Actuating Shape Memory Polymer for Thermoresponsive Soft Robotic Gripper and Programmable Materials

For soft robotics and programmable metamaterials, novel approaches are required enabling the design of highly integrated thermoresponsive actuating systems. In the concept presented here, the necessary functional component was obtained by polymer syntheses. First, poly(1,10-decylene adipate) diol (PDA) with a number average molecular weight M_n of 3290 g·mol⁻¹ was synthesized from 1,10-decanediol and adipic acid. Afterward, the PDA was brought to reaction with 4,4′-diphenylmethane diisocyanate and 1,4-butanediol. The resulting polyester urethane (PEU) was processed to the filament, and samples were additively manufactured by fused-filament fabrication. After thermomechanical treatment, the PEU reliably actuated under stress-free conditions by expanding on cooling and shrinking on heating with a maximum thermoreversible strain of 16.1%. Actuation stabilized at 12.2%, as verified in a measurement comprising 100 heating-cooling cycles. By adding an actuator element to a gripper system, a hen’s egg could be picked up, safely transported and deposited. Finally, one actuator element each was built into two types of unit cells for programmable materials, thus enabling the design of temperature-dependent behavior. The approaches are expected to open up new opportunities, e.g., in the fields of soft robotics and shape morphing.     

Mediated Generation of Conjugate Acid by UV and Blue Sensitizers with Upconversion Nanoparticles at 980 nm

NIR and UV exposure of systems comprising upconversion nanoparticles ( UCNP ) based on NaYF₄:Tm/Yb@NaYF₄, a sensitizer absorbing either in the blue or UV region, and an onium salt with weak coordinating anion resulted in formation of conjugate acid (con-H⁺). That was namely Ivocerin (di(4-methoxybenzoyl)diethylgermane), ITX (2-iso-propyl thioxanthone), anthracene, pyrene, rubrene, camphore quinone, and a strong fluorescent coumarin (1,1,6,6,8-pentamethyl-2,3,5,6-tetrahyhdro-1H,4H-11-oxa-3a-aza-benzo[de]anthracene-10-one). Quantification occurred by treatment with Rhodamine B lactone whose color switched to intensive red after photolytic formation of con-H⁺. Exposure with a NIR laser at 980 nm resulted in less con-H⁺ compared to 395 nm where all sensitizers absorb radiation. UCNP did not mainly interfered formation of con-H⁺. The different rates obtained in both experiments responsibly explain the failure and success to initiate polymerization of epoxides applying ether 980 nm or 395 nm excitation, respectively.     

Isolation of a 16π-Electrons 1,4-Diphosphinine-1,4-diide with a Planar C4P2 Ring

Herein, we report the first 1,4-diphosphinine-1,4-diide compound [(ADC^Ph)P]₂ ( 5-Ph ) (ADC^Ph=PhC{(NDipp)C}₂; Dipp=2,6-iPr₂C₆H₃) derived from an anionic dicarbene (ADC^Ph) as a red crystalline solid. Compound 5-Ph containing a 16π-electron planar fused-tricyclic ring system was obtained by the 4e reduction of [(ADC^Ph)PCl₂]₂ ( 4-Ph ) with Mg (or KC₈) in a quantitative yield. Experimental and computational results imply that the central 8π-electrons C₄P₂ ring of 5-Ph , which is fused between two 6π-electrons C₃N₂ aromatic rings, is antiaromatic. Thus, each of the phosphorus atoms of 5-Ph has two electron-lone-pairs, one in a p-type orbital is in conjugation with the C=C bonds of the C₄P₂ ring, while the second resides in a σ-symmetric orbital. This can be shown with the gold complex [(ADC^Ph)P(AuCl)₂]₂ ( 6-Ph ) obtained by reacting 5-Ph with (Me₂S)AuCl. A mixture of 5-Ph and 4-Ph undergoes comproportionation in the presence of MgCl₂ to form the intermediate oxidation state compound [(ADC^Ar)P]₂(MgCl₄) ( 7-Ph ), which is an aromatic species.     

Mechanistic Study of the Role of Primary Amines in Precursor Conversions to Semiconductor Nanocrystals at Low Temperature

Primary alkyl amines (RNH₂) have been empirically used to engineer various colloidal semiconductor nanocrystals (NCs). Here, we present a general mechanism in which the amine acts as a hydrogen/proton donor in the precursor conversion to nanocrystals at low temperature, which was assisted by the presence of a secondary phosphine. Our findings introduce the strategy of using a secondary phosphine together with a primary amine as new routes to prepare high‐quality NCs at low reaction temperatures but with high particle yields and reproducibility and thus, potentially, low production costs.     

Potassium 1,1′‐Dinitramino‐5,5′‐bistetrazolate: A Primary Explosive with Fast Detonation and High Initiation Power

Adequate primary explosives such as lead azide mostly contain toxic ingredients, which have to be replaced. A new candidate that shows high potential, potassium 1,1′‐dinitramino‐5,5′‐bistetrazolate (K₂DNABT), was synthesized by a sophisticated synthetic procedure based on dimethylcarbonate and glyoxal. It was intensively characterized for its chemical (X‐ray diffraction, EA, NMR and vibrational spectroscopy) and physico‐chemical properties (sensitivity towards impact, friction, and electrostatic, DSC). The obtained primary explosive combines good thermal stability with the desired mechanical stability. Owing to its high heat of formation (326 kJ mol^?1) and density (2.11 g cm^?3), impressive values for its detonation velocity (8330 m s^?1) and pressure (311 kbar) were computed. Its superior calculated performance output was successfully confirmed and demonstrated by different convenient energetic test methods.     

GeS2 and GeSe2 PECVD from GeCl4 and Various Chalcogenide Precursors

The plasma enhanced chemical vapor depositions of germanium chalcogenide thin films from germanium tetrachloride, hydrogen sulfide and alkyl chalcogenides were studied to determine the viability of these reagents for thin film deposition. Hydrogen sulfide is a commonly used reagent for this technique and was used to determine optimal reaction conditions for thin film deposition. Germanium tetrachloride, alkylsulfides and alkylselenides were also employed because of their lower potential toxicities and higher availabilities compared to their more typical congeners: germane, hydrogen sulfide and hydrogen selenide in the formation of germanium chalcogenides. Alkylsulfides were found to be unsuitable for the deposition of germanium sulfides, however alkylselenide precursors were used successfully for the deposition of germanium selenides. The relative mass flow rates, reactor pressure, substrate temperature and plasma power density were studied for their effects on germanium chalcogenide deposition. These parameters affected the composition, deposition rate, film quality, and spectroscopic properties of the deposited films.     

Ferric Ion Driven Assembly of Catalase-like Supramolecular Photosensitizing Nanozymes for Combating Hypoxic Tumors

A facile approach to assemble catalase-like photosensitizing nanozymes with a self-oxygen-supplying ability was developed. The process involved Fe³⁺-driven self-assembly of fluorenylmethyloxycarbonyl (Fmoc)-protected amino acids. By adding a zinc(II) phthalocyanine-based photosensitizer (ZnPc) and the hypoxia-inducible factor 1 (HIF-1) inhibitor acriflavine (ACF) during the Fe³⁺-promoted self-assembly of Fmoc-protected cysteine (Fmoc-Cys), the nanovesicles Fmoc-Cys/Fe@Pc and Fmoc-Cys/Fe@Pc/ACF were prepared, which could be disassembled intracellularly. The released Fe³⁺ could catalyze the transformation of H₂O₂ enriched in cancer cells to oxygen efficiently, thereby ameliorating the hypoxic condition and promoting the photosensitizing activity of the released ZnPc. With an additional therapeutic component, Fmoc-Cys/Fe@Pc/ACF exhibited higher in vitro and in vivo photodynamic activities than Fmoc-Cys/Fe@Pc, demonstrating the synergistic effect of ZnPc and ACF.