Best practice in interventional management of urolithiasis: an update from the European Association of Urology guidelines panel for urolithiasis 2022

The European Association of Urology (EAU) has updated its guidelines on clinical best practice in urolithiasis for 2021. We therefore aimed to present a summary of best clinical practice in surgical intervention for patients with upper tract urolithiasis. The panel performed a comprehensive literature review of novel data up to May 2021. The guidelines were updated and a strength rating was given for each recommendation, graded using the modified Grading of Recommendations, Assessment, Development, and Evaluations methodology. The choice of surgical intervention depends on stone characteristics, patient anatomy, comorbidities, and choice. For shockwave lithotripsy (SWL), the optimal shock frequency is 1.0-1.5 Hz. For ureteroscopy (URS), a postoperative stent is not needed in uncomplicated cases. Flexible URS is an alternative if percutaneous nephrolithotomy (PCNL) or SWL is contraindicated, even for stones >2 cm. For PCNL, prone and supine approaches are equally safe. For uncomplicated PCNL cases, a nephrostomy tube after PCNL is not necessary. Radiation exposure for endourological procedures should follow the as low as reasonably achievable principles. This is a summary of the EAU urolithiasis guidelines on best clinical practice in interventional management of urolithiasis. The full guideline is available at https://uroweb.org/guidelines/urolithiasis. The European Association of Urology has produced guidelines on the best management of kidney stones, which are summarised in this paper. Kidney stone disease is a common condition; computed tomography (CT) is increasingly used to diagnose it. The guidelines aim to decrease radiation exposure to patients by minimising the use of x-rays and CT scans. We detail specific advice around the common operations for kidney stones.

Vitrimers: Using Dynamic Associative Bonds to Control Viscoelasticity, Assembly, and Functionality in Polymer Networks.

Vitrimers have been investigated in the past decade for their promise as recyclable, reprocessable, and self-healing materials. In this Viewpoint, we focus on some of the key open questions that remain regarding how the molecular-scale chemistry impacts macroscopic physical chemistry. The ability to design temperature-dependent complex viscoelastic spectra with independent control of viscosity and modulus based on knowledge of the dynamic bond and polymer chemistry is first discussed. Next, the role of dynamic covalent chemistry on self-assembly is highlighted in the context of crystallization and nanophase separation. Finally, the ability of dynamic bond exchange to manipulate molecular transport and viscoelasticity is discussed in the context of various applications. Future directions leveraging dynamic covalent chemistry to provide insights regarding fundamental polymer physics as well as imparting functionality into polymers are discussed in all three of these highlighted areas.

Impact of dynamic covalent chemistry and precise linker length on crystallization kinetics and morphology in ethylene vitrimers.

Vitrimers, dynamic polymer networks with topology conserving exchange reactions, have emerged as a promising platform for sustainable and reprocessable materials. While prior work has documented how dynamic bonds impact stress relaxation and viscosity, their role on crystallization has not been systematically explored. Precise ethylene vitrimers with 8, 10, or 12 methylene units between boronic ester junctions were investigated to understand the impact of bond exchange on crystallization kinetics and morphology. Compared to linear polyethylene which has been heavily investigated for decades, a long induction period for crystallization is seen in the vitrimers ultimately taking weeks in the densest networks. An increase in melting temperatures (Tm) of 25-30 K is observed with isothermal crystallization over 30 days. Both C10 and C12 networks initially form hexagonal crystals, while the C10 network transforms to orthorhombic over the 30 day window as observed with wide angle X-ray scattering (WAXS) and optical microscopy (OM). After 150 days of isothermal crystallization, the three linker lengths led to double diamond (C8), orthorhombic (C10), and hexagonal (C12) crystals indicating the importance of precision on final morphology. Control experiments on a precise, permanent network implicate dynamic bonds as the cause of long-time rearrangements of the crystals, which is critical to understand for applications of semi-crystalline vitrimers. The dynamic bonds also allow the networks to dissolve in water and alcohol-based solvents to monomers, followed by repolymerization while preserving the mechanical properties and melting temperatures.

Spontaneous Patterning during Frontal Polymerization.

Complex patterns integral to the structure and function of biological materials arise spontaneously during morphogenesis. In contrast, functional patterns in synthetic materials are typically created through multistep manufacturing processes, limiting accessibility to spatially varying materials systems. Here, we harness rapid reaction-thermal transport during frontal polymerization to drive the emergence of spatially varying patterns during the synthesis of engineering polymers. Tuning of the reaction kinetics and thermal transport enables internal feedback control over thermal gradients to spontaneously pattern morphological, chemical, optical, and mechanical properties of structural materials. We achieve patterned regions with two orders of magnitude change in modulus in poly(cyclooctadiene) and 20 °C change in glass transition temperature in poly(dicyclopentadiene). Our results suggest a facile route to patterned structural materials with complex microstructures without the need for masks, molds, or printers utilized in conventional manufacturing. Moreover, we envision that more sophisticated control of reaction-transport driven fronts may enable spontaneous growth of structures and patterns in synthetic materials, inaccessible by traditional manufacturing approaches.

Effect of Linker Length and Temperature on the Thermal Conductivity of Ethylene Dynamic Networks.

Dynamic covalent networks are a class of polymers containing exchangeable bonds. The influence of the thermodynamics and kinetics of dynamic bond exchange on the thermal conductivity and mechanical properties of dynamic networks is important for understanding how they differ from thermoplastics and thermosets. In this work, a series of ethylene dynamic networks are synthesized from benzene diboronic acid and alkane diols with different precise ethylene linker lengths. The thermal conductivity of these ethylene dynamic networks at 40 °C decreases from 0.19 to 0.095 W/(m K) when the ethylene linker length increases from 4 to 12 carbons. The thermal conductivity also has a strong temperature dependence, decreasing by a factor of 3 over the temperature range from -80 °C to 100 °C. The minimum thermal conductivity model predicts these trends of the thermal conductivity with variations in ethylene linker length and temperature.

Effect of precise linker length, bond density, and broad temperature window on the rheological properties of ethylene vitrimers.

Dynamic networks which undergo topology conserving exchange reactions, sometimes called vitrimers, show properties intermediate to thermosets and thermoplastics. The dynamic nature of the networks results in complex rheological properties and has attracted much attention in the past decade for self-healing, malleable and recyclable polymers. Here, we investigate a series of precise, high crosslink density telechelic ethylene vitrimers as a function of temperature and crosslink density. The networks show a rubbery plateau at high frequencies and a terminal flow regime at lower frequencies. With increasing crosslink density, the rubbery plateau modulus shows a monotonic increase and the terminal flow shifts to lower frequencies. The plateau modulus at high frequency increases as a function of temperature, as expected for a conserved network topology. When plotted against inverse temperature, the zero shear viscosities show a characteristic Arrhenius behavior, and the activation energy monotonically increases with crosslink density. Crossover frequency and shift factors (from time temperature superposition) also show Arrhenius behavior with activation energies in good agreement with those determined from zero shear viscosity. A positive deviation from this Arrhenius trend is observed beginning as high as 100 K above the glass transition temperature for C6 and C8 networks. Further investigations of such networks are critical for the development of sustainable and recyclable replacements for commercial plastics.

Mechanistic insight into the improved Li ion conductivity of solid polymer electrolytes.

Polymer based solid electrolytes (SEs) are envisaged as futuristic components of safer solid state energy devices. But the semi-crystalline nature and slow dynamics of the host polymer matrix are found to hamper the ion transport through the solid polymer network and hence solid state devices are still far beyond the scope of practical application. In this study, we unravel the synergistic roles of Li salt (LiClO4) and two different polymers - polyethylene oxide (PEO) and polydimethyl siloxane (PDMS), in the Li ion transport through their solid blend based electrolyte. A detailed study using dielectric spectroscopy and thermo-mechanical analysis is conducted to understand the tunability of the PEO chain dynamics with LiClO4 and the mechanism of hopping of Li ions by forming ion pairs with oxygen dipoles on the PEO backbone is established. Despite the lack of PDMS's capability to solvate ions and promote ion transport directly, its proper mixing within the PEO host matrix is demonstrated to enhance ion transport due to the influence of PDMS on the segmental dynamics of PEO. A detailed molecular dynamics study supported by experimental validation suggests that even inert polymers can affect the dynamics of the active host matrix and increase ion transport, leading to next generation high ionic conductivity solid matrices, and opens new avenues in designing polymer based transparent electrolytes.