Coaxial Alginate Hydrogels: From Self-Assembled 3D Cellular Constructs to Long-Term Storage

Alginate as a versatile naturally occurring biomaterial has found widespread use in the biomedical field due to its unique features such as biocompatibility and biodegradability. The ability of its semipermeable hydrogels to provide a favourable microenvironment for clinically relevant cells made alginate encapsulation a leading technology for immunoisolation, 3D culture, cryopreservation as well as cell and drug delivery. The aim of this work is the evaluation of structural properties and swelling behaviour of the core-shell capsules for the encapsulation of multipotent stromal cells (MSCs), their 3D culture and cryopreservation using slow freezing. The cells were encapsulated in core-shell capsules using coaxial electrospraying, cultured for 35 days and cryopreserved. Cell viability, metabolic activity and cell–cell interactions were analysed. Cryopreservation of MSCs-laden core-shell capsules was performed according to parameters pre-selected on cell-free capsules. The results suggest that core-shell capsules produced from the low viscosity high-G alginate are superior to high-M ones in terms of stability during in vitro culture, as well as to solid beads in terms of promoting formation of viable self-assembled cellular structures and maintenance of MSCs functionality on a long-term basis. The application of 0.3 M sucrose demonstrated a beneficial effect on the integrity of capsules and viability of formed 3D cell assemblies, as compared to 10% dimethyl sulfoxide (DMSO) alone. The proposed workflow from the preparation of core-shell capsules with self-assembled cellular structures to the cryopreservation appears to be a promising strategy for their off-the-shelf availability.     

Kinetics of the hydroformylation of soybean oil by ligand-modified homogeneous rhodium catalysis

The kinetics and mechanism of the hydroformylation of soybean oil by homogeneous ligand-modified rhodium catalysts were investigated at 70–130°C and 4000–11,000 kPa. The effects of reaction rates on systematic variations in reaction parameters were evaluated in order to develop an industrial process to convert vegetable oils to polyaldehydes. The activation energies in the presence of triphenylphosphine (Ph₃P) (61.1±0.8 kJ/mol) (mean±SD) and triphenyl phosphite [(PhO)₃P] (77.4±5.0 kJ/mol) were determined. The catalyst was deactivated at temperatures higher than 100°C. An evaluation of the effects of the reaction parameters on initial rates yielded the rate laws for Ph₃P {rate=k [olefin][Rh(CO)₂Acac]^1.1 [Ph₃P]^−0.5 (pH₂+pCO)^1.4, where Rh(CO)₂Acac is (acetylacetonato)dicarbonylrhodium (I)} and (PhO)₃P {rate=[olefin] [Rh(CO)₂Acac]^1.2 [(PhO)₃P]^−0.8 (pH₂+pCO)^0.9 at total pressures lower than 7000 kPa, and rate =[olefin] [Rh(CO)₂Acac]^1.2 [(PhO)₃P]^−0.8(pH₂+pCO)^1.7 at total pressures higher than 7000 kPa}.     

Nondestructive and noncontact method for determining the spring constant of rectangular cantilevers

We present here an experimental setup and suggest an extension to the long existing added-mass method for the calibration of the spring constant of atomic force microscope cantilevers. Instead of measuring the resonance frequency shift that results from attaching particles of known masses to the end of cantilevers, we load them with water microdrops generated by a commercial inkjet dispenser. Such a device is capable of generating drops, and thus masses, of extremely reproducible size. This makes it an ideal tool for calibration tasks. Moreover, the major advantage of water microdrops is that they allow for a nearly contactless calibration: no mechanical micromanipulation of particles on cantilevers is required, neither for their deposition nor for removal. After some seconds the water drop is completely evaporated, and no residues are left on the cantilever surface or tip. We present two variants: we vary the size of the drops and deposit them at the free end of the cantilever, or we keep the size of the drops constant and vary their position along the cantilever. For the second variant, we implemented also numerical simulations. Spring constants measured by this method are comparable to results obtained by the thermal noise method, as we demonstrate for six different cantilevers.     

Crystallization of Stoichiometric SbSI Glass

Congruent crystallization of antimony sulphoiodide (SbSI) glass of stoichiometric composition, which is prepared successfully for the first time using rapid melt‐quenching, has been investigated using differential scanning calorimetry (DSC). The results for glass powder show a glass transition at 127°C and two separate exothermal peaks with maxima around 140°C and 190°C. The ratio of the intensities of the exothermal peak at ~190°C to the peak at ~140°C increases as the particle size and heating rate are increased, but their total enthalpy remains constant at 62 ± 2 J/g for all DSC runs. Surface heating of the glass induced by a 520 nm CW laser shows two contracted regions: needle‐like crystalline formations at low temperature and bulk crystallization at high temperature. The observed phenomena and DSC results suggest two different kinds of crystallization of the SbSI phase: one‐dimensional crystallization at low temperature which starts from the sample surface and three‐dimensional bulk crystallization that continues the transformation to crystalline state at higher temperatures. The origin of the two different crystallizations can be traced to the strong anisotropy of the SbSI crystal structure due to the weak van der Waals interaction between covalent‐ionic chains (Sb₂S₂I₂)_n.     

Peculiarities in thermal evolution of precipitated amorphous calcium phosphates with an initial Ca/P ratio of 1:1

Thermal evolution of amorphous calcium phosphate (ACP) powder from a fast nitrate synthesis with a Ca/P ratio of 1:1 were studied in the range of 20–980?°C. The powder consisted of amorphous dicalcium phosphate anhydrate (CaHPO₄) after heating to 200?°C. CaHPO₄ gradually condensed to amorphous calcium pyrophosphate Ca₂P₂O₇ (CPP) between 200 to 620?°C. Amorphous CPP crystallized at 620–740?°C to a metastable polymorph α′-CPP of the high-temperature phase α-CPP and β-CPP. The α′-CPP/ β-CPP phase ratio reached a maximum at 800?°C (60?wt% α′-CPP/40?wt% β-CPP), and α′-CPP gradually transformed to β-CPP at a higher temperature. Some β-TCP occurred at 900?°C, so that a three-phasic mixture was obtained in the powder heated to 980?°C. The occurrence of metastable α′-CPP is attributed to Ostwald’s step rule, and a mechanism for β-TCP formation is proposed. The advantages of prospective biomaterials from these powders are discussed.