Quantification of Synergistic Two-Color Covalent Bond Formation.

The emergence of highly wavelength resolved reactivity information for complex photochemical reaction processes allows the establishment of multi-color reaction modes. One particularly powerful mode is the synergistic two-color reaction, where two colors of light have to be present in the same volume element to either enable or enhance photochemical reactivity that leads to a specific photoproduct. Herein, we introduce a two-color synergistic photochemical reaction system based on a diaryl indenone epoxide (DIO) photoswitch and the cis-to-trans isomerization of a bridged ring-strained azobenzene (SA), which respond to ultraviolet (365 nm) and visible light (430 nm), respectively, with different rates, forming a well-defined heterocyclic photoadduct, DIOSA, that we structurally confirm via single crystal x-ray diffraction (SXRD). To quantitatively capture the effectiveness of the dual-color irradiation as a function of the reaction conditions such as light intensity and starting material ratio as a function of product yield, we introduce a parameter, the photochemical synergistic ratio. A reduced synergistic ratio - that extrapolates to conditions of infinitesimal conversions - allows to compare the efficiency of the synergistic photochemistry at varying reaction conditions.

Unlocking the Potential of Polythioesters.

As the demand for sustainable polymers increases, most research efforts have focused on polyesters, which can be bioderived and biodegradable. Yet analogous polythioesters, where one of the oxygen atoms has been replaced by a sulfur atom, remain a relatively untapped source of potential. The incorporation of sulfur allows the polymer to exhibit a wide range of favorable properties, such as thermal resistance, degradability, and high refractive index. Polythioester synthesis represents a frontier in research, holding the promise of paving the way for eco-friendly alternatives to conventional polyesters. Moreover, polythioester research can also open avenues to the development of sustainable and recyclable materials. In the last 25 years, many methods to synthesize polythioesters have been developed. However, to date no industrial synthesis of polythioesters has been developed due to challenges of costs, yields, and the toxicity of the by-products. This review will summarize the recent advances in polythioester synthesis, covering step-growth polymerization, ring-opening polymerization (ROP), and biosynthesis. Crucially, the benefits and challenges of the processes will be highlighted, paying particular attention to their sustainability, with the aim of encouraging further exploration and research into the fast-growing field of polythioesters.

Expanding the phenotypic and genotypic characteristics of trichohepatoenteric syndrome: a report of eight patients from five unrelated families.

BACKGROUND: Trichohepatoenteric syndrome (THES) is characterized by neonatal-onset intractable diarrhea. It often requires long-term total parenteral nutrition (TPN). In addition, other characteristic findings of the syndrome include growth retardation, facial dysmorphism, hair abnormalities, various immunological problems and other rare system findings. Two genes and their associated pathogenic variants have been associated with this syndrome: SKIC3 and SKIC2. METHODS AND RESULTS: In this case series, the clinical findings and molecular analysis results of a total of 8 patients from 5 different families who presented with persistent diarrhea and were diagnosed with THES were shared. Pathogenic variants were detected in the SKIC3 gene in 6 of our patients and in the SKIC2 gene in 2 patients. It was planned to compare the clinical findings of our patients with other patients, together with literature data, and to present yet-undefined phenotypic features that may be related to THES. In our case series, in addition to our patients with a novel variant, patient number 2 had a dual phenotype (THES and Spondyloepimetaphyseal dysplasia, sponastrime type) that has not been reported yet. Delay in gross motor skills, mild cognitive impairment, radioulnar synostosis, osteoporosis, nephropathy and cystic lesions (renal and liver) were observed as unreported phenotypic findings. CONCLUSIONS: We are expanding the clinical and molecular repertoire of the syndrome regarding patients diagnosed with THES. We recommend that the NGS (next-generation sequencing) multigene panel should be used as a diagnostic tool in cases with persistent diarrhea.

Access to Main-Chain Photoswitching Polymers via Hydroxyl-yne Click Polymerization.

Main-chain stimuli-responsive polymers synthesized via polymerization techniques that do not rely on metal-based catalysis are highly desirable for economic reasons and to avoid metal-polymer interactions. Herein, we introduce a metal-free head-to-tail organobase-catalyzed hydroxyl-yne click polymerization of an AB-type monomer to realize photoswitchable polymers featuring α-bismines as main-chain repeating units. The prepared main-chain α-bisimine-based polymers show excellent photoswitching in solution. We further post-functionalize the obtained polymers with various thiol compounds via thiol-Michael reactions to significantly lower the glass transition temperature (Tg), likely to be beneficial for the photoswitching process in the solid state. Thus, the herein introduced polymerization technique not only provides metal-free access to main-chain stimuli-responsive polymers, but also allows for the flexible post-modification of the obtained polymers to generate advanced macromolecular architectures with tunable properties.

The Correlation between Economic Convergence and Health Indices in Developed Countries.

Background: Economic convergence signifies diminishing income disparities among global or regional economies and their eventual disappearance. It is also linked to economic growth and key health indicators. We aimed to assess the association between economic convergence and key health indicators in developed countries called G7 (USA, UK, Germany, France, Italy, Japan, and Canada). Methods: We examined G7 health and economic indicators from 2000 to 2021 using panel data analysis. We compared balanced and unbalanced panel datasets to address missing data and applied suitable methods to handle missing health indicators. Results: Little's MCAR test (X 2 = 3.2872, P - value = 0.3494) confirmed random missing data in the unbalanced panel, enabling us to impute missing values as missing observations were below 5%. Unit root tests on balanced and unbalanced panel data validated the health convergence hypothesis, showing no unit roots in economic growth rate, current health expenditure, and female and male population indicators (P<0.05). Interestingly, the hypothesis for hospital bed counts in the unbalanced panel, differing from the balanced panel, offers new insights into addressing incomplete health data. Conclusion: While G7 have economic similarities, their health indicators diverge (excluding hospital bed counts). Variations in health indicators stem from healthcare system structures, funding mechanisms, resource allocation, and health investments, even among economies of similar size. Therefore, G7 member states should develop tailored national health policies based on their specific circumstances and priorities, utilizing economic convergence data for effective health resource planning.

Photo- and halochromism of spiropyran-based main-chain polymers.

Advanced functional polymeric materials based on spiropyrans (SPs) feature multi-stimuli responsive characteristics, such as a change in color with exposure to light (photochromism) or acids (halochromism). The inclusion of stimuli-responsive molecules in general - and SPs in particular - as main-chain repeating units is a scarcely explored macromolecular architecture compared to side chain responsive polymers. Herein, we establish the effects of substitution patterns on SPs within a homopolymer main-chain synthesized via head-to-tail Acyclic Diene METathesis (ADMET) polymerization. We unambiguously demonstrate that varying the location of the ester group (-OCOR) on the chromophore, which is essential to incorporate the SPs in the polymer backbone, determines the photo- and halochromism of the resulting polymers. While one polymer shows effective photochromism and resistance towards acids, the opposite - weak photochromism and effective response to acid - is observed for an isomeric polymer, simply by changing the position of the ester-linker relative to the benzopyran oxygen on the chromene unit. Our strategy represents a simple approach to manipulate the stimuli-response of main-chain SP bearing polymers and highlights the critical importance of isomeric molecular constitution on main-chain stimuli-sensitive polymers as emerging materials.

Electrochemical Investigations of Sulfur-Decorated Organic Materials as Cathodes for Alkali Batteries.

Alkali metal-sulfur batteries (particularly, lithium/sodium- sulfur (Li/Na-S)) have attracted much attention because of their high energy density, the natural abundance of sulfur, and environmental friendliness. However, Li/Na-S batteries still face big challenges, such as limited cycle life, poor conductivity, large volume changes, and the "shuttle effect" caused by the high solubility of Li/Na-polysulfides. Herein, novel organosulfur-containing materials, i.e., bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)disulfide (BiTEMPS-OH) and 2,4-thiophene/arene copolymer (TAC) are proposed as cathode materials for Li and Na batteries. BiTEMPS-OH shows an initial discharge/charge capacity of 353/192 mAh g-1 and a capacity of 62 mAh g-1 after 200 cycles at 100 mA g-1 in ether-based Li-ion electrolyte. Meanwhile, TAC has an initial discharge/charge capacity of 270/248 mAh g-1 and better cycling performance (106 mAh g-1 after 200 cycles) than BiTEMPS-OH in the same electrolyte. However, the rate capability of TAC is limited by the slow diffusion of Li-ions. Both materials show inferior electrochemical performances in Na battery cells compared to the Li analogs. X-ray powder diffraction reveals that BiTEMPS-OH loses its crystalline structure permanently upon cycling in Li battery cells. X-ray photoelectron spectroscopy demonstrates the cleavage and partially reversible formation of S-S bonds in BiTEMPS-OH and the formation/decomposition of thick solid electrolyte interphase on the electrode surface of TAC.

Main-chain Macromolecular Hydrazone Photoswitches.

Hydrazones-consisting of a dynamic imine bond and an acidic NH proton-have recently emerged as versatile photoswitches underpinned by their ability to form thermally bistable isomers, (Z) and (E), respectively. Herein, we introduce two photoresponsive homopolymers containing structurally different hydrazones as main-chain repeating units, synthesized via head-to-tail Acyclic Diene METathesis (ADMET) polymerization. Their key difference lies in the hydrazone design, specifically the location of the aliphatic arm connecting the rotor of the hydrazone photoswitch to the aliphatic polymer backbone. Critically, we demonstrate that their main photoresponsive property, i.e., their hydrodynamic volume, changes in opposite directions upon photoisomerization (λ=410 nm) in dilute solution. Further, the polymers-independent of the design of the individual hydrazone monomer-feature a photoswitchable glass transition temperature (Tg ) by close to 10 °C. The herein established design strategy allows to photochemically manipulate macromolecular properties by simple structural changes.

Autosomal recessive otospondylo-mega-epiphyseal dysplasia: comprehensive clinical review of a pediatric cohort.

Autosomal recessive otospondylo-mega-epiphyseal dysplasia (OSMEDB) is characterized by short stature with short limbs, dysmorphic facial features, and hearing loss, which is caused by biallelic, loss-of-function, variants in the COL11A2 gene. Geno-phenotypic data from the medical records of eight affected individuals from five unrelated families was abstracted, recorded in an Excel spreadsheet and analyzed using simple frequency analysis. Either short femora or short extremities with or without other ultrasonographic abnormalities were demonstrated in five patients antenatally. The mean height was -2.29 SDS. Pectus deformity, including either chest asymmetry or pectus excavatum, was present in five patients. Bilateral hearing loss was verified in all patients. Severe speech delay and learning disabilities were present in two patients whose deafness was realized after the age of 12 months. Four novel loss-of-function variants in COL11A2 were found in this cohort. We present novel geno-phenotypic findings in a pediatric cohort with OSMEDB. The age of manifestation of short stature was variable, ranging from birth to middle childhood, and the severity of short stature varied even within the same family. Hearing loss may not be evident in the neonatal period and manifest later in OSMEDB. Intermittent hearing tests should be performed for early intervention of neurolinguistic delay and learning disabilities.

Charge controlled interactions between DNA-modified silica nanoparticles and fluorosurfactants in microfluidic water-in-oil droplets.

Microfluidic droplets are an important tool for studying and mimicking biological systems, e.g., to examine with high throughput the interaction of biomolecular components and the functionality of natural cells, or to develop basic principles for the engineering of artificial cells. Of particular importance is the approach to generate a biomimetic membrane by supramolecular self-assembly of nanoparticle components dissolved in the aqueous phase of the droplets at the inner water/oil interface, which can serve both to mechanically reinforce the droplets and as an interaction surface for cells and other components. While this interfacial assembly driven by electrostatic interaction of surfactants is quite well developed for water/mineral oil (W/MO) systems, no approaches have yet been described to exploit this principle for water/fluorocarbon oil (W/FO) emulsion droplets. Since W/FO systems exhibit not only better compartmentalization but also gas solubility properties, which is particularly crucial for live cell encapsulation and cultivation, we report here the investigation of charged fluorosurfactants for the self-assembly of DNA-modified silica nanoparticles (SiNP-DNA) at the interface of microfluidic W/FO emulsions. To this end, an efficient multicomponent Ugi reaction was used to synthesize the novel fluorosurfactant M4SURF to study the segregation and accumulation of negatively charged SiNP-DNA at the inner interface of microfluidic droplets. Comparative measurements were performed with the negatively charged fluorosurfactant KRYTOX, which can also induce SiNP-DNA segregation in the presence of cations. The segregation dynamics is characterized and preliminary results of cell encapsulation in the SiNP-DNA functionalized droplets are shown.