| Single-crystal XRD, space group | P21 |
|---|---|
| Single-crystal XRD, asymmetric unit | Two sulfamate anions, two L-Argininium cations, and one H2O molecule |
| Single-crystal XRD, material assignment | Salt hemihydrate of L-Arg and sulfamic acid |
| Single-crystal XRD, L-Argininium state | Deprotonated carboxylate center, protonated amino group, and guanidino side chain protonated by sulfamic acid |
| Single-crystal XRD, crystallographically distinct L-Argininium moieties | Two |
| Single-crystal XRD, sulfamate chains | N9—H9C...O6 hydrogen bonds along the crystallographic a axis |
| Single-crystal XRD, dimeric helical sulfamate chains | Two chains related by a screw axis and linked by N9—H9D...O10 hydrogen bonds |
| Single-crystal XRD, sulfamate sheets | Dimeric chains linked by water through O11—H9C...O6 hydrogen bonds into a corrugated two-dimensional sheet along the crystallographic ab plane |
| Single-crystal XRD, L-Argininium sheets | Corrugated two-dimensional sheets along the ab plane, formed through N7—H7B...N9 hydrogen bonds |
| Single-crystal XRD, L-Argininium-to-sulfamate sheet links | N6—H6...O6 and N5—H5A...O8 hydrogen bonds |
| Single-crystal XRD, crystallographically unique L-Argininium stack links | N3—H3A...N10, N3—H3B...O10, N4—H4A...O6, N1—H1C...O7, and N1—H1A...O9 hydrogen bonds to the sulfamate sheet; N4—H4B...O3, N7—H7A...O3, N2—H2A...O4, N8—H8B...O1, and N8—H8A...O2 hydrogen bonds to the corrugated L-Argininium sheet |
| Single-crystal XRD, H2O hydrogen-bond role | Hydrogen-bond donor and acceptor |
| TGA, weight loss from 65–120 °C | 3.64 % (≈ 3.44 % for one H2O molecule in the asymmetric unit) |
| TGA, decomposition | Above 135 °C |
| DSC, hydrate-to-anhydrate phase transition | Endotherm in the same temperature range as the TGA weight loss |
Suman Bhattacharya, Matthew Gleeson, Marie-Claire Schanne-Klein, Krishna Hari, Emma Kiely, Chiara Stringari, Emmanuel Beaurepaire, Sarah Guerin. “Modulating the polarization-resolved second harmonic generation response of a sulfamic acid multicomponent crystal via amino acid coformer selection.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007488/v1
The main paper refers to supporting information, but no separate supporting information file was found among the files available from the ChemRxiv record
| SEM | Condensed microneedle-shaped crystallites spread into domains with smooth surfaces; between rough-surfaced domains, crystallites protrude outwards in the vertical direction |
|---|---|
| SHG, smooth surfaces | Uniform signal |
| SHG signal power-scaling exponent | 2.05 |
| Polarization-resolved SHG profile | Four-lobe profile |
| Polarization-resolved SHG maximum | Excitation polarization around 40° relative to the needle long axis |
| Polarization-resolved SHG asymmetry | 10–30 % more signal at 40° excitation than at 120° relative to the needle long axis |
| Mean SHG modulation | 0.51 ± 0.2 |
| Polarization-resolved SHG angle-shift distribution | Centered close to 30° |
| Polarization-resolved SHG angle-shift map | Pyramidal needle tip shows an abrupt orientation change relative to the needle body; sloped sides display similar dark-blue and cyan colors |
| Fragment, effective nonlinear susceptibility relative to KDP | 0.9 ± 0.5 |
| Single-crystal XRD, space group | Pc |
|---|---|
| Single-crystal XRD, asymmetric unit | Two sulfamic acid units and one glycine moiety |
| Single-crystal XRD, glycine motif | Three-component charge-assisted hydrogen-bonded motif |
| Single-crystal XRD, sulfamic acid motif | N—H…O hydrogen-bonded tapes |
| SEM | Mixture of large platelets with smooth surfaces |
|---|---|
| SHG excitation power | 35 mW required before approaching PMT saturation |
| SHG image | Uniform signal across surfaces facing the laser, with reduced signal in facets sloped away from the laser |
| Polarization-resolved SHG profile | Two-lobe profile, narrower and closer to the β-glycine form than pure β- or γ-glycine microneedles |
| Polarization-resolved SHG angle-shift distribution | Narrow distribution reflecting the uniform response of each visible facet |
| Fragment polarization-resolved SHG Fourier analysis | Multiple directions for maximum SHG |
| Fragment, effective nonlinear susceptibility relative to KDP | 0.35 ± 0.2 |
| SHG signal over several months | No appreciable decrease |
| Single-crystal XRD, space group | P212121 |
|---|---|
| Single-crystal XRD, asymmetric unit | One L-Histidinium cation and one sulfamate anion |
| Single-crystal XRD, imidazole state | Protonated by sulfamic acid |
| Single-crystal XRD, L-Histidinium helical chains | Dimers formed by N4—H4...O5 hydrogen bonds along the crystallographic a axis |
| Single-crystal XRD, L-Histidinium sheets | Adjacent parallel chains linked by N2—H2B...O4 hydrogen bonds into a two-dimensional sheet across the ab plane |
| Single-crystal XRD, sheet links through sulfamate | N1—H1A...O5 and N3—H3...O2 hydrogen bonds |
| Single-crystal XRD, sulfamate chains | N1—H1B...O2 hydrogen bonds |
| TGA | No weight loss |
| DSC | Endotherm at approximately 203 °C, above which the material decomposes |
| SEM | Aggregates of needle-shaped crystallites from which further crystallites branch out, separated by areas where needle-shaped crystals protrude from the disc surface |
|---|---|
| SHG signal power scaling | Close to 2 |
| SHG signal in microneedle structures | High |
| Polarization-resolved SHG profile | Clear two-lobe profile |
| Polarization-resolved SHG maximum | Excitation polarization perpendicular to the microneedle long axis |
| Mean SHG modulation | 0.79 ± 0.1 |
| Polarization-resolved SHG angle-shift distribution | Narrow Gaussian distribution |
| Disc fragments, effective second-order nonlinear susceptibility relative to KDP | 3 ± 1.5 |
| SHG signal in microneedle structures | High |
|---|---|
| SHG signal power scaling | Close to 2 |
| Polarization-resolved SHG profile | Two-lobe profile with a higher minimum SHG value than the polycrystalline disc |
| Mean SHG modulation | 0.72 ± 0.2 |
| Polarization-resolved SHG angle-shift distribution | Narrow Gaussian distribution |
| Small protruding wire, effective second-order nonlinear susceptibility relative to KDP | 1 ± 0.5 |
| Single-crystal XRD, asymmetric unit | Two sulfamic acid units and five L-methionine units |
|---|---|
| Single-crystal XRD, L-methionine disorder | All five molecules disordered over two positions each |
| Single-crystal XRD, sulfamic acid state | Both moieties ordered and zwitterionic |
| Single-crystal XRD, space group | P21 |
| Single-crystal XRD, hydrogen-bonded structure | Parallel helical chains of L-methionine linked by sulfamic acid into a two-dimensional hydrogen-bonded net |
| Single-crystal XRD, hydrogen-bonded net stacking | Parallel along the crystallographic ac plane |
| TGA | No weight loss |
| DSC, phase transition | Approximately 142 °C |
| DSC, decomposition | Approximately 152 °C |
| SEM | Conglomeration of needle-shaped crystallites protruding from the surface at an offset angle |
|---|---|
| SHG signal power-scaling exponent | 1.94 |
| Surface morphology | Multifaceted, visibly smooth surfaces that vary widely in size |
| Polarization-resolved SHG profile | Two-lobe pattern |
| Polarization-resolved SHG maximum | Excitation polarization perpendicular to the needle long axis |
| Mean SHG modulation | 0.67 ± 0.21 |
| Polarization-resolved SHG angle-shift distribution | Consistent maximum signal perpendicular to the needle long axis |
| Fragment, effective nonlinear susceptibility relative to KDP | 1.7 ± 0.9 |
| SHG signal power-scaling exponent | 2.1 |
|---|---|
| Surface morphology | Flat surfaces with some irregular pitting |
| Polarization-resolved SHG profile | Mixture of two- and four-lobe profiles |
| Polarization-resolved SHG Fourier analysis | The uniform orange color presents as a single crystal |
| Mean SHG modulation | 0.73 ± 0.18 |
| Fragments, effective nonlinear susceptibility relative to KDP | 3.9 ± 1.9 |
| Single-crystal XRD, space group | P212121 |
|---|---|
| Single-crystal XRD, asymmetric unit | One sulfamic acid unit and two L-phenylalanine molecular units |
| Single-crystal XRD, molecular state | All three moieties are zwitterionic |
| Single-crystal XRD, sulfamic acid disorder | Both sulfamic acid moieties disordered over two positions and anisotropically modelled with 50 % occupancy |
| Single-crystal XRD, L-phenylalanine disorder | Aliphatic groups in both moieties disordered over two positions and isotropically refined with approximately 50 % occupancy |
| Single-crystal XRD, L-phenylalanine chains | N2AA—H2AD...O1B, N2AB—H2AA...O1A, N1BB—H1BA...O3B, and N1BB—H1BD...O3A hydrogen bonds along the a axis |
| Single-crystal XRD, sulfamic acid links between L-phenylalanine chains | N3A—H3AC...O4B, N3B—H3BC...O1A, and N1BB—H1BC...O7A hydrogen bonds |
| Single-crystal XRD, O...O interactions | Repulsive interactions between L-phenylalanine moieties |
| TGA | No weight loss until approximately 150 °C, followed by abrupt weight loss suggesting decomposition |
| DSC | Single endotherm at approximately 150 °C |
| SEM | Regular aggregation of needle-shaped crystallites |
|---|---|
| Surface morphology | Densely layered flat microneedles pointing in a uniform direction |
| Polarization-resolved SHG profile | Two-lobe shape with wider lobes than the other multicomponent crystals |
| Polarization-resolved SHG maximum | Excitation polarization around 30° relative to the needle long axis |
| Polarization-resolved SHG analysis | Uniform response for the microneedles; gaps that did not meet the R² filter of 0.7 were set to black |
| SHG signal power-scaling exponent | 2.1 |
| Mean SHG modulation | 0.59 ± 0.2 |
| Fragment polarization-resolved SHG Fourier analysis | Uniform color indicating a flat surface |
| Fragment angle-shift map | Distinct color along the fragment edges with lower modulation than the main domain |
| Fragment, effective nonlinear susceptibility relative to KDP | 2.0 ± 1 |