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The salt-tolerant marine microalgae Dunaliella tertiolecta is reported to generate significant amounts of intracellular glycerol as an osmoprotectant under high salt conditions. This study highlights the phylogenetic distribution and comparative glycerol biosynthesis of seven new Dunaliella isolates compared to a D. tertiolecta reference strain. Phylogenetic analysis indicates that all Dunaliella isolates are newly discovered and do not relate to the D. tertiolecta reference. Several studies have identified light color and intensity and salt concentration alone as the most inducing factors impacting glycerol productivity. This study aims to optimize glycerol production by investigating these described factors singularly and in combination to improve the glycerol product titer. Glycerol production data indicate that cultivation with white light of an intensity between 500 and 2000 µmol m-2 s-1 as opposed to 100 µmol m-2 s-1 achieves higher biomass and thereby higher glycerol titers for all our tested Dunaliella strains. Moreover, applying higher light intensity in a cultivation of 1.5 M NaCl and an increase to 3 M NaCl resulted in hyperosmotic stress conditions, providing the highest glycerol titer. Under these optimal light intensity and salt conditions, the glycerol titer of D. tertiolecta could be doubled to 0.79 mg mL-1 in comparison to 100 µmol m-2 s-1 and salt stress to 2 M NaCl, and was higher compared to singularly optimized conditions. Furthermore, under the same conditions, glycerol extracts from new Dunaliella isolates did provide up to 0.94 mg mL-1. This highly pure algae-glycerol obtained under optimal production conditions can find widespread applications, e.g., in the pharmaceutical industry or the production of sustainable carbon fibers.
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The synthesis of group IV metallocene precatalysts for the polymerization of propylene generally yields two different isomers: The racemic isomer that produces isotactic polypropylene (iPP) and the meso isomer that produces atactic polypropylene (aPP). Due to its poor physical properties, aPP has very limited applications. To avoid obtaining blends of both polymers and thus diminish the mechanical and thermal properties of iPP, the meso metallocene complexes need to be separated from the racemic ones tediously -rendering the metallocene-based polymerization of propylene industrially far less attractive than the Ziegler/Natta process. To overcome this issue, we established an isomerization protocol to convert meso metallocene complexes into their racemic counterparts. This protocol increased the yield of iPP by 400% while maintaining the polymer's excellent physical properties and was applicable to both hafnocene and zirconocene complexes, as well as different precatalyst activation methods. Through targeted variation of the ligand frameworks, methoxy groups at the indenyl moieties were found to be the structural motifs responsible for an isomerization to take place -this experimental evidence was confirmed by density functional theory calculations. Liquid injection field desorption ionization mass spectrometry, as well as 1H and 29Si nuclear magnetic resonance studies, allowed the proposal of an isomerization mechanism.
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[This corrects the article DOI: 10.1021/acs.macromol.3c02238.].
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Crescent-shaped hydrogel microparticles are shown to template uniform volume aqueous droplets upon simple mixing with aqueous and oil media for various bioassays. This emerging "lab on a particle" technique requires hydrogel particles with tunable material properties and dimensions. The crescent shape of the particles is attained by aqueous two-phase separation of polymers followed by photopolymerization of the curable precursor. In this work, the phase separation of poly(ethylene glycol) diacrylate (PEGDA, Mw 700) and dextran (Mw 40 000) for tunable manufacturing of crescent-shaped particles is investigated. The particles' morphology is precisely tuned by following a phase diagram, varying the UV intensity, and adjusting the flow rates of various streams. The fabricated particles with variable dimensions encapsulate uniform aqueous droplets upon mixing with an oil phase. The particles are fluorescently labeled with red and blue emitting dyes at variable concentrations to produce six color-coded particles. The blue fluorescent dye shows a moderate response to the pH change. The fluorescently labeled particles are able to tolerate an extremely acidic solution (pH 1) but disintegrate within an extremely basic solution (pH 14). The particle-templated droplets are able to effectively retain the disintegrating particle and the fluorescent signal at pH 14.
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Dextranos , Tamanho da Partícula , Polietilenoglicóis , Polietilenoglicóis/química , Dextranos/química , Concentração de Íons de Hidrogênio , Hidrogéis/química , Hidrogéis/síntese química , Propriedades de Superfície , Corantes Fluorescentes/química , Polimerização , Água/químicaRESUMO
A modular synthetic pathway for poly(diethyl vinylphosphonates) grafting-to gold nanoparticles is presented. Utilising an azide-dopamine derivative as nanoparticle coating agent, alkyne-azide click conditions were used to covalently tether the polymer to gold nanoparticles leading to stable and well distributed colloids for different applications.
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Purpose: To report the development of a new sacroiliac joint (SIJ) arthrodesis system that can be used for isolated fusion of the SIJ and, unlike known implant systems, in combination with lumbar instrumentation or as an alternative to existing sacropelvic fixation (SPF) methods, and the patient-reported outcomes in two cases. Materials and Methods: After a comprehensive review of 207 pelvic computed tomography (CT) datasets, an implant body was designed. Its shape was modeled based on the SIJ recess. A screw anchored in the ilium secures the position of the implant and allows connection to lumbar instrumentation. Two patients with confirmed SIJ syndrome underwent surgery with the anatomically adapted implant. They were evaluated preoperatively, 6 months, and 12 months postoperatively. Visual Analogue Scale (VAS), Oswestry Disability Index (ODI), Million Visual Analogue Scale (MVAS), Roland Morris Score (RMS), reduction of SIJ/leg pain, and work status were assessed. Bony fusion of the SIJ was evaluated by radiographs and CT 12 months after the procedure. Results: Analysis of pelvic CT data revealed a wedge-shaped implant body in four different sizes. In the two patients, VAS decreased from 88 to 33 points, ODI improved from 67 to 35%, MVAS decreased from 80 to 36%, and RMS decreased from 18 to 9 points 12 months after surgery. SIJ pain reduction was 80% and 90%, respectively. Follow-up CT and radiographs showed solid bony integration. Conclusion: The implant used takes into account the unique anatomy of the SIJ and also meets the requirements of a true arthrodesis. Initial results in two patients are promising. Biomechanical and clinical studies will have to show whether the considerable theoretical advantages of the new implant system over existing SIJ implants - in particular the possibility of connection to a lumbar stabilization system - and SPFs can be put into practice.
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A novel single-atom Ni(II) catalyst (Ni-OH) is covalently immobilized onto the nano-channels of mesoporous Santa Barbara Amorphous (SBA)-15 particles and isotropic Anodized Aluminum Oxide (AAO) membrane for confined-space ethylene extrusion polymerization. The presence of surface-tethered Ni complexes (Ni@SBA-15 and Ni@AAO) is confirmed by the inductively coupled plasma-optical emission spectrometry (ICP-OES) and X-ray photoelectron spectroscopy (XPS). In the catalytic spinning process, the produced PE materials exhibit very homogeneous fibrous morphology at nanoscale (diameter: ~50â nm). The synthesized PE nanofibers extrude in a highly oriented manner from the nano-reactors at ambient temperature. Remarkably high Mw (1.62×106 â g mol-1 ), melting point (124 °C), and crystallinity (41.8 %) are observed among PE samples thanks to the confined-space polymerization. The chain-walking behavior of surface tethered Ni catalysts is greatly limited by the confinement inside the nano-channels, leading to the formation of very low-branched PE materials (13.6/1000â C). Due to fixed supported catalytic topology and room temperature, the filaments are expected to be free of entanglement. This work signifies an important step towards the realization of a continuous mild catalytic-spinning (CATSPIN) process, where the polymer is directly synthesized into fiber shape at negligible chain branching and elegantly avoiding common limitations like thermal degradation or molecular entanglement.
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The present work reports on the ultrafast saturable absorption (SA), optical limiting (OL), and the nonlinear refractive response of hydride-terminated silicon nanosheets (SiNS-H) differently functionalized with styrene and tert-butyl methacrylate (tBuMA), namely, SiNS-styrene and SiNS-tBuMA, using 50 fs, 400 nm and 70 fs, 800 nm laser pulses. SiNS-styrene and SiNS-tBuMA exhibit dramatically enhanced nonlinear optical (NLO) responses compared to SiNS-H, with their absorptive nonlinearity strongly dependent on the laser excitation wavelength. More specifically, the studied functionalized SiNSs reveal strong SA behavior under 400 nm laser excitation, with NLO absorption coefficients, saturable intensities, and modulation depths comparable to various two-dimensional (2D) materials, known to exhibit strong SA, such as graphene, black phosphorous (BP), some transition metal dichalcogenides (TMDs), and some MXenes. On the other hand, under 800 nm laser excitation, SiNS-styrene and SiNS-tBuMA show highly efficient OL performance with OL onset values of about 0.0045 and 0.0065 J cm-2, respectively, which are significantly lower than those of other 2D nanostructures. In addition, it is shown that both SiNS samples have great potential in already existing Si-based optoelectronic devices for optical-switching applications since they exhibit very strong NLO refraction comparable to that of bulk Si. The results of the present work demonstrate that the chemical functionalization of SiNSs provides a highly efficient strategy for the preparation of 2D Si-based nanostructures with enhanced NLO response in view of several optoelectronic and photonic applications, such as OL, SA, and all-optical switching.
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Complex coacervation describes the liquid-liquid phase separation of oppositely charged polymers. Active coacervates are droplets in which one of the electrolyte's affinity is regulated by chemical reactions. These droplets are particularly interesting because they are tightly regulated by reaction kinetics. For example, they serve as a model for membraneless organelles that are also often regulated by biochemical transformations such as post-translational modifications. They are also a great protocell model or could be used to synthesize life-they spontaneously emerge in response to reagents, compete, and decay when all nutrients have been consumed. However, the role of the unreactive building blocks, e.g., the polymeric compounds, is poorly understood. Here, we show the important role of the chemically innocent, unreactive polyanion of our chemically fueled coacervation droplets. We show that the polyanion drastically influences the resulting droplets' life cycle without influencing the chemical reaction cycle-either they are very dynamic or have a delayed dissolution. Additionally, we derive a mechanistic understanding of our observations and show how additives and rational polymer design help to create the desired coacervate emulsion life cycles.
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The unique solid-solution structure and multi-element compositions of high-entropy alloy nanoparticles (HEA NPs) have garnered substantial attention. Various methods have been developed to prepare a diverse array of HEA NPs using different substrates for support and stabilization. In this study, we present a facile surface-mediated reduction method to prepare HEA NPs (AuAgCuPdPt) decorated germanane (HEA NPs@GeNSs), and employ X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) to characterize their structure, composition, and morphology. Subsequently, we demonstrate that the HEA NPs can be liberated from the surfaces of GeNSs as freestanding systems via straightforward exposure to UV light. We also explore germanium nanoparticles (GeNPs) as an alternative substrate for HEA NP formation/production, given their similarity to germanane and their Ge-H surface. Finally, we extend our investigation to bulk Ge wafers and demonstrate successful deposition of HEA NPs.
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We report the highly isoselective ring-opening polymerization (ROP) of racemic ß-butyrolactone (ß-BL) using in situ-generated catalysts based on Y[N(SiHMe2)2]3(THF)2 and salan-type pro-ligands. The catalyst system produces isotactic poly(3-hydroxybutyrate) (PHB) with record productivity (TOF up to 32 000 h-1) and the highest isoselectivity (Pm up to 0.89) in ROP of ß-BL achieved to date. In contrast to bacterial PHB, the chemically synthesized PHB has beneficial material properties, such as increased melt processing window attributed to a lowered melting temperature (Tm ≈ 140 °C) and drastically reduced brittleness. The produced PHB showed an elongation at break of 392%, thus demonstrating promising polyolefin-like thermomechanical material properties.
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A novel strategy allowing temporal control of dynamic bond exchange in covalently crosslinked polymer networks via latent transesterification catalysts is introduced. Obtained by a straightforward air- and water-tolerant synthesis, the latent catalyst is designed for an irreversible temperature-mediated release of a strong organic base. Its long-term inactivity at temperatures below 50 °C provides the unique opportunity to equip dynamic covalent networks with creep resistance and high bond-exchange rates, once activated. The presented thermally latent base catalyst is conveniently introducible in readily available building blocks and, as proof of concept, applied in a radically polymerized thiol-ene network. Light-mediated curing is used for 3D-printing functional objects, on which the possibility of spatially controlled reshaping and welding based on dynamic transesterification is illustrated. Since the catalyst is thermally activated, limitations regarding sample geometry and optical transparency do not apply, which facilitates a transfer to well-established industrial technologies. Consequently, fiber-reinforced and highly filled magneto-active thiol-ene polymer composites are fabricated by a thermal curing approach. The on-demand activation of dynamic transesterification is demonstrated by (magneto-assisted) reshaping experiments, highlighting a wide range of potential future applications offered by the presented concept.
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In life, molecular architectures, like the cytoskeletal proteins or the nucleolus, catalyze the conversion of chemical fuels to perform their functions. For example, tubulin catalyzes the hydrolysis of GTP to form a dynamic cytoskeletal network. In contrast, myosin uses the energy obtained by catalyzing the hydrolysis of ATP to exert forces. Artificial examples of such beautiful architectures are scarce partly because synthetic chemically fueled reaction cycles are relatively rare. Here, we introduce a new chemical reaction cycle driven by the hydration of a carbodiimide. Unlike other carbodiimide-fueled reaction cycles, the proposed cycle forms a transient 5(4H)-oxazolone. The reaction cycle is efficient in forming the transient product and is robust to operate under a wide range of fuel inputs, pH, and temperatures. The versatility of the precursors is vast, and we demonstrate several molecular designs that yield chemically fueled droplets, fibers, and crystals. We anticipate that the reaction cycle can offer a range of other assemblies and, due to its versatility, can also be incorporated into molecular motors and machines.
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Herein, this work reports fiber spinning of tailored isotactic polypropylene (iPP) by melt spinning and melt drawing, yielding an adjustable diameter of 40-400â µm. The crystallinity of all obtained fibers with a molecular weight between 330-1400â kg/mol is increased by thermal annealing and investigated via differential scanning calorimetry (DSC) as well as wide angle X-ray scattering (WAXS). The potential of ultrahigh molecular weight iPP (UHMW-iPP) fibers compared to fibers manufactured from industrially available iPP becomes evident when the mechanical performance is compared: fibers spun from UHMW-iPP (1400â kg/mol) enable a tensile strength of up to 400â MPa, whereas commercially available fibers (330â kg/mol) show a tensile strength of approximately 50â MPa. However, UHMW-iPP exhibits a short timeframe, in which extrusion is possible, thereafter extrusion rupture occurs, probably induced by an increased melt viscosity.
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Silicone elastomers are usually produced via addition or condensation curing by means of platinum- or tin-based catalysis. The employed catalysts remain in the final rubber and cannot be recovered, thus creating various economic and environmental challenges. Herein, a light-mediated curing method using multifunctional silacyclopropenes as crosslinker structures was introduced to create an effective alternative to the conventional industrial crosslinking. To evaluate the potential of the photoreaction a model study with small monofunctional silirenes was conducted. These investigations confirmed the required coupling reactivity upon irradiation and revealed an undesired rearrangement formation. Further optimization showed the reaction selectivity to be strongly influenced by the substitution of the three-membered ring system and the reaction temperature. The synthesis of multifunctional silirenes was described based on the most suitable model compound to create active crosslinker scaffolds for their application in silicone curing. This photo-controlled process produces catalyst and additive free elastomers from liquid silicones, including hydride-, hydroxy-, or vinyl terminated polydimethylsiloxanes.
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Syngas, a mixture of CO and H2 , is a high-priority intermediate for producing several commodity chemicals, e.g., ammonia, methanol, and synthetic hydrocarbon fuels. Accordingly, parallel sunlight-driven catalytic conversion of CO2 and protons to syngas is a key step toward a sustainable energy cycle. State-of-the-art catalytic systems and materials often fall short as application-oriented concurrent CO and H2 evolution requires challenging reaction conditions which can hamper stability, selectivity, and efficiency. Here a light-harvesting metal-organic framework hosting two molecular catalysts is engineered to yield colloidal, water-stable, versatile nanoreactors for photocatalytic syngas generation with highly controllable product ratios. In-depth fluorescence, X-ray, and microscopic studies paired with kinetic analysis show that the host delivers energy efficiently to active sites, conceptually yielding nanozymes. This unlocked sustained CO2 reduction and H2 evolution with benchmark turnover numbers and record incident photon conversions up to 36%, showcasing a highly active and durable all-in-one material toward application in solar energy-driven syngas generation.
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Prospective observational study. To evaluate patient-reported outcomes after navigation-guided minimally invasive hybrid lumbar interbody fusion (nMIS-HLIF) for decompression and fusion in degenerative spondylolisthesis (Meyerding grade I-II). Posterior lumbar interbody fusion (PLIF) and transforaminal lumbar interbody fusion (TLIF) are well-known standard procedures for lumbar spinal fusion. nMIS-HLIF is a navigation-guided combined percutaneous and open procedure that combines the advantages of PLIF and TLIF procedures for the preparation of a single-port endoscopic approach. 33 patients underwent nMIS-HLIF. Core outcome measure index (COMI), oswestry disability index (ODI), numeric rating scale (NRS) back, NRS leg, and short form health-36 (SF-36) were collected preoperatively and at follow-up of 6 weeks, 3 months, 6 months, and 1 year. The impact of body mass index (BMI) was also analyzed. Computed tomography reconstruction was used to assess realignment and verify fused facet joints and vertebral bodies at the 1-year follow-up. 28 (85%) completed the 1-year follow-up. The median BMI was 27.6 kg/m2, age 69 yrs. The mean reduction in listhesis was 8.4% (Pâ <â .01). BMI was negatively correlated with listhesis reduction (Pâ =â .032). The improvements in the NRS back, NRS leg, ODI, and COMI scores were significant at all times (Pâ <â .001-Pâ <â .01). The SF-36 parameters of bodily pain, physical functioning, physical component summary, role functioning/physical functioning, and social functioning improved (Pâ <â .003). The complication rate was 15.2% (nâ =â 5), with durotomy (nâ =â 3) being the most frequent. To reduce the complication rate and allow transitioning to a fully endoscopic approach, expandable devices have been developed. The outcomes of nMIS-HLIF are comparable to the current standard open and minimally invasive techniques. A high BMI hinders this reduction. The nMIS-HLIF procedure is appropriate for learning minimally invasive dorsal lumbar stabilization. The presented modifications will enable single-port endoscopic lumbar stabilization in the future.
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Fusão Vertebral , Espondilolistese , Idoso , Humanos , Parafusos Ósseos , Osso Cortical/cirurgia , Vértebras Lombares/diagnóstico por imagem , Vértebras Lombares/cirurgia , Procedimentos Cirúrgicos Minimamente Invasivos/métodos , Medidas de Resultados Relatados pelo Paciente , Estudos Retrospectivos , Fusão Vertebral/métodos , Espondilolistese/cirurgia , Resultado do TratamentoRESUMO
For more than 40â years, the synthesis of C2 -symmetric indenyl-based racemic metallocenes for the isoselective polymerization of propylene relied on a tedious separation of the produced rac and meso isomers. Status quo, latter are considered wasteful as they produce atactic polypropylene (aPP) rather than isotactic polypropylene (iPP) if activated with methylaluminoxane (MAO). Unexpectedly, the in situ activation of meso hafnocene I yielded perfectly isotactic polypropylene. We verified an isomerization of the meso compound to the corresponding racemic one upon triisobutylaluminum (TIBA) addition via nuclear magnetic resonance (NMR) spectroscopy and established an easy and convenient polymerization protocol, enabling productivities comparable to pure rac-I if applied to pure meso-I or a mixture of both isomers. With this established isomerization protocol, the potential yield of iPP was enhanced by more than 400 %. This protocol was also shown to be applicable to other meso hafnocenes and some initial mechanistic insights were received.
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A method to functionalize Si-H containing substrates with vinyl substituted silacyclopropenes has been developed. This provides an efficient and versatile technique to generate multi-functional silacyclopropene derivatives, ranging from small molecules to polymeric materials like polysiloxanes. Thus, access is given to a new class of functionalized materials that exhibits potential in a variety of possible applications.
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Polímeros , SiloxanasRESUMO
Chemical recycling of polymers is an elegant approach to achieve a circular economy and address the sustainability and end-of-life issues of plastics. Herein, we report the ring-opening polymerization of a bicyclic lactone that is easily accessible from norcamphor. High molecular weight polyesters (Mn up to 164 kg mol-1) are obtained using ZnEt2 as catalyst, while the polymerizability of the monomer is good even at high temperatures. More importantly, the polymers can be completely depolymerized under thermolysis conditions to selectively recover the pristine monomer. Thus, the monomer design strategy of using ring-fused/hybridized lactones enables an innovative monomer-polymer system that shows both high polymerizability and high depolymerizability.