Rational Development of Guanidinate and Amidinate Based Cerium and Ytterbium Complexes as Atomic Layer Deposition Precursors: Synthesis,Modeling, and Application

Owing to the limited availability of suitable precursors for vapor phase deposition of rare-earth containing thin-film materials, new or improved precursors are sought after. In this study, we explored new precursors for atomic layer deposition (ALD) of cerium (Ce) and ytterbium (Yb) containing thin films. A series of homoleptic tris-guanidinate and tris-amidinate complexes of cerium (Ce) and ytterbium (Yb) were synthesized and thoroughly characterized. The C-substituents on the N-C-N backbone (Me, NMe₂, NEt₂, where Me=methyl, Et=ethyl) and the N-substituents from symmetrical iso-propyl (iPr) to asymmetrical tertiary-butyl (tBu) and Et were systematically varied to study the influence of the substituents on the physicochemical properties of the resulting compounds. Single crystal structures of [Ce(dpdmg)₃] 1 and [Yb(dpdmg)₃] 6 (dpdmg=N,N'-diisopropyl-2-dimethylamido-guanidinate) highlight a monomeric nature in the solid-state with a distorted trigonal prismatic geometry. The thermogravimetric analysis shows that the complexes are volatile and emphasize that increasing asymmetry in the complexes lowers their melting points while reducing their thermal stability. Density functional theory (DFT) was used to study the reactivity of amidinates and guanidinates of Ce and Yb complexes towards oxygen (O₂) and water (H₂O). Signified by the DFT calculations, the guanidinates show an increased reactivity toward water compared to the amidinate complexes. Furthermore, the Ce complexes are more reactive compared to the Yb complexes, indicating even a reactivity towards oxygen potentially exploitable for ALD purposes. As a representative precursor, the highly reactive [Ce(dpdmg)₃] 1 was used for proof-of-principle ALD depositions of CeO₂ thin films using water as co-reactant. The self-limited ALD growth process could be confirmed at 160 °C with polycrystalline cubic CeO₂ films formed on Si(100) substrates. This study confirms that moving towards nitrogen-coordinated rare-earth complexes bearing the guanidinate and amidinate ligands can indeed be very appealing in terms of new precursors for ALD of rare earth based materials.     

Thermally Induced Synthesis of Anthracene-, Pyrene- and Naphthalene-Fused Porphyrins

The synthesis of π-extended porphyrins containing anthracenyl moieties still represents an important challenge. Here, we report on the synthesis of a series of unsubstituted naphthyl-, pyrenyl- and anthracenyl-fused zinc porphyrin derivatives. To this aim, meso-substitued porphyrins are synthesized and the fusion of the PAHs (Polycyclic Aromatic Hydrocarbon) on the β-positions are performed through thermally induced dehydro-aromatization. The fused zinc-porphyrin derivatives are fully characterized and their optical absorption and photoluminescence properties are reported. We also demonstrate that zinc can be removed from the porphyrin core, giving rise to pure C, H, N materials. This work constitutes the first step towards the synthesis of the fully-fused tetra-anthracenylporphyrin.     

Stability Enhancement of a Dimeric HER2-Specific Affibody Molecule through Sortase A-Catalyzed Head-to-Tail Cyclization

Natural backbone-cyclized proteins have an increased thermostability and resistance towards proteases, characteristics that have sparked interest in head-to-tail cyclization as a method to stability-enhance proteins used in diagnostics and therapeutic applications, for example. In this proof-of principle study, we have produced and investigated a head-to-tail cyclized and HER2-specific Z_HER2:342 Affibody dimer. The sortase A-mediated cyclization reaction is highly efficient (>95%) under optimized conditions, and renders a cyclic Z_HER3:342-dimer with an apparent melting temperature, T_m, of 68 °C, which is 3 °C higher than that of its linear counterpart. Circular dichroism spectra of the linear and cyclic dimers looked very similar in the far-UV range, both before and after thermal unfolding to 90 °C, which suggests that cyclization does not negatively impact the helicity or folding of the cyclic protein. The cyclic dimer had an apparent sub-nanomolar affinity (K_d ~750 pM) to the HER2-receptor, which is a ~150-fold reduction in affinity relative to the linear dimer (K_d ~5 pM), but the anti-HER2 Affibody dimer remained a high-affinity binder even after cyclization. No apparent difference in proteolytic stability was detected in an endopeptidase degradation assay for the cyclic and linear dimers. In contrast, in an exopeptidase degradation assay, the linear dimer was shown to be completely degraded after 5 min, while the cyclic dimer showed no detectable degradation even after 60 min. We further demonstrate that a site-specifically DyLight 594-labeled cyclic dimer shows specific binding to HER2-overexpressing cells. Taken together, the results presented here demonstrate that head-to-tail cyclization can be an effective strategy to increase the stability of an Affibody dimer.     

Rheological and Solubility Properties of Soy Protein Isolate

Soy protein isolate (SPI) powders often have poor water solubility, particularly at pH values close to neutral, which is an attribute that is an issue for its incorporation into complex nutritional systems. Therefore, the objective of this study was to improve SPI solubility while maintaining low viscosity. Thus, the intention was to examine the solubility and rheological properties of a commercial SPI powder at pH values of 2.0, 6.9, and 9.0, and determine if heat treatment at acidic or alkaline conditions might positively influence protein solubility, once re-adjusted back to pH 6.9. Adjusting the pH of SPI dispersions from pH 6.9 to 2.0 or 9.0 led to an increase in protein solubility with a concomitant increase in viscosity at 20 °C. Meanwhile, heat treatment at 90 °C significantly improved the solubility at all pH values and resulted in a decrease in viscosity in samples heated at pH 9.0. All SPI dispersions measured under low-amplitude rheological conditions showed elastic-like behaviour (i.e., G′ > G″), indicating a weak “gel-like” structure at frequencies less than 10 Hz. In summary, the physical properties of SPI can be manipulated through heat treatment under acidic or alkaline conditions when the protein subunits are dissociated, before re-adjusting to pH 6.9.     

Recycling of Primary Lithium Batteries Production Residues

Production waste of primary lithium batteries constitutes a considerable secondary lithium feedstock. Although the recycling of lithium batteries is a widely studied field of research, the metallic residues of non-rechargeable lithium battery production are disposed of as waste without further recycling. The risks of handling metallic Li on a large scale typically prevent the metal from being recycled. A way out of this situation is to handle Li in an aqueous solution, from where it can be isolated as Li₂CO₃. However, the challenge in hydrometallurgical treatment lies in the high energy release during dissolution and generation of H₂. To reduce these process-related risks, the Li sheet metal punching residues underwent oxidative thermal treatment from 300 to 400 °C prior to dissolution in water. Converting Li metal to Li₂O in this initial process step results in an energy release reduction of ∼70 %. The optimal oxidation conditions have been determined by experimental design varying three factors: temperature, Li metal sheet thickness, and residence time. With 96.9±2.6 % almost the entire Li amount is converted to Li₂O, after 2.5 h treatment at 400 °C for a Li sheet thickness of 1.99 mm. Final precipitation with CO₂ yields 85.5±3.0 % Li₂CO₃. Using pure Li sheets, the product Li₂CO₃ is obtained in battery-grade quality (>99.5 %). Non-precipitated Li is recirculated into the process on the stage of dissolving Li₂O, thus avoiding loss of material.     

Tailoring the Thermal Conductivity of Rubber Nanocomposites by Inorganic Systems: Opportunities and Challenges for Their Application in Tires Formulation

The development of effective thermally conductive rubber nanocomposites for heat management represents a tricky point for several modern technologies, ranging from electronic devices to the tire industry. Since rubber materials generally exhibit poor thermal transfer, the addition of high loadings of different carbon-based or inorganic thermally conductive fillers is mandatory to achieve satisfactory heat dissipation performance. However, this dramatically alters the mechanical behavior of the final materials, representing a real limitation to their application. Moreover, upon fillers’ incorporation into the polymer matrix, interfacial thermal resistance arises due to differences between the phonon spectra and scattering at the hybrid interface between the phases. Thus, a suitable filler functionalization is required to avoid discontinuities in the thermal transfer. In this challenging scenario, the present review aims at summarizing the most recent efforts to improve the thermal conductivity of rubber nanocomposites by exploiting, in particular, inorganic and hybrid filler systems, focusing on those that may guarantee a viable transfer of lab-scale formulations to technological applicable solutions. The intrinsic relationship among the filler’s loading, structure, morphology, and interfacial features and the heat transfer in the rubber matrix will be explored in depth, with the ambition of providing some methodological tools for a more profitable design of thermally conductive rubber nanocomposites, especially those for the formulation of tires.     

Coating Cellulosic Material with Ag Nanowires to Fabricate Wearable IR-Reflective Device for Personal Thermal Management: The Role of Coating Method and Loading Level

Textiles coated with silver nanowires (AgNWs) are effective at suppressing radiative heat loss without sacrificing breathability. Many reports present the applicability of AgNWs as IR-reflective wearable textiles, where such studies partially evaluate the parameters for practical usage for large-scale production. In this study, the effect of the two industrial coating methods and the loading value of AgNWs on the performance of AgNWs-coated fabric (AgNWs-CF) is reported. The AgNWs were synthesized by the polyol process and applied onto the surface of cotton fabric using either dip- or spray-coating methods with variable loading levels of AgNWs. X-ray diffraction, scanning electron microscopy (SEM), infrared (IR) reflectance, water vapor permeability (WVP), and electrical resistance properties were characterized. The results report the successful synthesis of AgNWs with a 30 μm length. The results also show that the spray coating method has a better performance for reflecting the IR radiation to the body, which increases with a greater loading level of the AgNWs. The antibacterial results show a good inhibition zone for cotton fabric coated by both methods, where the spray-coated fabric has a better performance overall. The results also show the coated fabric with AgNWs maintains the level of fabric breathability similar to control samples. AgNWs-CFs have potential utility for cold weather protective clothing in which heat dissipation is attenuated, along with applications such as wound dressing materials that provide antibacterial protection.     

The tribological performance of fullerene‐like hydrogenated carbon films under ionic liquid lubrication

Fullerene‐like hydrogenated carbon films were deposited on Si substrate by plasma‐enhanced chemical vapor deposition. The microstructures of films were characterized by high‐resolution transmission electron microscopy and Raman spectrum. The tribological performance of films was tested by reciprocating ball‐on‐disc tester under 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ionic liquid. The surface morphology and chemical composition of wear tracks and wear rates were investigated by optical microscope, X‐ray photoelectron spectroscopy, and 3D surface profiler. The results indicated that the film with a typical fullerene‐like structure embedded into the amorphous sp² and sp³ carbon networks could be prepared successfully, and the film shows a higher hardness (26.7 GPa) and elastic recovery (89.9%) compared with the amorphous carbon film. Furthermore, the film shows a lower friction coefficient at low contact load and friction frequency, and excellent wear‐resistance performance at high load and frequency under ionic liquid lubrication. Meanwhile, the wear life of fullerene‐like hydrogenated carbon films could be improved significantly using ionic liquid as a lubrication material. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis,Crystal Structure,Spectroscopic Characterization,Thermal Stability and Magnetic Properties of a Dinuclear Copper(Ⅱ) Complex

A new copper(Ⅱ) complex [Cu2(MNA)2(2,2‘-bipy)2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid(MNA) and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It crystallizes in monoclinic,space group P 1,with a = 10.4191(11),b = 12.8883(13),c = 16.1114(16) ?,α = 70.8090(10),β = 80.568(2),γ = 77.440(2)o,V = 1984.3(4) ?3,Dc = 1.551 g/cm3,Z = 2,F(000) = 962,the final GOOF = 1.051,R = 0.0431 and w R= 0.0980.The crystal structure shows that the whole molecule consists of two independent dinuclear units,in which two copper ions are bridged by two μ2-η1:η0 3-carboxylate groups of MNA2-.The coordination environment of Cu(Ⅱ) ion is Cu O3N2,giving a distorted square pyramidal geometry.The spectroscopic characterization,thermal stability and magnetic properties of the complex were investigated.     

Synthesis,Crystal Structure,Fluorescence, Thermal Stability and Magnetic Properties of the Dinuclear Manganese(Ⅱ) Complex [Mn_2(L)_2(2,2'-bipy)_2(H_2O)_5]_2·3H_2O

A new dinuclear manganese complex [Mn2(L)2(2,2'-bipy)2(H2O)5]2·3H2O has been synthesized with Mn SO4·H2O, 2,2'-bibenzoic acid(H2L) and 2,2'-bipyridine(2,2'-bipy) in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group P1 with a = 9.9944(10), b = 21.939(2), c = 25.628(3) ?, α = 108.429(3), β = 100.613(4), γ = 102.821(3)o, V = 4997.9(9) ?3, Dc = 1.355 g/cm3, Z = 2, F(000) = 2108, GOOF = 1.074, the R = 0.0626 and w R = 0.1531. The structure of the complex contains two [Mn2(L)2(2,2'-bipy)2] units, ten coordinated H2 O molecules and three uncoordinated H2 O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.