Simultaneous Formation Research Articles

A sol-gel templating route for the synthesis of hierarchical porous calcium phosphate glasses containing zinc

Hierarchical porous phosphate-based glasses (PPG) have great potential in biomedicine. Micropores (pore size <2 nm) increase the surface area, mesopores (pore size 2–50 nm) facilitate the absorption and diffusion of therapeutic ions and molecules making them ideal controlled delivery systems, while macropores (pore size >50 nm) facilitate the movement and diffusion of cells and fluids. In addition, the bioresorbability of PPG allows for their complete solubility in body fluid, alongside simultaneous formation of new tissue. Making PPG via the traditional melt-quenching (MQ) synthesis method used for phosphate-based glasses (PG), is not straightforward. Hence, we present here a route for preparing such glasses using a combination of sol-gel (SG) and templating methods. Hierarchical PPG in the P2O5–CaO–Na2O system with the addition of 1, 3 and 5 mol % of Zn2+ were prepared with pore dimensions ranging from the micro-to the macro scales using Pluronic 123 (P123) as a surfactant. The presence of micropores (0.30–0.46 nm), mesopores (1.75–9.35nm) and macropores (163–207 nm) was assessed via synchrotron-based Small-Angle X-ray Scattering (SAXS), with the presence of the latter two confirmed by Scanning Electron Microscopy (SEM). Structural characterisation performed using 31P solid state magic angle spinning nuclear magnetic resonance (MAS NMR) and Fourier Transform Infrared (FTIR) spectroscopies shows the presence of Q2, Q1 and Q0 phosphate species with a predominance of Q1 species in all compositions. Dissolution studies in deionised (DI) water confirm that controlled release of phosphates, Ca2+, Na+ and Zn2+ is achieved over a period of 7 days. In particular, the release of Zn2+ is proportional to its loading, making its delivery particularly easy to control.

Revisiting the structure of [PdAu9(PPh3)8(CN)]2+ produced by atmospheric pressure plasma irradiation of [PdAu8(PPh3)8]2+ in methanol.

Some of the authors of the present research group have previously reported mass spectrometric detection of [PdAu9(PPh3)8(CN)]2+ (PdAu9CN) by atmospheric pressure plasma (APP) irradiation of [MAu8(PPh3)8]2+ (PdAu8) in methanol and proposed based on density functional theory (DFT) calculations that PdAu9CN is constructed by inserting a CNAu or NCAu unit into the Au-PPh3 bond of PdAu8 [Emori et al., J. Chem. Phys. 155, 124312 (2021)]. In this follow-up study, we revisited the structure of PdAu9CN by high-resolution ion mobility spectrometry on an isolated sample of PdAu9CN with the help of dispersion-corrected DFT calculation. In contradiction to the previous proposal, we conclude that isomers in which an AuCN unit is directly bonded to the central Pd atom of PdAu8 are better candidates. This assignment was supported by Fourier transform infrared and ultraviolet-visible spectroscopies of isolated PdAu9CN. The simultaneous formation of [Au(PPh3)2]+ and PdAu9CN suggests that the AuCN species are formed by APP irradiation at the expense of a portion of PdAu8. These results indicate that APP may offer a unique method for transforming metal clusters into novel ones by generating in situ active species that were not originally added to the solution.

Investigation on the cavitation characteristic of a novel cylindrical rotational hydrodynamic cavitation reactor

Hydrodynamic cavitation reactors are of great promise for the applications of chemical process intensification and water treatment. In this work, a novel cylindrical rotational hydrodynamic cavitation reactor (CRHCR) with rectangular grooves and oblique tooth protrusions on the rotor surface was studied. The three-dimensional characterization of cavitation within the CRHCR was observed from the front and left views by the high-speed camera experiments. Interestingly, a new phenomenon of simultaneous formation of the attached cavitation and shear cavitation was found in the CRHCR. The synergistic effect of attached cavitation and shear cavitation contributes to the enhancement of the cavitation performance of CRHCR. In addition, the evolution of attached cavitation is explored. It is found that attached cavitation forms a trapezoidal-shaped cavitation cloud in the groove, which undergoes three various stages: incipient, development, and collapse. Finally, the pulsation frequency and cavitation intensity of shear cavitation in the chamber were investigated. The results show that the cavitation pulsation frequency is the same at the same rotational speed in the chamber near diverse oblique teeth. As the rotational speed increases, the cavitation pulsation frequency increases linearly. These findings in this paper are of great benefit to understanding the mechanism of the cavitation effect of CRHCR.

Multiple micro-cavity vibro-polaritons formation with different vibrational bands of the methylene group

We present an experimental technique to accurately predict the formation of vibro-polaritons from a molecular polymeric film embedded in a resonant mid-infrared cavity. Using simple Fourier-transform reflectance measurement, we extract the complex dielectric function of a polyethylene film using Kramers-Kronig relations. The fitted dielectric function can be plugged into a numerical code to predict the strength and dispersion of the strong light-matter coupling regime between the quantized electromagnetic modes of a microcavity and the vibrational bands of the molecules. As a demonstration, we experimentally resolve the simultaneous formation of multiple vibro-polariton modes issued from the strong coupling of some vibrational bands of the methylene group (CH2) in a 2.5-μm-thick polyethylene film embedded in a microcavity. We measure a Rabi splitting of 6.3 THz for the stretching doublet around 87.5 THz and a Rabi splitting of 1.1 THz for the scissoring doublet around 43.7 THz, in excellent agreement with numerical predictions.

Formation of chirality in propagating spin waves

A general approach to quantify chirality, or absence of parity symmetry, of spin waves has been developed and applied to spin waves propagating in obliquely magnetized ferromagnetic films. Using theoretical arguments and numerical calculations, it is shown that, upon increasing spin wave wavevector, initially achiral spin waves develop chiral properties through the “parity exchange” mechanism, which implies, in particular, that chiral spin waves appear in pairs. The most striking example of the parity exchange mechanism is the simultaneous formation of two chiral waves: the magnetostatic surface wave and the recently discovered heterosymmetric spin wave, which were previously considered independent of each other. Another manifestation of the parity exchange is the formation of strongly chiral waves near the anti-crossings of spin wave branches of unequal symmetry. These findings illustrate viable paths to engineering spin wave systems with prescribed chiral spectra that had not previously been considered.

De Novo Synthesis of 2,2'-Bipyridines and Related Bis-azines via Cascade Coupling and Double Pyridannulation of Isocyanides.

Herein, we present a new and general protocol for the assembly of 2,2'-bipyridyls from nonpyridine substrates without using any metal catalysts or organometallic reagents. The process starts from the coupling of two 1,3-dienyl isocyanides followed by a 6π-electrocyclization/aromatization cascade featuring the simultaneous formation of two pyridine rings in a single operation. Notably, this strategy is also applicable to the construction of nonsymmetrical 2-(2-pyridyl)-quinolines/-quinoxalines. Furthermore, the aggregation-induced emission (AIE) characteristics endow our approach with great potential in biorelevant fields.

An Overview of the Synthesis of 3,4-Fused Pyrrolocoumarins of Biological Interest.

3,4-Fused pyrrolocoumarins, synthetically prepared or naturally occurring, possess interesting biological properties. In this review, the synthetic strategies for the synthesis of the title compounds are presented along with their biological activities. Two routes are followed for that synthesis. In one, the pyrrole ring is formed from coumarin derivatives, such as aminocoumarins or other coumarins. In the other approach, the pyranone moiety is built from an existing pyrrole derivative or through the simultaneous formation of coumarin and pyrrole frameworks. The above syntheses are achieved via 1,3-dipolar cycloaddition reactions, Michael reaction, aza-Claisen rearrangement reactions, multi-component reactions (MCR), as well as metal-catalyzed reactions. Pyrrolocoumarins present cytotoxic, antifungal, antibacterial, α-glucosidase inhibition, antioxidant, lipoxygenase (LOX) inhibition, and fluorescent activities, as well as benzodiazepine receptor ability.

One-Step Preparation of Magnetic Lipid Bubbles: Magnetothermal Effect Induces the Simultaneous Formation of Gas Nuclei and Self-Assembly of Phospholipids.

In recent years, enveloped micro-nanobubbles have garnered significant attention in research due to their commendable stability, biocompatibility, and other notable properties. Currently, the preparation methods of enveloped micro-nanobubbles have limitations such as complicated preparation process, large bubble size, wide distribution range, low yield, etc. There exists an urgent demand to devise a simple and efficient method for the preparation of enveloped micro-nanobubbles, ensuring both high concentration and a uniform particle size distribution. Magnetic lipid bubbles (MLBs) are a multifunctional type of enveloped micro-nanobubble combining magnetic nanoparticles with lipid-coated bubbles. In this study, MLBs are prepared simply and efficiently by a magneto internal heat bubble generation process based on the interfacial self-assembly of iron oxide nanoparticles induced by the thermogenic effect in an alternating magnetic field. The mean hydrodynamic diameter of the MLBs obtained was 384.9 ± 8.5 nm, with a polydispersity index (PDI) of 0.248 ± 0.021, a zeta potential of -30.5 ± 1.0 mV, and a concentration of (7.92 ± 0.46) × 109 bubbles/mL. Electron microscopy results show that the MLBs have a regular spherical stable core-shell structure. The superparamagnetic iron oxide nanoparticles (SPIONs) and phospholipid layers adsorbed around the spherical gas nuclei of the MLBs, leading the particles to demonstrate commendable superparamagnetic and magnetic properties. In addition, the effects of process parameters on the morphology of MLBs, including phospholipid concentration, phospholipid proportiona, current intensity, magnetothermal time, and SPION concentration, were investigated and discussed to achieve controlled preparation of MLBs. In vitro imaging results reveal that the higher the concentration of MLBs loaded with iron oxide nanoparticles, the better the in vitro ultrasound (US) imaging and magnetic resonance imaging (MRI) results. This study proves that the magneto internal heat bubble generation process is a simple and efficient technique for preparing MLBs with high concentration, regular structure, and commendable properties. These findings lay a robust foundation for the mass production and application of enveloped micro-nanobubbles, particularly in biomedical fields and other related domains.

Investigation of selective metal-complexation in terpyridine and phenanthroline based polymeric systems

In the current study, we present the synthesis of a polymeric template featuring two adjoining ligand moieties (i.e. terpyridine and phenanthroline), which are capable to selectively bind ligand counterparts by the simultaneous formation of heteroleptic complexes. This represents the first example for the incorporation of the specific heteroleptic [Cu(tpy)(phen)]2+ binding motif, based on unmodified ligands in a polymeric architecture. The polymeric template is intensively investigated by isothermal titration calorimetry to characterize the complex formation, while electron paramagnetic resonance spectroscopy is applied to study structural geometries as well as electronic properties of the polymeric supramolecular structure in comparison to corresponding model complexes. The utilized methods provide strong evidence for a highly specific heteroleptic complex formation at the polymer ligand moieties.

Suppressing proton-induced HER and cathode fading by an aprotic hybrid electrolyte for long-cycle stability of aqueous Na||Zn hybrid batteries

Aqueous zinc metal batteries with unique advantages of intrinsic safety and low cost are considered as one of the most promising next-generation energy-storage technologies. However, their lifespan is significantly constrained by the electrolyte, specifically due to limitations caused by proton-induced HER and dendritic growth at the anode side and dissolution phenomena at the cathode. Unlike most studies on the protic electrolyte systems, herein, a new aprotic hybrid electrolyte of Na/Zn tetrafluoroborate-trimethyl phosphate with ultralow proton activity tuned by reconstruction of hydrogen bonding network and ultrahigh interfacial stability endowed by simultaneous formation of SEI and CEI were designed for the first time. Attributed to the synergistic effect of proton activity attenuation and ZnF2-Zn3(PO4)2 SEI formation, HER-trigged corrosion current was decreased by 96.52%, which leads to an exceptionally high coulombic efficiency up to 99.63%, and operational lifespan exceeding 2000 hours at 1 mA cm−2/ 1 mAh cm−2 for Zn||Cu asymmetric cell and Zn||Zn symmetric cell, respectively. Furthermore, the suppression of excess hydrated proton co-insertion reaction and construction of inorganic-organic CEI enabled the PBAs||Zn full cell a prolonged cycling life of 6000 cycles with an ultralow decay rate of 0.004% per cycle. The special electrolyte utilizing cheap tetrafluoroborate salts in conjunction with cost-effective PBA cathode and Zn anode provides a new choice for low-cost, high-safety, non-toxic batteries for practical applications.

Ampholytic Peptides Consisting of an Alternating Lysine/Glutamic Acid Sequence for the Simultaneous Formation of Polyion Complex Vesicles.

Nanoarchitectures such as micelles and vesicles that self-assemble via electrostatic interactions between their charged polymeric components have been widely used as material delivery platforms. In this work, ampholytic peptides with a sequence of alternating lysine and glutamic acid residues were designed and synthesized via chemoenzymatic polymerization. This alternating sequence was achieved by trypsin-catalyzed polymerization of a dipeptide monomer. Due to the electrostatic interaction between the anionic and cationic residues, the prepared ampholytic peptides spontaneously formed nanosized assemblies with a size of 100-200 nm in water. Modification with tetra(ethylene glycol) (TEG) at the N-terminus of these ampholytic alternating peptides resulted in the formation of stable nanosized assemblies, while peptides consisting of random sequences of lysine and glutamic acid formed large aggregates with deteriorated stability even with TEG modification. Morphological observations using a field-emission scanning electron microscope and an atomic force microscope revealed that the obtained assemblies were spherical and hollow, indicating the spontaneous formation of vesicles from the TEG-modified ampholytic alternating peptides. These vesicles were able to encapsulate a model fluorescent protein within their hollow structures without structural collapse causing loss of fluorescence, demonstrating the potential of these nanocarriers for use in material delivery systems.

Hereditary urolithiasis at a young age on the example of a clinical case

To study the clinical features and course of urolithiasis in a young female patient, to suggest the cause of the simultaneous sudden formation of kidney stones in the patient and her mother within a year. Main provisions: urolithiasis (KSD) is one of the most common diseases of the urinary tract. The relevance of effective treatment of this problem arises from the steady increase in the number of patients around the world, especially in Russia. According to many researchers, this trend is due to the increase in life expectancy, changes in lifestyle and nutrition, as well as changes in the composition of water and climate conditions. Approximately two thirds of patients, develop the disease at the age from 30 to 60. Characteristic features of urolithiasis are repeated recurrence and a high incidence of complex forms, which complicates the treatment of such patients significantly. Diagnostic algorithm and treatment of urolithiasis are demonstrated in this article on the example of a medical history of a young patient with rapidly progressing urolithiasis. A similar disease with the same symptoms of urolithiasis was revealed in the patient’s parent a week later, which suggests a hereditary predisposition factor or manifestation of urolithiasis being dependent on the hard drinking water. The simultaneous sudden formation of kidney stones within a year in a patient at a young age and her mother emphasizes the hereditary nature of the disease. Probably, the peculiarities of national cuisine or the individual preferences of patients played a significant role in the development of the pathology. The composition of drinking water is extremely important. The patient is from the Republic of Bashkortostan, where water hardness is 7.8–8.0, which does not meet the standard.

Simultaneous Li-Doping and Formation of SnO2-Based Composites with TiO2: Applications for Perovskite Solar Cells.

Tin oxide (SnO2) has been recognized as one of the beneficial components in the electron transport layer (ETL) of lead-halide perovskite solar cells (PSCs) due to its high electron mobility. The SnO2-based thin film serves for electron extraction and transport in the device, induced by light absorption at the perovskite layer. The focus of this paper is on the heat treatment of a nanoaggregate layer of single-nanometer-scale SnO2 particles in combination with another metal-dopant precursor to develop a new process for ETL in PSCs. The combined precursor solution of Li chloride and titanium(IV) isopropoxide (TTIP) was deposited onto the SnO2 layer. We varied the heat treatment conditions of the spin-coated films comprising double layers, i.e., an Li/TTIP precursor layer and SnO2 nanoparticle layer, to understand the effects of nanoparticle interconnection via sintering and the mixing ratio of the Li-dopant on the photovoltaic performance. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) measurements of the sintered nanoparticles suggested that an Li-doped solid solution of SnO2 with a small amount of TiO2 nanoparticles formed via heating. Interestingly, the bandgap of the Li-doped ETL samples was estimated to be 3.45 eV, indicating a narrower bandgap as compared to that of pure SnO2. This observation also supported the formation of an SnO2/TiO2 solid solution in the ETL. The utilization of such a nanoparticulate SnO2 film in combination with an Li/TTIP precursor could offer a new approach as an alternative to conventional SnO2 electron transport layers for optimizing the performance of lead-halide perovskite solar cells.

The process of reparative regeneration of the damaged stomach in rabbits

This research is relevant due to the increasing incidence of pathological conditions in the rabbit stomach requiring surgical intervention for treatment. In order to improve and expedite the recovery process post-surgery, the research team decided to thoroughly investigate the reparative and regenerative processes in the rabbit stomach wall at various stages of healing. To achieve this, studies were conducted on the first, third, seventh, tenth, fourteenth, and twenty-first days post-operative intervention, comparing them with histological analysis of the stomach wall in rabbits that did not undergo surgery. Histological investigations revealed an interesting phenomenon within the first 24 hours after stomach injury in rabbits: the muscular layer underwent contraction, leading to closure of the defect, albeit with simultaneous formation of folds in the wound area. Additionally, small fragments of the muscular layer were observed on the outer surface of the stomach, partially degraded. By the third day, active fibroblast proliferation was evident in the damaged submucosal layer, a crucial stage in the regeneration process. By the seventh day, initial restoration of the submucosal layer was observed, although the defect was not yet completely resolved. By the tenth day, all components of the stomach wall, including the muscular layer, submucosal layer, and muscular lamina of the mucous membrane, were fully restored, albeit with the muscular lamina in the defect zone remaining hypertrophic. By the fourteenth day, the muscular lamina of the mucous membrane exhibited uneven thickening, and the newly formed mucous membrane contained cavities and necrotic tissue. By the twenty-first day, the stomach wall was completely restored, with properly formed structures.

Novel Technique for Median Cleft Lip Comprising the Simultaneous Formation of the Columella, Philtrum, and Cupid's Bow.

Numerous surgical techniques for median cleft lip repair have been described; however, most cause excessively sharp peaks or the collapse of Cupid's bow. We report a technique for median cleft lip repair using a mucosal skin flap and full-thickness skin graft and 15 years of follow-up. Our technique provides acceptable formation of the columella, philtrum, and the two peaks of Cupid's bow. In this paper, we cite our previously reported techniques and add new findings and discussion based on the long-term postoperative outcomes of this procedure. Advantages and disadvantages of this technique are discussed, and a possible solution to achieve a more satisfactory result is suggested. Advantages and disadvantages of this new technique are discussed, and a possible solution to achieve a more satisfactory result is suggested.

Arginine Acts as both Co-Solvent and Catalyst in Regioselective Eutectic-Mediated Dimerization of Levulinic Acid.

A simple, solvent-free arginine-catalyzed aldol dimerization of levulinic acid was achieved via the simultaneous formation of a eutectic mixture. Dimers of levulinic acid are valued as biomass-derived fine chemical precursors, with potential to upgrade to bio-jet fuels or N-containing functional chemicals. Typically, these dimers are produced as isomeric mixtures using high temperatures and a variety of solid inorganic catalysts or mineral acids. In this study, an organocatalytic and regioselective dimerization was achieved at 22 % conversion on either a bench or kilogram scale using mild temperatures and only L-arginine as both a co-solvent and catalyst. The intricate H-bonding network comprising the eutectic solvent was harnessed to produce only one product, minimizing side reactivity and preserving the reactants for recycling.

Bioactivity of radiopaque 45S5 bioactive glass with progressive additions of Bi2O3: A dissolution study under static conditions

The integration of bioactive glasses (BGs) into hard tissues in in-vivo models can be evaluated through X-ray radiographs. The image contrast plays an important role and should be enhanced to improve accurate minimal invasive diagnostics of the performance of BGs containing implants after surgery. The present work shows the effect of the progressive addition of Bi2O3 (up to 12.2 wt%) on the structure, thermal properties, radiopacity, and bioactivity of 45S5-like BG obtained by quenching of the melt prepared from oxide precursors. The BG chemical composition, phase composition, structure, chemical state, thermal properties, and radiopacity were respectively investigated by X-ray fluorescence (XRF), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and radiopacity analysis according to the ISO13116:2014 norm. The bioactivity of the glasses was monitored by immersing them in a simulated body fluid (SBF) under static conditions. The apatite formation ability and ion concentration in SBF after 3, 7, 14, and 21 days were investigated by XRD, scanning electron microscopy (SEM), inductively coupled plasma optical emission spectroscopy (ICP-OES), and ICP mass spectrometry (ICP-MS). All samples were found to be X-ray amorphous. Simultaneous formation of [BiO3] and [BiO6] units is noted in the BG. The glass radiopacity increased up to 1.8 and 4.2 times compared to the reference glasses without Bi2O3. Bi2O3 additions in the glass slow down the formation of apatite-like structures as a result of the network forming role of [BiO3] and [BiO6] units in the BG. Nevertheless, the BGs with the 12.2 wt % Bi2O3 still shows the ability to form apatite deposits after 7 days of immersion in simulated body fluid (SBF).

Construction of 3-Methyl-2-Substituted Benzo[b]furans and 3-Methyl-2-Substituted Benzo[b]thiophenes Using Solid Calcium Carbide as a Substitute for Gaseous Acetylene.

A concise method for the facile construction of 3-methyl-2-substituted benzo[b]furans and 3-methyl-2-substituted benzo[b]thiophenes using low-cost, abundant, and easy-to-use solid calcium carbide instead of flammable and explosive gaseous acetylene as an original alkyne source, o-bromophenyl ethers or o-bromophenyl thioethers as substrates through an intramolecular carbanion-yne cyclization in a 5-exo-dig manner, and subsequent double-bond isomerization is described. The simultaneous formation of two C-C bonds is realized in a one-step route. The wide substrate scope, high yield, and simple workup manipulations are also merits of this method. The synthetic strategy can also be suitable for the gram scale.

Integrated treatment of wax and scale removal in old wells of the Tanjung Field

The majority of oil wells in the Tanjung Field are old wells with reservoir characterized by low pressure and temperature, as well as high water production. The characteristic of oil in the Tanjung Field has a relatively high wax content of 17.61%. This condition has led to several wells in the Tanjung Field experiencing issues with the simultaneous formation of wax and scale deposits within the wellbore equipment. The simultaneous occurrence of wax and scale can significantly impact the production rate. Therefore, addressing this production issue efficiently requires a method known as wax scale removal (WSR). WSR can effectively tackle the problem of wax and scale deposits occurring simultaneously in production equipment. In this method, a solvent for dissolving wax deposits and an acid for dissolving scale are injected together using the huff and puff technique.

The ALMA Survey of 70 μm Dark High-mass Clumps in Early Stages (ASHES). XI. Statistical Study of Early Fragmentation

Fragmentation during the early stages of high-mass star formation is crucial for understanding the formation of high-mass clusters. We investigated fragmentation within 39 high-mass star-forming clumps as part of the Atacama Large Millimeter/submillimeter Array Survey of 70 μm Dark High-mass Clumps in Early Stages (ASHES) survey. Considering projection effects, we have estimated core separations for 839 cores identified from the continuum emission and found mean values between 0.08 and 0.32 pc within each clump. We find compatibility of the observed core separations and masses with the thermal Jeans length and mass, respectively. We also present subclump structures revealed by the 7 m array continuum emission. Comparison of the Jeans parameters using clump and subclump densities with the separation and masses of gravitationally bound cores suggests that they can be explained by clump fragmentation, implying the simultaneous formation of subclumps and cores within rather than a step-by-step hierarchical fragmentation. The number of cores in each clump positively correlates with the clump surface density and the number expected from the thermal Jeans fragmentation. We also find that the higher the fraction of protostellar cores, the larger the dynamic range of the core mass, implying that the cores are growing in mass as the clump evolves. The ASHES sample exhibits various fragmentation patterns: aligned, scattered, clustered, and subclustered. Using the Q -parameter, which can help distinguish between centrally condensed and subclustered spatial core distributions, we finally find that in the early evolutionary stages of high-mass star formation, cores tend to follow a subclustered distribution.