A flexible and wearable thermoelectric generator (TEG) could enable the conversion of human body heat into electrical power, which would help to realize a self-powered wearable electronic system. To overcome the difficulty of wearing existing flexible film TEGs, a novel 3D fabric TEG structure is designed in this study. By using a 3D fabric as the substrate and yarns coated with thermoelectric materials as legs, a wearable and flexible TEG can be realized. The designed generator has a sandwich structure, similar to the classical inorganic generator, which allows the generation of a temperature difference in the fabric thickness direction, thus making it wearable and showing promising application in body heat conversion. To verify the effectiveness of the designed generator structure, a prototype was fabricated, using a locknit spacer fabric as the substrate and yarns coated with waterborne polyurethane/carbon nanotube thermoelectric composites as legs. The results suggest that the fabricated spacer fabric TEG prototype could work successfully, although the performance of this prototype is of a low level. To further improve the efficiency of the 3D fabric generator and apply it in wearable electronics in the future, highly efficient inorganic thermoelectric materials can be applied, and modifications on the conductive connections can be made.

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The complex formation between silver(I) and cysteine (H2Cys), penicillamine (H2Pen) or glutathione (H3Glu) in alkaline aqueous solution was examined using extended X-ray absorption fine structure (EXAFS) and 109Ag NMR spectroscopic techniques. The complexes formed in 0.1 mol·dm−3 Ag(I) solutions with cysteine and penicillamine were investigated for ligand/Ag(I) (L/Ag) mole ratios increasing from 2.0 to 10.0. For the series of cysteine solutions (pH 10 - 11) a mean Ag-S bond distance 2.45 ± 0.02 Å consistently emerged, while for penicillamine (pH 9) the average Ag-S bond distance gradually increased from 2.40 to 2.44 ± 0.02 Å. EXAFS and 109Ag NMR spectra of a concentrated Ag(I)-cysteine solution (CAg(I) = 0.8 mol·dm−3, L/Ag = 2.2) showed the mean Ag-S bond distance 2.47 ± 0.02 Å and δ(109Ag) = 1103 ppm, consistent with prevailing, partially oligomeric AgS3 coordinated species, while for penicillamine (CAg(I) = 0.5 mol·dm−3, L/Ag = 2.0) the mean Ag-S bond distance 2.40 ± 0.02 Å and δ(109Ag) = 922 ppm indicate that mononuclear AgS2 coordinated complexes dominate. For Ag(I)-glutathione solutions (CAg(I) = 0.01 mol·dm−3, pH ~ 11), mononuclear AgS2 coordinated species with the mean Ag-S bond distance 2.36 ± 0.02 Å dominate for L/Ag mole ratios from 2.0 to 10.0. The crystal structure of the silver(I)-cysteine compound (NH4)Ag2(HCys)(Cys)·H2O (1) precipitating at pH ~ 10 was solved and showed a layer structure with both AgS3 and AgS3N coordination to the cysteinate ligands. A redetermination of the crystal structure of Ag(HPen)·H2O (2) confirmed the proposed digonal AgS2 coordination environment to bridging thiolate sulfur atoms in polymeric intertwining chains forming a double helix. A survey of Ag-S bond distances for crystalline Ag(I) complexes with S-donor ligands in different AgS2, AgS2(O/N) and AgS3 coordination environments was used, together with a survey of 109Ag NMR chemical shifts, to assist assignments of the Ag(I) coordination in solution.

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A spectroscopic investigation of the complexes formed between the Pb(II) ion and D-penicillamine (H2Pen), a chelating agent used in the treatment of lead poisoning, was carried out on two sets of alkaline aqueous solutions with CPb(II) ≈ 10 and 100 mM, varying the H2Pen/Pb(II) mole ratio (2.0, 3.0, 4.0, 10.0). UV-vis. spectra of the 10 mM Pb(II) solutions consistently showed an absorption peak at 298 nm for S− → Pb(II) ligand-to-metal charge-transfer. The downfield 13C NMR chemical shift for the penicillamine COO− group confirmed Pb(II) coordination. The 207Pb NMR chemical shifts were confined to a narrow range between 1806 and 1873 ppm for all Pb(II)-penicillamine solutions, indicating only small variations in the speciation even in large penicillamine excess. Those chemical shifts are considerably deshielded relative to the solid-state 207Pb NMR isotropic chemical shift of 909 ppm obtained for crystalline penicillaminatolead(II) with Pb(S,N,O-Pen) coordination. The Pb LIII-edge extended X-ray absorption fine structure (EXAFS) spectra obtained for these solutions were well modeled with two Pb-S and two Pb-(N/O) bonds with mean distances 2.64 ± 0.04 Å and 2.45 ± 0.04 Å, respectively. The combined spectroscopic results, reporting δ(207Pb) ~1870 ppm and λmax ~ 298 nm for a PbIIS2NO site, are consistent with a dominating 1:2 lead(II):penicillamine complex with [Pb(S,N,O-Pen)(S-HnPen)]2−n (n = 0 – 1) coordination in alkaline solutions, and provide useful structural information on how penicillamine can function as an antidote against lead toxicity in-vivo.

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