Acid-catalyzed esterification and biotin/fluorescent labeling of glutathione polysulfides based on stability under heating and pH change.
Yazaki, Masana; Zhang, Yaozhuo; Zhou, Lin; Morise, Ryo; Akaike, Takaaki; Arisawa, Mieko; Chemical communications (Cambridge, England) 62 (2026) 2668–2671; doi:10.1039/d5cc07029e

data_7135482
_publ_section_title
;
 Acid-catalyzed esterification and biotin/fluorescent labeling of
 glutathione polysulfides based on stability under heating and pH change.
;
_journal_issue                   8
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2668
_journal_page_last               2671
_journal_paper_doi               10.1039/d5cc07029e
_journal_volume                  62
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H32 N6 O12 S3, 2(H2 O)'
_chemical_formula_sum            'C20 H36 N6 O14 S3'
_chemical_formula_weight         680.73
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-27
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-08-18 deposited with the CCDC.	2026-01-02 downloaded from the CCDC.
;
_cell_angle_alpha                83.7804(13)
_cell_angle_beta                 88.7700(14)
_cell_angle_gamma                89.4031(17)
_cell_formula_units_Z            1
_cell_length_a                   5.34785(12)
_cell_length_b                   9.40623(18)
_cell_length_c                   14.69319(20)
_cell_measurement_reflns_used    12877
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      75.8720
_cell_measurement_theta_min      3.0000
_cell_volume                     734.57(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -52.00 -26.00   0.50    0.12    -- -104.00  63.00-150.00   52
  2  \w    -27.00  17.00   0.50    0.12    --  -65.16  45.00 -90.00   88
  3  \w    -27.00  17.00   0.50    0.12    --  -65.16  45.00 -30.00   88
  4  \w    -52.00 -27.00   0.50    0.12    -- -104.00  63.00   0.00   50
  5  \w    -73.00 -21.00   0.50    0.12    -- -104.00  77.00  90.00  104
  6  \w    -97.00  -7.00   0.50    0.12    --  -65.16 114.00  88.00  180
  7  \w    -96.00 -25.00   0.50    0.12    -- -104.00 114.00  88.00  142
  8  \w    -32.00  -4.00   0.50    0.12    --  -40.00 -67.00  81.62   56
  9  \w    -38.00  -9.00   0.50    0.12    --  -44.00 -64.00 155.80   58
 10  \w    -32.00  -4.00   0.50    0.12    --  -40.00 -67.00  63.25   56
 11  \w    -37.00  -9.00   0.50    0.12    --  -44.00 -65.00 -25.05   56
 12  \w    -34.00  -8.00   0.50    0.12    --  -44.00 -66.00 -86.53   52
 13  \w    -19.00   8.00   0.50    0.05    --  -28.00 -73.00-145.28   54
 14  \w    -43.00 -17.00   0.50    0.12    --  -52.00 -62.00 -64.58   52
 15  \w    -54.00 -25.00   0.50    0.12    --  -60.00 -59.00 -77.42   58
 16  \w    -51.00 -24.00   0.50    0.12    --  -60.00 -60.00 -41.34   54
 17  \w    -54.00 -25.00   0.50    0.12    --  -60.00 -56.00-123.42   58
 18  \w    -51.00 -16.00   0.50    0.12    --  -52.00 -60.00  -0.19   70
 19  \w    -48.00 -20.00   0.50    0.12    --  -56.00 -61.00 107.53   56
 20  \w    -51.00 -24.00   0.50    0.12    --  -60.00 -60.00 146.21   54
 21  \w    -54.00 -28.00   0.50    0.12    --  -64.00 -53.00  68.34   52
 22  \w    -54.00 -25.00   0.50    0.12    --  -60.00 -56.00  92.28   58
 23  \w    -54.00 -28.00   0.50    0.12    --  -64.00 -55.00  41.20   52
 24  \w    -54.00 -28.00   0.50    0.12    --  -64.00 -53.00  12.75   52
 25  \w    -54.00 -25.00   0.50    0.12    --  -60.00 -56.00-149.60   58
 26  \w    -54.00 -25.00   0.50    0.12    --  -60.00 -56.00-171.52   58
 27  \w   -158.00 -40.00   0.50    0.12    --  -76.00 -52.00-101.23  236
 28  \w   -147.00 -30.00   0.50    0.12    --  -65.16 -52.00 -67.24  234
 29  \w   -162.00 -44.00   0.50    0.12    --  -80.00 -52.00 -77.60  236
 30  \w   -170.00 -52.00   0.50    0.12    --  -88.00 -52.00-116.12  236
 31  \w   -175.00 -64.00   0.50    0.12    -- -100.00 -52.00 -24.81  222
 32  \w   -162.00 -44.00   0.50    0.12    --  -80.00 -52.00 -15.29  236
 33  \w   -158.00 -40.00   0.50    0.12    --  -76.00 -52.00  12.13  236
 34  \w   -175.00 -60.00   0.50    0.12    --  -96.00 -52.00  64.26  230
 35  \w   -162.00 -44.00   0.50    0.12    --  -80.00 -52.00  90.12  236
 36  \w   -175.00 -67.00   0.50    0.12    -- -104.00 -51.00  29.86  216
 37  \w   -175.00 -68.00   0.50    0.12    -- -104.00 -50.00 120.00  214
 38  \w   -147.00 -30.00   0.50    0.12    --  -65.16 -50.00 170.16  234
 39  \w    -99.00 -68.00   0.50    0.12    -- -104.00 -52.00   1.25   62
 40  \w   -103.00 -72.00   0.50    0.12    -- -104.00 -52.00-109.37   62
 41  \w   -175.00 -68.00   0.50    0.12    -- -104.00 -50.00 -78.78  214
 42  \w   -175.00 -68.00   0.50    0.12    -- -104.00 -50.00 -90.00  214
 43  \w    -96.00 -70.00   0.50    0.12    -- -104.00 -50.00 -60.00   52
 44  \w   -174.00 -56.00   0.50    0.12    --  -92.00 -50.00-137.21  236
 45  \w   -175.00 -68.00   0.50    0.12    -- -104.00 -52.00-153.92  214
 46  \w   -175.00 -68.00   0.50    0.12    -- -104.00 -50.00-150.00  214
 47  \w   -158.00 -40.00   0.50    0.12    --  -76.00 -50.00  61.63  236
 48  \w   -158.00 -40.00   0.50    0.12    --  -76.00 -50.00 136.72  236
 49  \w   -175.00-143.00   0.50    0.12    -- -104.00 -50.00 100.71   64
 50  \w   -175.00 -68.00   0.50    0.12    -- -104.00 -48.00 159.98  214
 51  \w    -97.00 -69.00   0.50    0.12    -- -104.00 -50.00 100.71   56
 52  \w   -149.00 -97.00   0.50    0.12    --  -65.16-114.00  -2.00  104
 53  \w   -147.00 -90.00   0.50    0.12    --  -65.16-125.00 -30.00  114
 54  \w   -175.00 -97.00   0.50    0.12    -- -104.00-114.00  -2.00  156
 55  \w     12.00  97.00   0.50    0.12    --   65.16-114.00  -2.00  170
 56  \w     19.00 100.00   0.50    0.12    --   65.16-125.00 -90.00  162
 57  \w     65.00  90.00   0.50    0.12    --  118.75-111.00-120.00   50
 58  \w     35.00  60.00   0.50    0.12    --  118.75-111.00-120.00   50
 59  \w     35.00  97.00   0.50    0.12    --  118.75-114.00  -2.00  124
 60  \w     36.00  61.00   0.50    0.12    --  118.75-111.00  90.00   50
 61  \w     65.00  91.00   0.50    0.12    --  118.75-111.00  90.00   52
 62  \w     35.00  69.00   0.50    0.12    --  118.75-111.00 150.00   68
 63  \w     30.00  90.00   0.50    0.12    --  118.75 -93.00 171.66  120
 64  \w     32.00  84.00   0.50    0.12    --  118.75 -91.00   0.00  104
 65  \w     29.00  92.00   0.50    0.12    --  118.75 -91.00  30.00  126
 66  \w     66.00  92.00   0.50    0.12    --  118.75 -91.00  90.00   52
 67  \w     32.00  63.00   0.50    0.12    --  118.75 -91.00  90.00   62
 68  \w     67.00  92.00   0.50    0.12    --  118.75 -91.00-120.00   50
 69  \w     54.00  92.00   0.50    0.12    --  118.75 -91.00-180.00   76
 70  \w     29.00  55.00   0.50    0.12    --  118.75 -91.00-120.00   52
 71  \w     40.00  89.00   0.50    0.12    --  118.75 -91.00 -90.00   98
 72  \w     29.00  92.00   0.50    0.12    --  118.75 -91.00 -60.00  126
 73  \w     46.00  92.00   0.50    0.12    --  118.75 -91.00 120.00   92
 74  \w    -86.00  21.00   0.50    0.05    --    0.00 -38.00  60.00  214
 75  \w    -38.00  21.00   0.50    0.05    --    0.00  77.00 -60.00  118
 76  \w    -35.00  59.50   0.50    0.05    --    0.00  57.00-150.00  189
 77  \w    101.00 178.00   0.50    0.12    --  118.75  63.00-180.00  154
 78  \w    133.00 168.00   0.50    0.12    --  118.75  50.00-150.00   70
 79  \w     83.00 122.00   0.50    0.12    --  118.75  50.00-150.00   78
 80  \w    119.00 172.00   0.50    0.12    --  118.75  77.00 -60.00  106
 81  \w    145.00 177.00   0.50    0.12    --  118.75  63.00  60.00   64
 82  \w    145.00 173.00   0.50    0.12    --  118.75  50.00 120.00   56
 83  \w    109.00 140.00   0.50    0.12    --  118.75  63.00  60.00   62
 84  \w     84.00 110.00   0.50    0.12    --  118.75  50.00 120.00   52
 85  \w     84.00 140.00   0.50    0.12    --  118.75  50.00  90.00  112
 86  \w    131.00 171.00   0.50    0.12    --  118.75  50.00 150.00   80
 87  \w     83.00 119.00   0.50    0.12    --  118.75  50.00 150.00   72
 88  \w    131.00 161.00   0.50    0.12    --  118.75  50.00  60.00   60
 89  \w     86.00 156.00   0.50    0.12    --  118.75  50.00   0.00  140
 90  \w     84.00 113.00   0.50    0.12    --  118.75  50.00  60.00   58
 91  \w     94.00 123.00   0.50    0.12    --  118.75  50.00 -30.00   58
 92  \w    144.00 175.00   0.50    0.12    --  118.75  50.00  90.00   62
 93  \w    151.00 176.00   0.50    0.12    --  118.75  50.00 -30.00   50
 94  \w     83.00 178.00   0.50    0.12    --  118.75  50.00  30.00  190
 95  \w    123.00 156.00   0.50    0.12    --  118.75  50.00 -60.00   66
 96  \w    139.00 172.00   0.50    0.12    --  118.75  50.00-120.00   66
 97  \w     85.00 117.00   0.50    0.12    --  118.75  50.00-180.00   64
 98  \w     83.00 131.00   0.50    0.12    --  118.75  50.00-120.00   96
 99  \w     85.00 111.00   0.50    0.12    --  118.75  50.00 -60.00   52
100  \w     86.00 111.00   0.50    0.12    --  118.75  38.00 -30.00   50
101  \w     92.00 156.00   0.50    0.12    --  118.75  38.00  30.00  128
102  \w    136.00 175.00   0.50    0.12    --  118.75  38.00 -30.00   78
103  \w    130.00 174.00   0.50    0.12    --  118.75  38.00 -90.00   88
104  \w     86.00 123.00   0.50    0.12    --  118.75  38.00 -90.00   74
105  \w     59.00  92.00   0.50    0.12    --  118.75  25.00-180.00   66
106  \w    108.00 159.00   0.50    0.12    --  118.75  25.00-180.00  102
107  \w    118.00 144.00   0.50    0.12    --  118.75 111.00-180.00   52
108  \w    150.00 176.00   0.50    0.12    --  118.75 111.00-180.00   52
109  \w    139.00 174.00   0.50    0.12    --  118.75 111.00   0.00   70
110  \w    102.00 178.00   0.50    0.12    --  118.75 114.00  88.00  152
111  \w    -54.00  -6.50   0.50    0.05    --    0.00 114.00  88.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0150184000
_diffrn_orient_matrix_UB_12      -0.1259065000
_diffrn_orient_matrix_UB_13      0.0760691000
_diffrn_orient_matrix_UB_21      -0.0949455000
_diffrn_orient_matrix_UB_22      0.0984671000
_diffrn_orient_matrix_UB_23      0.0707756000
_diffrn_orient_matrix_UB_31      -0.2716408000
_diffrn_orient_matrix_UB_32      -0.0399551000
_diffrn_orient_matrix_UB_33      -0.0182427000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            19904
_diffrn_reflns_point_group_measured_fraction_full 0.930
_diffrn_reflns_point_group_measured_fraction_max 0.914
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.480
_diffrn_reflns_theta_min         3.026
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.998
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87754
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.539
_exptl_crystal_description       plate
_exptl_crystal_F_000             358
_exptl_crystal_size_max          0.076
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.336
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 2329 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.017(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     404
_refine_ls_number_reflns         5503
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0341
_refine_ls_R_factor_gt           0.0326
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0504P)^2^+0.0466P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0820
_refine_ls_wR_factor_ref         0.0829
_reflns_Friedel_coverage         0.850
_reflns_Friedel_fraction_full    0.867
_reflns_Friedel_fraction_max     0.840
_reflns_number_gt                5296
_reflns_number_total             5503
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc07029e2.cif
_cod_data_source_block           am2307d_auto
_cod_database_code               7135482
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S'
_shelx_estimated_absorpt_t_max   0.915
_shelx_estimated_absorpt_t_min   0.804
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All O(H) groups, All O(H,H) groups
2. Restrained distances
 O13-H13A = O13-H13B
 0.87 with sigma of 0.02
 O14-H14C = O14-H14D
 0.87 with sigma of 0.02
 H13A-H13B
 1.38 with sigma of 0.04
 H14C-H14D
 1.38 with sigma of 0.04
3.a Ternary CH refined with riding coordinates:
 C2(H2), C6(H6B), C12(H12A), C16(H16)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C4(H4A,H4B), C5(H5D,H5E), C9(H9A,H9B), C11(H11A,H11B), C14(H14A,
 H14B), C15(H15A,H15B), C19(H19A,H19B)
3.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N3(H3), N4(H4), N6(H6A)
3.d Idealised Me refined as rotating group:
 N2(H2A,H2B,H2C), N5(H5A,H5B,H5C)
3.e Idealised tetrahedral OH refined as rotating group:
 O6(H6), O12(H12)
;
_shelx_res_checksum              60421
_shelx_hkl_checksum              98298
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.480
_oxdiff_exptl_absorpt_empirical_full_min 0.625