alachlor in a 100-nm radius 50% PEG-S 50% hex-s-cappedsuprasphere: (1.3 ± 0.3) x 10 6 / (6.02 x ) mol/ (4.2 x 10 6 x 1 x dm 3 ) = (0.5 ± 0.1) M. Occupancy of the void space by Alachlor based on its vdw volume: (1.3 ± 0.3) x 10 6 x nm 3 / (1.1 x 10 6 nm 3 ) = (31 ± 7)%. p-dcb: Based on 1 H NMR data in Supplementary Fig. 19, the integrated peak area ratio of the phenyl group form p-dcb at 7.35 ppm / methyl group from the thiolate ligand at 0.93 ppm in CD 2 Cl 2 after phase transfer is 0.13 ± The mole ratio of p-dcb /thiolate ligand in a 100-nm radius 50% PEG-S 50% hex-s-suprasphere is 0.1 ± Numbers of molecules of p-dcb per 100-nm radius 50% PEG-S 50% hex-s-capped-suprasphere: 236*27400*(0.1 ± 0.04) = (0.6 ± 0.2) x The concentration of p-dcb in a100-nm radius 50% PEG-S 50% hex-s-capped-suprasphere: (0.6 ± 0.2) x 10 6 / (6.02 x ) mol / (4.2 x 10 6 x 1 x dm 3 ) = (0.2 ± 0.1) M. Occupancy of the void space for p-dcb based on its vdw volume: (0.6± 0.2) x 10 6 x nm 3 / (1.1 x 10 6 nm 3 ) = (6 ± 2)%. p-xylene: Based on 1 H NMR data in Supplementary Fig. 20, the integrated peak area ratio of the methyl group form p-xylene at 2.74 ppm to methyl group from the thiolate ligand at 0.88 ppm in CD 2 Cl 2 after phase transfer is 0.5 ± 0.1. The mole ratio of p-xylene/thiolate ligand in a 100-nm radius 50% PEG-S 50% hex-s-suprasphere is 0.25 ± Numbers of p-xylene per 100-nm radius 50% PEG-S 50% hex-s-capped-suprasphere: 236*27400*(0.25 ±0.05) = (1.6 ± 0.3) x The concentration of p-xylene in a 100-nm radius 50% PEG-S 50% hex-s-capped-supr-asphere: (1.6 ± 0.3) x 10 6 / (6.02 x ) mol/ (4.2 x 10 6 x 1 x dm 3 ) = (0.6 ± 0.1) M. Occupancy of the void space based on the vdw volume of p-xylene: (1.6 ± 0.3) x 10 6 x nm 3 / (1.1 x 10 6 nm 3 ) = (17 ± 3)%. For 0.5 mm bisphenol A mm TNT (50% PEG-S-50% hex-s-capped-suprasphere): Based on the 1 H NMR data in Supplementary Fig. 21, the integrated peak-area ratio of the phenyl group from bisphenol A at 6.73 ppm / methyl group from the thiolate ligand at 0.89 ppm in CD 2 Cl 2 after phase transfer is 0.18 ± The mole ratio of bisphenol A /thiolate ligand in a 100-nm radius 50% PEG-S-50% hex-s-capped-suprasphere is 0.14 ± Numbers of bisphenol A per 100-nm radius 50% PEG-S-50% hex-s-capped-suprasphere are 236*27400*(0.14 ± 0.03) = (0.9 ± 0.2) x The concentration of bisphenol A in a 100-nm radius 50% PEG-S-50% hex-s-capped-suprasphere: (0.9 ± 0.2) x 10 6 / (6.02 x ) mol / (4.2 x 10 6 x 1 x dm 3 ) = (0.4 ± 0.1) M. Occupancy of the void space by bisphenol A, based on its vdw volume: (0.9 ± 0.2) x 10 6 x nm 3 / (1.1 x 10 6 nm 3 ) = (18 ± 4)%. Based on the 1 H NMR data in Supplementary Fig. 21, the integrated peak-area ratio of the methyl group from TNT at 2.71 ppm / methyl group from the thiolate ligand at 0.89 ppm in CD 2 Cl 2 after phase transfer is 0.22 ± The mole ratio of TNT/thiolate ligand in a 100-nm radius 50% PEG-S-50% hex-s-capped-suprasphere is 0.22 ± Numbers of TNT per 100-nm 22

23 radius 50% PEG-S-50% hex-s-capped-suprasphere are 236*27400*(0.22 ± 0.05) = (1.4 ± 0.3) x The concentration of TNT in a 100-nm radius 50% PEG-S-50% hex-s-capped-suprasphere: (1.4 ± 0.3) x 10 6 / (6.02 x ) mol / (4.2 x 10 6 x 1 x dm 3 ) = (0.6 ± 0.1) M. Occupancy of the void space by TNT, based on its vdw volume: (1.4 ± 0.3) x 10 6 x nm 3 / (1.1 x 10 6 nm 3 ) = (22 ± 5)%. For 0.5 mm bisphenol A mm TNT (100% PEG-S-capped-suprasphere): Based on the 1 H NMR data in Supplementary Fig. 22c, the integrated peak-area ratio of the phenyl group form bisphenol A at 6.73 ppm / methyl group from the thiolate ligand at 0.89 ppm in CD 2 Cl 2 after phase transfer is 0.4 ± 0.1. The mole ratio of bisphenol A /thiolate ligand in a 100-nm radius PEG-S-capped-suprasphere is 0.3 ± 0.1. Numbers of bisphenol A per 100-nm radius PEG-S-suprasphere are 236*27400*(0.3 ± 0.1) = (1.9 ± 0.6) x The concentration of bisphenol A in a 100-nm radius PEG-S-capped-suprasphere: (1.9 ± 0.6) x 10 6 / (6.02 x ) mol / (4.2 x 10 6 x 1 x dm 3 ) = (0.7 ± 0.2) M. Occupancy of the void space by bisphenol A, based on its vdw volume: (1.9 ± 0.6) x 10 6 x nm 3 / (1.1 x 10 6 nm 3 ) = (39 ± 12)%. References: 1 Zeiri, O., Wang, Y., Neyman, A., Stellacci, F. & Weinstock, I. A. Ligand-shell-directed assembly and depolymerization of patchy nanoparticles. Angew. Chem. Int. Ed. 52, (2013). 2 Wang, Y., Zeiri, O., Neyman, A., Stellacci, F. & Weinstock, I. A. Nucleation and island growth of alkanethiolate ligand domains on gold nanoparticles. ACS Nano 6, (2012). 3 Zhao, Y. H., Abraham, M. H. & Zissimos, A. M. Fast calculation of van der waals volume as a sum of atomic and bond contributions and its application to drug compounds. J. Org. Chem. 68, (2003). 23