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1 Supplementry Informtion Spontneously mplified homochirl orgnic-inorgnic nno-helix complex vi self-prolifertion Hlei Zhi, Yn Qun, Li Li, Xing-Yng Liu, Xurong Xu c nd Ruikng Tng*,c Centre for Biomterils nd Biopthwys nd Deprtment of Chemistry, Zhejing University, Hngzhou, , Chin. Deprtment of Physics nd Deprtment of Chemistry, Ntionl University of Singpore, Singpore , Singpore. c Qiushi Acdemy for Advnced Studies, Zhejing University, Hngzhou, Zhejing , Chin. 1

Purple: sodium ions. The hydrogen toms linked with chirl cron tom (white) were specificlly noted.

2 1. Supporting figures Fig. S1. Schemtic structure of L (left) nd R (right) formed AOT molecules. The chirlity - here only referred the cron tom linked with SO 3 groups. Gry: Cron toms. Red: Oxygen toms. Yellow: sulphur toms. Purple: sodium ions. The hydrogen toms linked with chirl cron tom (white) were specificlly noted. Note: AOT itself is very difficult to purify the rcemic mixtures. We simplify the rcemic mixture to e L- or R- form ccording to the resulted L- or R- helix. c d e f Fig. S2. Homochirl helix clusters. -c) L-hnded, nd d-f) R-hnded. Br= 1 μm. 2

Note: vrious concentrtions of AOT nd BSA lone were tested ut the hyrid helixes filed to form.

3 Fig. S3. ) The formed HAP nnoprticles y using AOT lone. ) Poor crystlline clcium phosphte nnoprticles y using BSA lone. Note: vrious concentrtions of AOT nd BSA lone were tested ut the hyrid helixes filed to form. Br= 2μm. c d e f g Fig. S4. Homochirl helix network (L-hnded). ) Over view of the formed helix network. -g) Mgnified views of different regions noted y the lck circles. Br = 1 μm. 3

Fig. S5. SEM imge of dispersed nno-helixes (KUDOS, 35 KHz). Insert: n isolted nnohelix. Br = 500 nm. 600 dispersed helixes were counted in five different smples.

4 Fig. S5. SEM imge of dispersed nno-helixes (KUDOS, 35 KHz). Insert: n isolted nnohelix. Br = 500 nm. 600 dispersed helixes were counted in five different smples. The mount of L- or R- hnded helixes were 297 nd 303, respectively. Fig. S6. TGA (drk line) nd DSC (light line) results of nno helixes. The orgnic content ws clculted from 200 C to 350 C, while the remins (ove 350 o C) were ttriuted to the inorgnic content. Note: rushite (CHPO 4 2H 2 O) hs two crystl wter, which could e lost t temperture of C. 1 AOT nd BSA could e degrded t temperture elow 350 C. 2 Therefore, the weight loss efore 200 C ws due to wter (including sored wter nd crystl wter in the hyrid) nd tht during 200 C to 350 C ws ttriuted to the orgnic components. 4

5 Fig. S7. EDS result of nno-helixes. The presence of elements of cron, oxygen, phosphorus, sulphur nd clcium ws shown respectively, which indicte the presence of AOT nd clcium phosphte. Fig, S8. 31 P{ 1 H}CPMAS spectr mesured for nno helixes. The spectr ws recorded t spinning frequency of 10 khz nd the contct time ws set to 2.5 ms. More thn four resolved peks were oserved in the spectr, rendering the spectrl ssignment very difficult. To further chrcterize the phosphorus environments, series of 31 P{ 1 H} CPMAS spectr of the two smples nd selected model compounds with vrile contct times were mesured nd the signl intensities were nlyzed to extrct the τ cp nd T H 1ρ vlues, s summrized in Tle 1. By the comprison of the τ cp vlues of models nd the smples, we concluded tht ll the phosphorus species elonged to either HPO 4 2- or H 2 PO 4 - environment, in which considerle protons existed in the vicinity of 31 P nuclei. 5

6 Fig. S9. 13 C{ 1 H}CPMAS spectr mesured for the nno helixes. The roden resonnce in the cronyl region indicted tht the cronyl group is crucil in intercting with the minerls, which suggested tiny mount of sored BSA existed. Fig. S10. () Synthesized BSA protected Au nnoprticles. The size of Au nnoprticles ws etween 1-2 nm. () Nno-helixes formed y using BSA-Au insted of pure BSA. The tiny dots were BSA protected Au nnoprticles, which preferred to sored on the regions of inorgnic phse (drk lines). Brs in () nd () is 20nm. We note tht the BSA only sor on the surfce of nno-helixes. On one hnd, the BSA molecules re hrd to e incorported into the inner structure due to its lrge dimension (140 x 40 x 40 Å3). On the other hnd, the distriution of Au nnoprticles will e homogeneous if it cts s prt of component during the helix formtion. 6

c d Fig. S11. (-d). TEM results of seed growth experiment.

intense ultrsonic tretment (KUDOS, 35 KHz, 20 min) nd the helix clusters or networks were collpsed into dispersed helixes

Then the dispersed helixes were dded s seeds into freshly prepred rection solutions nd the rection solutions were collected y

The time for forming homochirl helixes formtion homochirl helix clusters could e reduced to out 3h.

7 c d Fig. S11. (-d). TEM results of seed growth experiment. In the experiment of seed growth, 1/20 percent of otined product ( the complex of nnohelixes, Fig 2 nd Fig S2) ws underwent intense ultrsonic tretment (KUDOS, 35 KHz, 20 min) nd the helix clusters or networks were collpsed into dispersed helixes (Fig. S5). Then the dispersed helixes were dded s seeds into freshly prepred rection solutions nd the rection solutions were collected y centrifugtion nd oserved with Trnsmission electron microscopy (TEM). The time for forming homochirl helixes formtion homochirl helix clusters could e reduced to out 3h. We noted tht the time for the formtion of helix cluster is reduced nd the numerous smll clusters quickly form nd quickly ppered within 1h to 2h. In comprison, no products form t this stge if no seeds re dded. This indicted tht mother helix could ct s the seed to induce the prolifertion of new helix to form homochirl helix clusters, rther thn to ggregte helixes into homochirl helix clusters. 7

8 2. Tles Tle S1. Summry of NMR dt determined for model compounds nd nno helixes. The spin-locking field for 1 H ws set to 50 khz, while liner rmping ws pplied in the 31 P chnnel to fulfil Hrtmn-Hhn mtching condition. Smple Site iso (ppm) T 1 τ CP T 1 ρ (s) (ms) (ms) Hydroxyptite C 10 (PO 4 ) 6 (OH) 2 P 2.8 n.d ± 0.12 > 50 Brushite CHPO 4 2H 2 O P 1.4 n.d. c c.. 10 Monetite P n.d ± ± 4.4 CHPO 4 P n.d ± ± 5.1 Glyphoste C 3 H 8 NO 5 P P 13.1 n.d ± ± 5.5 P A ± ± 0.8 P B ± ± 0.6 Nno helixes P C ± ± 1.0 P D ± ± 0.8 P E ± ± 1.4 Note: Error of the chemicl shift dt is estimted to e 0.1 ppm. Tle S2. Free clcium ion concentrtion in BSA, AOT nd BSA+AOT solutions (200ml). Items BSA AOT Free [C 2+ ] Blnk 0 mg/ml 0 mm 1.25 mm BSA 0.5mg/ml 0 mm 1.1 mm AOT 0 mg/ml 0.5mM 0.78 mm BSA+AOT 0.5 mg/ml 0.5mM 0.62 mm Note: BSA molecule contins 585 mino cid residues nd hs moleculr weight of D (5539 g/mol ). The 100 AOT molecule cn ind 94 C 2+, while mino cid residues only cn ind 28 C 2+. Thus, AOT molecule is more cple in inding C 2+. 8

9 3. References 1 Dosen, A.; Giese, R. F. Am. Minerl. 2011, 96, Omstov, M.; Rychly, J.; Trchov, M.; Kovrov, J. Des. Monomers Polym. 2004, 7,

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