File Name : supplmental_figure_1.tiff
Caption : sup. fig. 1: native agarose gel of p22 pc, p22-int, p22-xaema. the observed shift in electrophoretic mobility shows the temperature induced transformation of p22 pc to ex, and the large shift in mobility shows the transformation of p22-int to p22-xaema because of the net positive charge of the poly(aema) in the running-buffer.
File Name : supplemental_figure_2.tiff
Caption : sup. fig. 2: dynamic light scattering (dls) of p22 ex-int, p22-xaema, p22-xaema-co, p22-xaema-ey, p22-xaema-co/ey. the measured hydrodynamic diameter for the constructs are p22 ex-int (61.39 ± 6.89 nm), p22-xaema (62.34 ± 15.19 nm), p22-co (61.72 ± 13.99 nm), p22-ey (62.10 ± 15.33 nm), p22-co/ey (61.93 ± 15.36 nm).
File Name : supplemental_figure_3.tiff
Caption : sup. fig. 3: characterization of the p22-xaema-co/ey material by sds-page denaturing gel electrophoresis, transmission electron microscopy, and uv-vis spectroscopy. (a) two different views of the same sds-page denaturing gel with samples: (l) protein ladder (10-180 kda), (1) p22-xaema-control 1, (2) p22-xaema-control 2, (3) p22-xaema-control 3, (4) p220.25xco/0.25xey, (5) p220.25xco/0.50xey, (6) p220.25xco/0.75xey, (7) p220.25xey/0.25xco, (8) p220.25xey/0.50xco, (9) p220.25xey/0.75xco (i) sds-page analysis shows a stained gel with a large protein band starting at the expected molecular weight (46 kda) with streaking to higher molecular weight bands indicative of polymers of different sizes formed from the p22 subunit. unstained gel exposed to uv light showing the fluorescence of eosin-y migrating with the p22 protein-polymer material. (ii) transmission electron microscopy (tem) image of the p22-co/ey material showing that p22 maintains its structure after chemical modifications. (b) two uv-vis spectra of the p22-co/ey hybrid materials. (i) samples 4-6. uv-vis spectra showing the absorbance change at 525 nm indicating increased labeling of eosin-y. (ii) samples 7-9. uv-vis spectra showing the absorbance change at 320 nm indicating increased labeling of cobaloxime while the absorbance at 525 nm stays the same indicating constant eosin-y labeling.
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Caption : sup. fig. 4: synthesis of chloro(3-pyridyl isothiocyanate)cobaloxime. co(dmgh)(dmgh2)cl2 (2) was reacted with 3-pyridyl isothiocyanate in methanol, which yielded the desired product chloro(3-pyridyl isothiocyanate)cobaloxime (3) with a yield of 85 %.
File Name : supplemental_figure_5.tiff
Caption : sup. fig. 5: sub-stoichiometric labeling strategy of co-ncs and ey-ncs. (a) sequential labeling allows for precise control over the amount of each small molecule attached to the internal polymer. (b) table of the sub-stoichiometric labeling amounts in relation to the estimated amount of amines on the xaema polymer.
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Caption : sup fig. 6: proposed mechanism for the reduction of cobaloxime and the photochemical production of nadh and hydrogen. (a) the reduction of coiii to coi requires two photoexcited ey, this reduced co (cored) can react with protons to give a co-h species. (b) the co-h species can react in three manners in these reaction conditions, either with nad+, with a h+ or with itself, leading to nadh or h2 production, respectively.
File Name : supplemental_figure_7.tiff
Caption : sup fig. 7: ey-ncs photodegradation monitored by uv-vis. (a) three different concentrations of free in solution ey-ncs photodegradation monitored by tracking the characteristic absorbance at 525 nm. decay constants for free in solution samples (1), (2) and (3) are 1.521 min-1, 1.076 min-1, and 4.092 min-1 respectively. (b) ey-ncs photodegradation monitored by tracking the characteristic absorbance at 525 nm of the samples: (1), (2), (3), (4), (5), and (6) with decay constants: 0.1561 min-1, 0.2614 min-1, 0.3578 min-1, 0.2004 min-1, 0.2163 min-1, 0.2085 min-1, respectively
File Name : supplemental_table_1.tiff
Caption : sup. table 1: co-ncs and ey-ncs catalysts per cage. cobaloxime concentrations were calculated from icp-ms analysis and eosin-y concentrations were calculated from the characteristic absorbance at 525 nm, using an extinction coefficient of 112,000 m-1cm-1. all measurements were performed in at least duplicate and all uncertainty reflects one standard deviation.
File Name : supplemental_table_2.tiff
Caption : sup. table 2: ph dependence on turnovers for nadh and hydrogen for both p22-co/ey and catalysts free in solution. all turnovers were calculated with respect to the cobaloxime concentration and all measurements were performed in triplicate.