Supplementary Information  


Fluorescent in situ Sequencing on Polymerase Colonies

Robi D. Mitra1, Jay Shendure1, Jerzy Olejnik2, and George M. Church1*

 

1Lipper Center for Computational Genetics and Department of Genetics, Harvard Medical School, 200 Longwood Ave., Boston, MA 02115.  

2AmberGen, Inc.  1106 Commonwealth Ave, Boston, MA 02215.

*Corresponding author: church@arep.med.harvard.edu


A.  Polymerase Trapping

B.  Sulfhydryl-cleavable Deoxynucleotide Analogue Structures & Synthesis  

C.  Synthesis of Photocleavable Fluorophore Deoxyuridine Triphosphate Conjugates

D.  Photocleavable Deoxynucleotide Analogue Incorporation & Cleavage

E.  Titration of Reversibly Dye-labeled Nucleotide Analogues and Natural Deoxynucleotides

F.  Linearity and Multiple Nucleotide Incorporations

G.  Primers & Template Sequences

H.  PolCall Software

I.  Updated Experimental Protocols

J.  Polony Sequencing Cost Estimates


A.  Polymerase Trapping

To ascertain how long DNA polymerase remains trapped on DNA within a polony, we trapped Klenow polymerase onto a polony template and washed the slide in a large volume of low salt buffer with shaking for seventy-two hours.  After washing, a fluorescent nucleotide extension reaction was performed without adding additional DNA polymerase.  The incorporated fluorescence was approximately the same as when the washing step was omitted (figure S1), indicating that the DNA polymerase remains bound to the DNA for at least 72 hours. 

 

Figure S1.  DNA polymerase was trapped on denatured polonies with annealed sequencing primer.  The slides were washed for zero or 72 hours and a single base extension reaction was performed.  Similar amounts of incorporated fluorescence were observed (n=10).


B.  Sulfhydryl-cleavable Deoxynucleotide Analogue Structures & Synthesis

We designed structures of sulfydryl-cleavable deoxynucleotide analogues, and had the molecules custom-synthesized (Perkin Elmer / NEN).  The structures are presented in the main paper (figure 4a) and below (figure S2).  Details of the synthesis and the nucleotide analogues themselves are available from Perkin Elmer / NEN.  

 

Figure S2. Structures of sulfhydryl-cleavable deoxynucleotide analogues.  The structure of Cy5-SS-dCTP is presented in the main body of the manuscript.


C. Synthesis of Photocleavable Fluorophore Deoxyuridine Triphosphate Conjugates

Two compounds were synthesized, BODIPY-FL-PC-dUTP and Cy5-PC-dUTP.  The synthesis scheme is presented in Figure S3.

Compound 1 (Olejnik, J., E. Krzymanska-Olejnik, and K. J. Rothschild. 1998. Methods Enzymol. 291:135-54). (100 mg, 0.19 mmol) was dissolved in anhydrous acetonitrile (10 ml) and to this solution 50 µl (0.285 mmol, 1.5 eq.) of N,N-diisopropylethylamine was added followed by N,N’-disuccinimidyl carbonate (75 mg, 0.285 mmol, 1.5 eq.). The mixture was stirred at room temperature overnight, volatiles removed under reduced pressure and the intermediate 2 purified on a silica gel column using a step (0 – 1.5%) gradient of MeOH in CHCl3. Yield – 50 mg (39%)

5-aminoallyl-deoxyuridine triphosphate (3) (5-aminoallyl-dUTP, Sigma) (1 mg, 1.9 µmol) was dissolved in 100 µl of 50 mM NaHCO3 (pH 8.5) and to this solution a solution of 5 mg of compound 2 (7.6 µmol, 4 eq.) in 200 µl of acetonitrile was added. The mixture was incubated at room temperaure for 2 hrs and purified using preparative RP-HPLC (Waters NovaPak C18, 10 x 100 mm) using 0-90% gradient of acetonitrile in 50 mM triethylammonium acetate (pH 4.5) over 45 minutes with flow rate 1 ml/min. The fractions containing the compound 4 were pooled and freeze dried to give ~1 µmol of material. This material was dissolved in 100 µl of water and to this solution 200 µl of concentrated ammonia was added. The solution was incubated overnight at room temperature, freeze-dried and compound 5 isolated using RP-HPLC as described above. Yield – 0.6 µmol.

BODIPY-FL-PC-dUTP

Compound 5 (0.23 µmol) was dissolved in 100 µl of 50 mM NaHCO3 and then 73 µl (8 eqs.) of BODIPY-FL-SE (25 mM solution in DMF, Molecular Probes) was added. Reaction mixture was incubated for 2 hrs at room temperature and the product isolated using RP-HPLC as described above. Fractions containing the desired product were pooled and freeze-dried to give 36 nmoles of compound 6 (based on BODIPY-FL fluorophore absorption, Absorption max = 505 nm, e = 80,000).

Compound 6 was further characterized by photocleavage/HPLC analysis (Figure S4) as well as absorption spectra extracted from the HPLC traces (not shown)

Cy5-PC-dUTP

Compound 5 (0.24 µmol) was dissolved in 40 µl of 50 mM NaHCO3 and then 0.72 µmol of Cy5 – monoreactive NHS (Amersham-Pharmacia) in 100 µl of DMF was added. Reaction mixture was incubated for 2 hrs at room temperature and the product isolated using RP-HPLC initially on R2/10 RP column (Perseptive Biosystems, 4.6x100 mm) followed by another purification on NovaPak C18, (Waters, 10 x 100 mm). In both case a gradient (0-90%) of acetonitrile in 50 mM triethylammonium acetate (pH 4.5) over 45 minutes with flow rate 1 ml/min. was used. Fractions containing the desired product were identified by performing photocleavage followed by analytical HPLC, pooled and freeze-dried to give 60.5 nmoles of compound 7 (based on Cy5 fluorophore 550 nm absorption maximum, e = 250,000). We were unable to purify this conjugate to homogeneity, even though two different reverse phase HPLC separations were performed. The preparation was used for polony sequencing experiments – the estimated purity was ~50% based on the extent of the conversion of conjugate to the intermediate 5 upon irradiation (Figure S4). The impurity was determined to be the hydrolyzed Cy5-NHS reagent, which did not interfere with the subsequent polony sequencing reactions.

Figure S3.  Scheme for synthesis of photoclevable fluorophore deoxyuridine triphosphate conjugates.

 

Figure S4.  Photocleavage/HPLC analysis of BODIPY-FL-PC-dUTP and Cy5-PC-dUTP.


 

D.  Photo-cleavable Deoxynucleotide Analogue Structure, Cleavability & Extension Efficiencies

 

We designed & synthesized a dUTP analogue, Cy5-PC-dUTP, with a photocleavable linker between the nucleotide and the fluorophore (figure S3a).  To see if DNA polymerase would recognize this analogue, we performed experiments identical to the ones described in Figure 4 of the main paper, except the extension was performed with the Cy5-PC-dUTP nucleotide analogue, and light was used as the cleaving agent (figure S3b and S3c).  As expected, we see two types of polonies, green and yellow, and by further base extensions it was confirmed that the nucleotide was correctly incorporated.  To characterize the rate and extent the fluorescent signal can be removed by exposure to light, we exposed the slide to 365 nm light, imaging the slide at various intervals.  After 29 minutes of exposure, the fluorescence was greatly reduced, although not completely removed (figure S3d).   The decay of the fluorescent signal can be fitted to an exponential curve that decays with a time constant of 2.6 minutes to a steady state value equal to 7.5% of the original fluorescence.

Figure S3 . (A)  Structure of Cy5-PC-dCTP.  This molecule has a photolabile group between the fluorophore and the deoxynucleotide so that the label can be removed after incorporation.  (B)  Extension of an immobilized primer:template with Cy5-PC-dCTP.  The yellow polonies indicate the nucleotide analogue is recognized by DNA polymerase.  (C)  After exposure to 365 nm light, the fluorescence can be removed from the slide.  (D)  The signal decays exponentially with a time constant of five minutes to a steady state value that is 7.5% of the original signal.

 

E.  Titration of Reversibly Dye-labeled Nucleotide Analogues and Natural Deoxynucleotides.

Because fluorophores tend to "quench" one another when they are in close proximity, we hypothesized that it might be advantageous to perform extension with a mixture of unlabeled and labeled nucleotide, so that when repeated bases occur in the sequence, multiple labeled nucleotides are unlikely to be incorporated into adjacent positions in the growing DNA strand.  DNA polymerase incorporates natural nucleotides more efficiently than fluorescent nucleotides, so we performed extension reactions with varying ratios of fluorescent to natural nucleotides and quantified the amount of fluorescence incorporated (figure S4).  The results indicate a linear relationship between the fraction of fluorescent nucleotide present in the extension reaction and the normalized signal intensity values.

Figure S4.  Titration of natural and reversibly dye labeled nucleotides.  Single base extension reactions were performed using 2 micromolar natural nucleotide and varying amounts of reversibly dye labeled nucleotide.  The results are plotted above.  The x-axis represents the fraction of total nucleotide concentration included in the extension reaction that is dye labeled.  Cy5-SS-dATP is represented by green squares, Cy5-SS-dCTP is represented by blue triangles,Cy5-SS-dGTP by red diamonds, and Cy5-SS-dUTP by  yellow circles.  All fluorescent values are normalized to the incorporated fluorescent signal observed when the extension reactions are performed with 100% reversibly dye labeled base (at 2 micromolar).


F. Linearity and Multiple Nucleotide Incorporations. 

To determine if we could attain a linear fluorescence response by using a mixture of fluorescent and natural nucleotides, we used the synthetic oligonucleotide T6 as a template for polony amplification.  We denatured the polonies, hybridized to a Cy3-labeled sequencing primer, and trapped the polymerase onto the immobilized primer:template duplex.  We then performed serial base additions with the Cy5-dATP, Cy5-dCTP, Cy5-dGTP, and Alexa 488-dUTPs according to the protocol outlined in Fig. 1b on the main text.  Each fluorescent analogue was mixed with the corresponding natural nucleotide so that, on average, 1 in 25 of every nucleotide incorporated was fluorescent.  The nucleotide analogues used here did not have a reversible linker, so the change in fluorescent signal was measured after each base addition.  The results are shown in Figure S5 below.  For this template, the added fluorescence signal was linear with the number of incorporated bases, both for multiple incorporations of the same base (e.g. base "T" at the third addition step) and also for incorporations of different bases (because here the fluorophore was not removed after any cycle, yet the signal remained linear).  However, different template sequences did not yield a linear response, indicating that sequence context can affect linearity (data not shown).

Figure S5.  Linearity and Multiple Nucleotide Incorporations.  The X-axis indicates sequential base addition (without cleaving).  The Y-axis indicates the increase in fluorescence at each step.  Approximately linear relationships in signal are observed for mononucleotide vs. dinucleotide incorporations (e.g. C vs. CC and T vs. TT), as well as for incorporations of different bases (e.g. C vs. G).


G.  Primers & Template Sequences

All oligonucleotides were obtained from Operon (CA).  The character Q in the sequences listed below designates an acrydite group (Mosaic Technologies).  The bolded region indicates the sequence within the template that is complementary to the sequencing primer.   The oligonucleotide templates used in this work are listed here:

Template OT1     5' - Qtc aag ctg cgc aac tgt tgg gaa ggg cga tcg gct taa aca gac gct cga gac cgg gc-3'.

Template OT2     5' - Qtg gcg taa tca tgg tca tag ctg ttt cct gtg tga act aaa cag acg ctc gag acc ggg c -3'. 

Template OT3     5' - Qtc ggc caa cgc gcg ggg aga ggc ggt ttg cgt atc agt aaa cag acg ctc gag acc ggg c - 3'. 

Template OT4     5' - Qcc cag tca cga cgt tgt aaa acg acg gcc agt gtc gat aaa cag acg ctc gag acc ggg c -3'. 

Template LC1     5' - cca cta cgc ctc cgc ttt cct ctc tgc aag ctt ggc gta atc atg gtc ata gct gtt tcc tgt gtg aaa ttg tta tag aga atg agg aac ccg ggg cag -3'

Template T1     5' - cca cta cgc ctc cgc ttt cct ctc tat ggg cag tcg gtg ata gag tgg tgg agt gtg tgt gtg tgt gag aga atg agg aac ccg ggg cag - 3'.

Template T2      5' - cca cta cgc ctc cgc ttt cct ctc tat ggg cag tcg gtg ata gag tgg tgg aca cac aca cac aca cag aga atg agg aac ccg ggg cag - 3'.

Template T3      5' - cca cta cgc ctc cgc ttt cct ctc tat ggg cag tcg gtg ata gag tgg tgg atc acg tgt gtg agc act aga gaa tga gga acc cgg ggc ag - 3'.

Template T4      5' - cca cta cgc ctc cgc ttt cct ctc tat ggg cag tcg gtg ata gag tgg tgg atc ggt cgt tcg gct gag aga atg agg aac ccg ggg cag - 3'.

Template T5      5' - cca cta cgc ctc cgc ttt cct ctc tat ggg cag tcg gtg ata gag tgg tgg acg aca gct ctc aca tag aga atg agg aac ccg ggg cag - 3'.

Template T6       5' - cca cta cgc ctc cgc ttt cct ctc aaa gaa cat gtg agc aaa agg cca gca aaa ggc cag gaa ccg taa aaa ggc aga gaa tga gga acc cgg ggc ag - 3'.

The PCR amplification and sequencing primers used in this work are listed here:

Primer Seq1      5' - gcc cgg tct cga gcg tct gtt ta - 3'. 

Primer PR1-Fac    5' - Qcca cta cgc ctc cgc ttt cct ctc - 3'.

Primer PR1-R    5' - ctg ccc cgg gtt cct cat tct ct - 3'.

Primer T6-Seq     5' - ctg ccc cgg gtt cct cat tct - 3'.

PR1-R was used as both an amplification primer and a sequencing primer.


H.  PolCall Software

We have established a separate website describing the software in detail and providing open source-code:  

Polony Software Page


I.    Updated Experimental Protocols

We have established a separate website describing the latest in polony protocol development for various applications:

Polony Protocols Page


J.     Polony Sequencing Cost Estimates 

Summary of Cost Analysis

Raw data rate:                     25 pixels/bp, 1Mpixel per 6sec/CPU = 24 CPU days.

Amortization:                      5 years, 80% duty cycle, 12.5 minutes/cycle =  $3433 per 6.9x1010 bp

Overhead:                            $200 /sq ft/yr  * 60 sq.ft  (600 cu.ft) =  $42

Reagents:                            At 20  microliters/cycle 200 bases/slide =  $979

Library Preparation:          (includes DNA preparation) $28

Electricity:                            2 kwatts 24hr*17days* 0.13$/kwatt-hr =  $104

Labor for repair:                 10% of instrument cost  = $343

Labor for operation:          Slide PCR, slide dips, scans, etc. = $499

Total:                                     $5428 per Diploid Genome (11x or >99.99 coverage) or 7.9 cents per Megabase

 

White Paper on Polony Sequencing

Detailed Cost Summary (Word Document)  

Detailed Cost Summary (Excel Spreadsheet)