Cu–Ni hetero-bimetallic compounds,Part 1: Preparation,structure and properties of [Cu0.05Ni0.95(bpy)2(ox)]·4H2O

New bimetallic compound [Cu_xNi_1?x(bpy)₂(ox)]·4H₂O (x = 0.05, ox = oxalato, bpy = 2,2′-bipyridine) was synthesized and chemically characterized. Its crystal structure is molecular. The octahedron around the metal central atom is deformed due to coordination by one bidentate oxalate anion and two bpy ligands. There are four uncoordinated water molecules in the asymmetric unit. The metal site is occupied by both Cu(II) and Ni(II) atoms in the 5:95 ratio. The complex molecules interact with water molecules through hydrogen bonds and, moreover, π–π interactions between aromatic rings lead to a 1D arrangement of molecules. The susceptibility data measured down to 2 K were analyzed using strong-coupling theory and the best agreement with the experimental data were found for g = 2.1, D/k = 5.6, E/k = 0.35, J/k = 0.2. The dehydration starts at 30 °C. As a final product of its thermal decomposition a solid solution of Cu_xNi_1?xO was detected by X-ray powder diffraction.     

Cosmological expansion and local systems: a Lemaître–Tolman–Bondi model

We propose a Lemaître–Tolman–Bondi system mimicking a two-body system to address the problem of the cosmological expansion versus local dynamics. This system is strongly bound but participates in the cosmic expansion and is exactly comoving with the cosmic substratum.     

Estimation of pore size in a microstructure phantom using the optimised gradient waveform diffusion weighted NMR sequence

There has been increasing interest in nuclear magnetic resonance (NMR) techniques that are sensitive to diffusion of molecules containing NMR visible nuclei for the estimation of microstructure parameters. A microstructure parameter of particular interest is pore radius distribution. A recent in silico study optimised the shape of the gradient waveform in diffusion weighted spin-echo experiments for estimating pore size. The study demonstrated that optimised gradient waveform (GEN) protocols improve pore radius estimates compared to optimised pulse gradient spin-echo (PGSE) protocols, particularly at shorter length scales. This study assesses the feasibility of implementing GEN protocols on a small bore 9.4 T scanner and verifies their additional sensitivity to pore radius. We implement GEN and PGSE protocols optimised for pore radii of 1, 2.5, 5, 7.5, 10 μm and constrained to maximum gradient strengths of 40, 80, 200 mT m(-1). We construct microstructure phantoms, which have a single pore radius for each phantom, using microcapillary fibres. The measured signal shows good agreement with simulated signal, strongly indicating that the GEN waveforms can be implemented on a 9.4 T system. We also demonstrate that GEN protocols provide improved sensitivity to the smaller pore radii when compared to optimised PGSE protocols, particularly at the lower gradient amplitudes investigated in this study. Our results suggest that this improved sensitivity of GEN protocols would be reflected in clinical scenarios.     

A Simple,Robust, and Convenient HPLC Assay for Urinary Lactulose and Mannitol in the Dual Sugar Absorption Test

Background: Heterogeneous laborious analytical methodologies for the determination of urinary lactulose and mannitol limit their utility in intestinal permeability testing. Methods: We developed an assay using a Shimadzu HPLC system, an Aminex HPX87C column, and refractive index detection. The test was calibrated using a series of dilutions from standard stock solutions of lactulose and mannitol ‘spiked’ into urine samples. The utility to quantify urinary excretion during the dual sugar absorption test over 6 h was also determined. Results: Lactulose and mannitol were eluted isocratically at 5.7 and 10.1 min, respectively, with water as a mobile phase at a flow rate of 0.3 mL min⁻¹, 858 psi, 60 °C. The calibration curves for both sugars were linear up to 500 µg mL⁻¹ with a limit of detection in standard solutions at 4 µg mL⁻¹ and in ‘spiked’ urine samples at 15 µg mL⁻¹. The intra-assay and inter-assay CVs were between 2.0–5.1% and 2.0–5.1% for lactulose and 2.5–4.4% and 2.8–3.9% for mannitol. The urinary profiles of the 6 h absorption of lactulose and mannitol showed similar peak-retention times to standard solutions and were well-resolved at 5.9 and 10.4 min, respectively. Conclusions: The assay was easy to automate, using commonly available equipment and convenient requiring no prior laborious sample derivatization. The simplicity, reproducibility, and robustness of this assay facilitates its use in routine clinical settings for the quantification of intestinal permeability.     

Injectable Hyaluronic Acid Hydrogel Containing Platelet Derivatives for Synovial Fluid Viscosupplementation and Growth Factors Delivery

Osteoarthritisis a highly prevalent musculoskeletal disorder characterized by degradation of cartilage and synovial fluid (SF). Platelet derivatives as platelet-rich plasma (PRP) and platelet lysate have great potential in the treatment of osteoarthritis because they contain biologically active substances including growth factors (GFs). Rapid release of GFs and their short biological half-life are factors that can limit the therapeutic impact of PRP therapy. Herein, the first work that describes hydrogels based on polyaldehyde derivative of hyaluronic acid (HA-OX) as carriers of platelet derivatives for in situ applications is presented, which can be a possible solution to the problem. HA-OX hydrogels containing 50% (w/w) of PRP or platelet lysate can be injected using a syringe due to low viscosity(<10 Pa s) and injection force (<20 N), and reach elastic modulus up to 2000 Pa. Insulin-like GF-1 and Platelet-derived GF-AB release from HA-OX hydrogels (mesh size 297–406 nm) by Fickian and non-Fickian diffusion respectively. The released PRP GFs maintain their ability to induce cell proliferation (87%–92%). Based on the obtained results, the unique concept of a new material that can restore viscoelastic properties of SF and at the same time gradually deliver GFs from platelet derivatives is designed.     

Tailorable and Biocompatible Supramolecular-Based Hydrogels Featuring two Dynamic Covalent Chemistries

Dynamic covalent chemistry (DCC) has proven to be a valuable tool in creating fascinating molecules, structures, and emergent properties in fully synthetic systems. Here we report a system that uses two dynamic covalent bonds in tandem, namely disulfides and hydrazones, for the formation of hydrogels containing biologically relevant ligands. The reversibility of disulfide bonds allows fiber formation upon oxidation of dithiol-peptide building block, while the reaction between NH−NH₂ functionalized C-terminus and aldehyde cross-linkers results in a gel. The same bond-forming reaction was exploited for the “decoration” of the supramolecular assemblies by cell-adhesion-promoting sequences (RGD and LDV). Fast triggered gelation, cytocompatibility and ability to “on-demand” chemically customize fibrillar scaffold offer potential for applying these systems as a bioactive platform for cell culture and tissue engineering.     

Comparison of salivary sodium and potassium concentrations measured by handheld ion-selective electrode meters and an automated biochemical analyser

Ion-selective electrode pocket meters available for use with saliva could be a convenient tool to assess how diseases, drugs, exercise or nutrition affect salivary composition. This study compared salivary sodium and potassium concentrations measured by handheld LAQUAtwin meters and a fully-automated biochemical analyzer. Agreement between two methods was assessed with Passing-Bablok regression and Bland-Altman plots. LAQUAtwin meters measured lower values of both analytes and provided repeatable though not accurate results. The meters may serve as an alternative to laboratory methods to gain insight into between-group differences in electrolyte concentrations, or a concentration change induced by an experimental procedure.     

Catalytic C−C/C−H Bond Activation Relay for Synthesis of Fluorescent Naphthoquinolizinium Salts

Herein, we report the design and synthesis of a series of novel cationic nitrogen-embedded polyaromatic hydrocarbons with a planar geometry. The synthetic pathway is based on catalytic C−C/C−H bond activation relay that enabled preparation of regioselectively 5,6,10,11-tetrasubstituted naphtho[2,1,8-ija]quinolizinium salts bearing various types of substituents. Single-crystal X-ray analyses of selected compounds confirmed planarity of the quinolizinium core. Most of the prepared compounds exhibited strong fluorescence (Φ_s up to >99 %) ranging from 420–600 nm depending on the substitution pattern. According to DFT calculations LUMO is always distributed over the quinolizinium framework regardless of the attached substituents, whereas delocalization of HOMO is related to the substitution pattern. Electrochemical measurements show irreversible reduction of all compounds, which is supported by the calculated location of LUMO orbitals.     

Supramolecular Capsule Catalysis Enables the Exploration of Terpenoid Chemical Space Untapped by Nature

Terpenes represent the largest and the most diverse class of natural compounds. This is remarkable as the whole variety is accessed from just a handful of highly conserved linear precursors. Modification of the cyclization precursors would enable a dramatic expansion of the accessible chemical space. However, natural enzymes do not enable us to tap into this potential, as they do not tolerate larger deviations from the prototypical substrate structure. Herein we report that supramolecular capsule catalysis enables facile access to diverse and novel terpenoid skeletons that formally can be traced back to C3-phenyl, benzyl, and homoprenyl derivatives of farnesol. Novel skeletons related to the presilphiperfolane core structure, as well as novel neoclovene derivatives were accessed efficiently in only four synthetic steps. Importantly, the products obtained carry functional groups that may be readily derivatized further.