Nerve Agent Surrogate

Transcription

1 Supporting Information A Porous Metal-Organic Replica of α-pbo 2 for Capture of Nerve Agent Surrogate Ruqiang Zou, Ruiqin Zhong, Songbai Han, Hongwu Xu, Anthony K. Burrell, Neil Henson, Jonathan L. Cape, Donald D. Hickmott, Tatiana V. Timofeeva, Toti E. Larson, and Yusheng Zhao S1

2 Complete Ref. 2c Park, Y. K.; Choi, S. B.; Kim, H.; Kim, K.; Won, B.-H.; Choi, K.; Choi, J. S.; Ahn, W. S.; Won, N.; Kim, S.; Jung, D. H.; Choi, S. H.; Kim, G. H.; Cha, S. H.; Jhon, Y. H.; Yang, J. K.; Kim, J. Angew. Chem., Int. Ed. 2007, 46, S2

3 Materials and General Methods. All the solvents and reagents for synthesis were commercially available and used as received. The infrared (IR) spectra were recorded on a NEXUS 870 FTIR spectrometer operating at a spectral resolution of 2 cm -1 accumulating 64 scans. Thermogravimetric analysis (TGA) was carried out using a DuPont Instruments 951 (Thermogravimetric Analyzer DTG-50) from room temperature to 600 C with a ramp rate of 10 C/min in a flowing nitrogen atmosphere. Powder X-ray diffractograms (PXRD) were recorded on a Siemens D-500 X-ray diffractometer operating at 45 kv and 35 ma and using Cu Kα radiation. BET surface area and nitrogen and hydrogen adsorption measurements were carried out with an ASAP 2020 surface area analyzer. Elemental analysis was carried out using a Eurovector CN elemental analyzer (Milan, Italy) configured to an Isoprime continuous flow isotope ratio mass spectrometer (GV Instruments, Manchester, UK). Synchrotron X-ray diffraction data were collected at the 11-BM beamline at the Advanced Photon Source, Argonne National Laboratory by following a standard procedure. The lattice parameters were refined by using Le Bail method with GSAS program. 3S The final refined Space group is C222 1 with the unit cell of a= (1), b= (1), and c= (1). The refinement of the XRD patterns for the sample is illustrated in Figure 4S and the detailed refinement results are listed in Table 2S. High performance liquid chromatography (HPLC) measurements on p-bromophenacyl ester derivatives of methylphosphonic acid were performed on a Dionex P680 HPLC system using a gradient elution (from 0-20 min 80:20 50 mm phosphate:meoh ramp to 50:50, then hold at 50:50 S3

4 to 35 min) with detection at 260 nm. Derivatization of the unbound fraction of methyl phosphonic acid as the p-bromophenacyl esters was performed mixing a 100 μl aliquot of methylphosphonate/ch 2 Cl 2 from the binding assay with 100 μl of 50 mm p-bromophenacyl bromide, 150 mm TEA in MeCN, then heating the mixture at 60 o C for 30 min; this reaction mixture was directly injected into HPLC. Synthesis of [Zn 2 Ca(BTC) 2 (H 2 O) 2 ](DMF) 2 1. A mixture of benzene-1,3,5-tricaboxylic acid (H 3 BTC) (0.2 mmol, 41 mg), Zn(NO 3 ) 2.6H 2 O (0.2 mmol, 59 mg) and Ca(OH) 2 (0.1 mmol, 7.4 mg) was dissolved in 20 ml of DMF/H 2 O (9:1) (DMF = N,N -dimethylformamide) while being stirred in a 25 ml Parr acid digestion autoclave. After dissolution of the reagents, 1 ml deionized water was added. The tightly capped Parr Bomb was heated to 95 C (the ramp rate = 3 C/min), and was held at this temperature for 48 h before which it was cooled back to 25 C (the ramp rate = 0.5 C/min). After decanted and rinsed with ethanol, the colorless needle crystals were washed with DMF to yield pure 1 with the formula: [Zn 2 Ca(BTC) 2 (H 2 O) 2 ](DMF) 2. The desolventized samples can be obtained via heating the needle-like crystals of 1 at 160 ºC for 4 h, 200 ºC for 4 h, and final 300 ºC for 6 h in vacuum to completely remove water and DMF solvent molecules in 1. Exposed to atmosphere air, the solvent free 1 immediately adsorbs water from air. The re-adsorbed water of the sample can be easily removed by heating to 120 C in vacuum for 2 h (See TGA curve). Single-Crystal X-ray Crystallography. Single-crystal X-ray diffraction was carried out on a S4

5 Bruker Apex2 CCD diffractometer with graphite-monochromatic Mo Kα1 radiation (λ = Å) using the ω-scan mode at 100 K. Crystal of 1 was glued on a polymer fiber, transferred to the diffractometer, and cooled in a nitrogen stream. Frames were collected with 0.2 intervals in φ and ω for 10 s per frame such that a hemisphere of data was collected. Lattice parameters were initially determined from least-squares analysis of more than 100 centered reflections and were then refined using all the data. None of the reflections showed evidence of significant crystal damage during data collection. Raw data collection and cell refinement were carried out with SMART; data reduction with SAINT+ to account for Lorentz and polarization effects. 1S Absorption corrections were applied using the SADABS routine. Space group assignment was based on systematic reflection absences, E-statistics, and successful refinement of the structures. Structures were solved by the direct method using SHELXTL and were refined by full-matrix least-squares on F2 using SHELX S Non-hydrogen atoms were refined with anisotropic displacement parameters during the final cycles. It should be noted O2 atom of BTC ligand was treated by disorder with a half occupation for each. Hydrogen atoms were placed in calculated positions with isotropic displacement parameters set to 1.2 Ueq of the attached atom. Further details for structural analysis are summarized in Tables 1S. References (1S) SAINT+, Bruker Analytical X-Ray Systems, Madison, WI, S5

6 (2S) Sheldrick, G. M., SHELX-97, Bruker Analytical X-Ray Systems, Madison, WI, (3S) A. C. Larson, R. B. Von Dreele, in: A. C. Larson, R. B. Von Dreele (Eds.), General Structure Analysis System (GSAS), Los Alamos National Laboratory, LAUR, S6

7 Table 1S Crystallographic Data and Structural Refinement Summary for 1 Chemical formula Zn 2 CaC 24 H 24 N 2 O 16 Fw Space group C222 1 a / Å (15) b / Å (19) c / Å (16) α / deg 90 β / deg 90 γ / deg 90 V / Å (6) T / K 193(2) D c / g cm Z 4 µ(mo-kα) / mm R a /wr b / a R = ( F o - F c )/ F o. b wr = [ ( F o 2 - F c 2 ) 2 / (F o 2 )] 1/2. S7

8 Weight / % % -5.20% [-2H 2 O (Cal %)] % [ -2DMF) Cal %)] Temperature / o C As made Desolventized Figure 1S TGA curves of the samples of 1: black, as made; and red, solvent free. S8

9 V ads. (STP) / cm 3 g _Ads 1_Des P / P 0 Figure 2S N 2 adsorption isotherm of the solvent free 1 at 77K. S9

10 Figure 3S Powder X-ray diffraction patterns of 1: black, the simulated; red, as made; and blue, solvent free. S10

11 Figure 4S Result of the Rietveld analysis of the Synchrotron XRD pattern of 1 at room temperature (CHI 2 =2.613, wr p =13.53%, R p =11.61%). The solid line represents the calculated profile. The + signs represent the raw data. Vertical bars indicate the position of Bragg peaks. The lowest curve is the difference between the observed and calculated patterns. S11

12 Table 2S Crystal structures from Rietveld refinement results of synchrotron XRD pattern of 1. Atom Wyck. x/a y/b z/c Occupancy Ca 4b (2) Zn 8c (5) (2) (4) 1 C1 8c (2) (2) (3) 1 C2 8c (3) (2) (3) 1 C3 8c (4) (2) (2) 1 C4 8c (2) (6) (2) 1 C5 8c (2) (2) (2) 1 C6 8c (4) (4) (2) 1 C7 8c (4) (4) (4) 1 C8 8c (2) (2) (3) 1 C9 8c (2) (3) (3) 1 C10 8c (3) (4) (4) 1 C11 8c (5) (2) (5) 1 C12 8c (5) (4) (2) 1 H2 8c (5) (4) (2) 1 H4 8c (2) (4) (2) 1 H6 8c (2) (4) (5) 1 H10 8c (5) (5) (4) 1 H11A 8c (4) (5) (4) 1 H11B 8c (4) (2) (5) 1 H11C 8c (2) (2) (4) 1 H12A 8c (4) (5) (2) 1 H12B 8c (4) (5) (5) 1 H12C 8c (3) (2) (2) 1 H1WA 8c (4) (6) (2) 1 H1WB 8c (5) (4) (7) 1 N1 8c (2) (1) (3) 1 O1 8c (2) (2) (4) 1 O2 8c (2) (6) (2) 1 O3 8c (4) (4) (4) 1 O4 8c (2) (2) (2) 1 S12

13 O5 8c (2) (3) (5) 1 O6 8c (3) (2) (5) 1 O7 8c (5) (4) (2) 1 O1W 8c (3) (6) (3) 1 S13