Binary Systems Research Articles

Excess properties and intermolecular interactions of 2-methoxyethanol + ethylenediamine binary system: Density, viscosity, spectral analyses, computational chemistry, and CO2 absorption property

To examine the fundamental physicochemical properties as well as intermolecular interactions for the 2-methoxyethanol (EGME) (1) + ethylenediamine (EDA) (2) binary system, this work systemically measured the density (ρ) and viscosity (η) values of the binary system with various mole ratios at P = 100.5 kPa and T = (298.15–318.15) K with the growth gap of 5 K. The as-measured values of the pure substances were compared with literature data. Multiple semi-empirical formulas were used to fit ρ and η values, and the absolute average deviations (AAD%) were calculated. After that, the excess molar volume (VmE), partial molar volume (V¯), apparent molar volume (Vφ), viscosity deviation (Δη), excess activation of Gibbs free energy (ΔG∗E), and several thermodynamic properties of the binary system were systemically analyzed. According to analysis results, it has been proven that the interaction exists between EGME and EDA molecules. And then, excess properties were fitted to the Redlich-Kister equation using multi-parametric nonlinear regression analyses, and standard deviations (σ) were calculated. In addition, based on various characterization methods including Raman, ultraviolet (UV), and nuclear magnetic resonance hydrogen (1H NMR) spectral analyses and density functional theory (DFT) calculation results, it is demonstrated that there is intermolecular hydrogen bonds in EGME (1) + EDA (2) binary system as the form of –OH⋯NH2–, which was consistent with the existence forms of intermolecular hydrogen bonds in different alcohol-amine systems from references. Finally, CO2 absorption capacity by pure EDA, pure EGME, and the EGME (1) + EDA (2) binary system were severally determined.

Expansion of Accreting Main-sequence Stars during Rapid Mass Transfer

Accreting main-sequence stars expand significantly when the mass accretion timescale is much shorter than their thermal timescales. This occurs during mass transfer from an evolved giant star onto a main-sequence companion in a binary system and is an important phase in the formation of compact binaries including X-ray binaries, cataclysmic variables, and gravitational-wave sources. In this study, we compute 1D stellar models of main-sequence accretors with different initial masses and accretion rates. The calculations are used to derive semianalytical approximations to the maximum expansion radius. We assume that mass transfer remains fully conservative as long as the inflated accretor fits within its Roche lobe, leading stars to behave like hamsters, stuffing excess material behind their expanding cheeks. We suggest a physically motivated prescription for the mass growth of such “hamstars,” which can be used to determine mass-transfer efficiency in rapid binary population synthesis models. With this prescription, we estimate that progenitors of high-mass X-ray binaries and gravitational-wave sources may have experienced highly nonconservative mass transfer. In contrast, for low-mass accretors, the accretion timescale can exceed the thermal timescale by a larger factor without causing significant radial expansion.

Bright Supernova Precursors by Outbursts from Massive Stars with Compact Object Companions

A fraction of core-collapse supernovae (SNe) with signs of interaction with a dense circumstellar matter are preceded by bright precursor emission. While the precursors are likely caused by a mass ejection before core collapse, their mechanism to power energetic bursts—sometimes reaching 1048–1049 erg, which is larger than the binding energies of red supergiant envelopes—is still under debate. Remarkably, such a huge energy deposition should result in an almost complete envelope ejection and hence a strong sign of interaction, but the observed SNe with precursors show in fact typical properties among the interacting SNe. More generally, the observed luminosity of 1040−1042 erg s−1 is shown to be challenging for a single SN progenitor. To resolve these tensions, we propose a scenario where the progenitor is in a binary system with a compact object (CO) and an outburst from the star leads to a super-Eddington accretion onto the CO. We show that for sufficiently short separations outbursts with moderate initial kinetic energies of 1046–1047 erg can be energized by the accreting CO so that their radiative output can be consistent with the observed precursors. We discuss the implications of our model in relation to CO binaries detectable with Gaia and gravitational-wave detectors.

The Dynamical Equations of the Restricted Three-Body Problem with Poynting-Robertson Drag Force and Variable Masses

The restricted three-body problem (R3BP) is a formulation which defines the motion of a passively gravitating test particle having infinitesimal mass and moving in the gravitational environment of two bodies, called primaries. The R3BP is still an exciting and active research field that has been getting attention of scientists and astronomers because of its applications in dynamics of the solar and stellar systems, lunar theory, and artificial satellites. The equations of motion are usually the starting point in the investigations of the dynamical predictions of the infinitesimal mass. Therefore, in this paper, we examine the derivations of the dynamical equations of the R3BP with Poynting-Robertson (P-R) Drag force and variable masses. In this model formulation, both primaries are assumed to vary their masses under the combined Mestschersky law (CML) and they move in the frame of the GyldenMestschersky equation (GME). Further, the bigger primary is assumed to be emitting radiation force, which is a component of the radiation pressure and the P-R drag. The non- autonomous dynamical equations of the model are derived and converted into the autonomized equations with constant coefficients using the Mestschersky transformation (MT), the CML, the particular solutions of the GMP, and a transformation for the time dependent velocity of light. We observed that the P-R drag of the bigger primary depends on the mass parameter, radiation pressure, velocity of light and the mass variation constant . The derived systems of equations with variable and constant coefficients can be used to model the long-term motion of satellites and planets in binary systems.

Pit-lake remediation by chemically activated Chlorocardium rodiei: Simultaneous metal ion removal from acidic waters

The current study investigates the valorization of waste wood from a tropical hardwood found in Guyana (Greenheart – Chlorocardium rodiei) to high surface area activated carbons (AC). We subsequently deployed these adsorbents to sequester Mn 2+, Fe3+, and Al3+ from the acidic waters of a recreational bauxite pit-lake. We studied the impact of activation parameters such as temperature, impregnation ratio and acid concentration on the texture and surface chemistry of ACs and demonstrate that optimized low pH at point-of-zero charge (pHpzc) ACs are efficient adsorbents for the target ions. A mesoporous AC with specific surface area of 2208 m2/g, 11 % surface oxygen and pHpzc of 1.98 was produced under optimized conditions. ACs removed 93–100 % of target ions from pit-lake waters at a native pH of 3.1. Al3+ exerted an antagonistic effect on Mn2+ adsorption in synthetic binary ion systems reducing adsorption by as much as 56 %. The Sips Model fitted the adsorption data best predicting maximum adsorption capacities for Mn2+, Fe3+ and Al3+ of 17.8 mg/g, 23.7 mg/g, and 6.12 mg/g for these low pHpzc optimized materials. These materials show great promise in removing heavy metals from acidic waters.

Waste-derived activated carbons for effective adsorptive removal of strontium, barium, and binary pollutants: A response surface methodology study

A double-pronged approach to pollution management is proposed by sustainably managing solid wastes and converting them to activated carbons that are then utilized for water treatment. In this study, gas-to-liquids (GTL) derived biosolids, carboard and their mixed samples are used to produce the activated carbons. In a laboratory batch study, a Box-Behnken experimental design was used with four factors and three levels to optimize the removal of single component strontium and barium, and the binary system of pollutants from an aqueous solution. The design incorporated response surface modeling (RSM) techniques with a total of 29 different experimental data points collected and analyzed in this study. The study was conducted considering four parameters: the initial pH of the solution (ranging from 4.0 to 8.0), temperature (ranging from 20 to 40 ℃), the percentage of cardboard (fixed at 0 %, 50 %, and 100 %), and the amount of adsorbent (between 0.05 and 0.5 g). These factors were assigned three levels, represented as −1, 0, and 1. A second-order polynomial regression equation was then developed to estimate the responses. The statistical significance of the independent variables and their interactions was assessed using analysis of variance (ANOVA) with a 95 % confidence level (α = 0.05). The results revealed that only temperature and dosage show significant effects on the responses and that optimum values of the selected parameters were obtained by solving the prediction equations, which were validated with less than 4 % error %. In an attempt to optimize the factors, a pH of 5.5, temperature of 40 ℃ and dose of 0.3 g is found for all three samples. Validation results for optimization also proved that varying the percentage cardboard showed little difference in the percentage removal of all the pollutants. The results from this study can be directly applied for any such systems trying to optimize these parameters and the prediction equations can be utilized effectively.

Sites of Planet Formation in Binary Systems. I. Evidence for Disk−Orbit Alignment in the Close Binary FO Tau

Close binary systems present challenges to planet formation. As binary separations decrease, so do the occurrence rates of protoplanetary disks in young systems and planets in mature systems. For systems that do retain disks, their disk masses and sizes are altered by the presence of the binary companion. Through the study of protoplanetary disks in binary systems with known orbital parameters, we seek to determine the properties that promote disk retention and therefore planet formation. In this work, we characterize the young binary−disk system FO Tau. We determine the first full orbital solution for the system, finding masses of 0.35−0.05+0.06M⊙ and 0.34 ± 0.05 M ⊙ for the stellar components, a semimajor axis of 22(−1+2) au, and an eccentricity of 0.21(−0.03+0.04) . With long-baseline Atacama Large Millimeter/submillimeter Array interferometry, we detect 1.3 mm continuum and 12CO (J = 2–1) line emission toward each of the binary components; no circumbinary emission is detected. The protoplanetary disks are compact, consistent with being truncated by the binary orbit. The dust disks are unresolved in the image plane, and the more extended gas disks are only marginally resolved. Fitting the continuum and CO visibilities, we determine the inclination of each disk, finding evidence for alignment of the disk and binary orbital planes. This study is the first of its kind linking the properties of circumstellar protoplanetary disks to a precisely known binary orbit. In the case of FO Tau, we find a dynamically placid environment (coplanar, low eccentricity), which may foster its potential for planet formation.

First Principles Evaluation of Phase Stability in the In-Sn Binary System

AbstractThe In-Sn binary alloy system exhibits several unusual features that challenge crystallographic and thermodynamic expectations. We combine first principles total energy calculation with simple thermodynamic modeling to address two key points. First, we evaluate energies along the Bain path to interpret the discontinuous transition between the phases α-In (Pearson type tI2) and β-In3Sn (also Pearson type tI2) that are identical in symmetry. Second, we demonstrate that the solid solution phases β-In3Sn and γ-InSn4 (Pearson type hP1) exist at high temperatures only, and they exhibit eutectoid decompositions at low temperatures.

Phase equilibria in the Al–Fe–Mo system

This paper presents the results of our comprehensive study of phase equilibria in the Al–Fe–Mo system using DTA, X-ray diffraction, SEM and electron probe microanalysis. The liquidus and solidus projections were constructed. It is shown that the ternary compound Al8FeMo3 (τ) melts congruently at >1500 °C and has a homogeneity range from 2 to 9 at.% Fe and from 23.5 to 25 at.% Mo. Isostructural phases (Mo), (αFe) and AlMo (W-type structure, cI2-Im-3m) at solidus temperatures form a continuous solid solution (αFe,Mo,AlMo). Unlike the AlMo binary phase, which is not retained by quenching, the ternary (αFe,Mo,AlMo) phase is easily quenched due to its lower decomposition temperature. Among the binary based phases, the Al8Fe5 (ε) phase has the widest homogeneity region, which extends up to 24 at.% Mo at solidus temperatures. It is shown that the addition of Mo stabilizes the Al8Fe5 (ε) phase, and the temperature of its formation in the ternary system increases to 1331 °C in contrast to 1234 °C in the binary. Moreover, according to XRD data, the Al8Fe5 (ε) phase in the ternary system has a rhombohedral structure of the Al8Cr5-type (hR78-R-3m), rather than cubic Cu5Zn8-type structure (cI52-I-43m), like the binary one. A new binary compound Al45Mo7 was identified for the first time. Its crystal structure is established as monoclinic Al45V7-type (mS104-C2/m) with the lattice parameters a = 20.534, b = 7.561, c = 10.910 Å, β = 107.33. It was shown to form by peritectic reaction L + Al5Mo ⇄ Al45Mo7 at ∼800 °C. Iron additions stabilize the Al4Mo phase, which in the binary system is stable above 942 °C.

High-cadence Timing of Binary Pulsars with CHIME

We performed near-daily observations of the binary pulsars PSR J0218+4232, PSR J1518+4904, and PSR J2023+2853 with the Canadian Hydrogen Intensity Mapping Experiment (CHIME). For the first time, we detected the Shapiro time delay in all three pulsar binary systems, using only 2–4 yr of CHIME/Pulsar timing data. We measured the pulsar masses to be 1.49−0.20+0.23 M ⊙, 1.470−0.034+0.030 M ⊙, and 1.50−0.38+0.49 M ⊙, respectively. The companion mass to PSR J0218+4232 was found to be 0.179−0.016+0.018 M ⊙. We constrained the mass of the neutron star companion of PSR J1518+4904 to be 1.248−0.029+0.035 M ⊙, using the observed apsidal motion as a constraint on the mass estimation. The binary companion to PSR J2023+2853 was found to have a mass of 0.93−0.14+0.17 M ⊙; in the context of the near-circular orbit, this mass estimate suggests that the companion to PSR J2023+2853 is likely a high-mass white dwarf. By comparing the timing model obtained for PSR J0218+4232 with previous observations, we found a significant change in the observed orbital period of the system of Pḃ=0.14(2)×10−12 ; we determined that this variation arises from “Shklovskii acceleration” due to the relative motion of the binary system, and used this measurement to estimate a distance of d = (6.7 ± 1.0) kpc to PSR J0218+4232. This work demonstrates the capability of high-cadence observations, enabled by the CHIME/Pulsar system, to detect and refine general-relativistic effects of binary pulsars over short observing timescales.

The puzzling orbital residuals of XTE J1710–281: Is a Jovian planet orbiting the binary system?

is a transient eclipsing binary system with a period close to 3.28 hours that hosts a neutron star. The average eclipse duration is 420 seconds, and eclipse arrival times reported in the literature span from 1999 to 2017. A previous analysis of the eclipse arrival times using the eclipse timing technique revealed a complex pattern of delays, indicating the presence of three orbital glitches. These glitches correspond to sudden variations in the orbital period and allow for the identification of four distinct epochs, during which the orbital period derivative was estimated to be $-1.8 $ s s$^ $ s s$^ $ s s$^ $, and $0.09 $ s s$^ $, respectively. We reanalyzed the 78 eclipse arrival times spanning 18 years utilizing the eclipse timing technique to derive the corresponding delays as a function of time. We find that the observed delays align well with a fitting model that employs an eccentric sine function characterized by an amplitude of $6.1 0.5$ s, an eccentricity of $0.38 0.17$, and a period of $17.1 1.5$ years. Additionally, we identified the orbital period to be 3.28106345(13) hours, with a reference epoch of $T_0=54112.83200(2)$ MJD. We obtained an upper limit to the orbital period derivative of $3.6 $ s s$^ From the average value of the eclipse duration, we estimate that the companion star has a mass of 0.22 for a neutron star mass of 1.4 and that the inclination of the source is $ degrees. The companion star is in thermal equilibrium. The orbital period derivative is consistent with a conservative mass transfer scenario, where the angular momentum loss due to magnetic braking dominates over gravitational radiation angular momentum loss if the former is present. The eccentric modulation can be explained by a third body with a mass of 2.7 Jovian masses, orbiting with a revolution period close to 17 years and an eccentricity of 0.38.

Distinguishing ΛCDM from Evolving Dark Energy with Om Two-point Statistics: Implications from the Space-borne Gravitational-wave Detector

The Omh 2(z i , z j ) two-point diagnostics was proposed as a litmus test of the ΛCDM model, and measurements of the cosmic expansion rate H(z) have been extensively used to perform this test. The results obtained so far suggested a tension between observations and predictions of the ΛCDM model. However, the data set of H(z) direct measurements from cosmic chronometers and baryon acoustic oscillations was quite limited. This motivated us to study the performance of this test on a larger sample obtained in an alternative way. In this paper, we propose that gravitational-wave (GW) standard sirens could provide large samples of H(z) measurements in the redshift range of 0 < z < 5, based on the measurements of the dipole anisotropy of luminosity distance arising from the matter inhomogeneities of the large-scale structure and the local motion of the observer. We discuss the effectiveness of our method in the context of the space-borne DECi-herz Interferometer Gravitational-wave Observatory, based on a comprehensive H(z) simulated data set from binary neutron star merger systems. Our results indicate that in the GW domain, the Omh 2(z i , z j ) two-point diagnostics could effectively distinguish whether ΛCDM is the best description of our Universe. We also discuss the potential of our methodology in determining possible evidence for dark energy evolution, focusing on its performance on the constant and redshift-dependent dark energy equation of state.

Pore size regulation of ZIFs for adsorptive separation of branched chain and aromatic amino acids

AbstractThis research endeavour aims to investigate the adsorptive separation of the branched chain (BCAA) and aromatic amino acids (AAA). Based on the different molecular sizes of BCAA and AAA, zeolitic imidazolate frameworks (ZIFs) with different pore structures were prepared by regulating the size of imidazole ligands. The structure and pore shape were characterized by Fourier transform infrared spectroscopy (FT‐IR), x‐ray diffraction (XRD), scanning electron microscope (SEM), and BET surface area (BET). The results indicated the successful synthesis of ZIF‐[Co(mIm)2], ZIF‐[Co(eIm)2], and ZIF‐[Co(pIm)2] with pore size distribution of 7.821, 6.943, and 9.394 Å, and particle size of these ZIFs was approximately 4 μm. ZIF‐[Co(eIm)2] was chosen as the optimal ZIFs for the separation of BCAA and AAA. The adsorption experiment was evaluated in the respective single and binary systems. The corresponding data in a single system demonstrated that ZIF‐[Co(eIm)2] showed good adsorption performance for BCAA and poor for AAA. Furthermore, the adsorption behaviour under experimental conditions conformed well to the pseudo‐second‐order kinetic model and Langmuir isotherm. ZIF‐[Co(eIm)2] had great separation ability for BCAA/AAA in their binary system. Finally, regeneration studies further manifested that ZIF‐[Co(eIm)2] exhibited fine reusability performance with adsorption efficiencies still higher than 70% after five cycles. This study exhibits a novel path for the design of adsorbents for efficient separation of BCAA/AAA.

Structural Properties and Photocatalytic Activity of TiO2/Au Nanocomposites Synthesized with Glucose

AbstractA one‐pot synthesis of plasmonic gold‐modified TiO2 nanocomposites is reported by using glucose reduction of HAuCl4 in presence of titanium tetraisopropoxide. The resulting nanocomposites are characterized by thermal‐gravimetric analyses, X‐ray diffraction combined with X‐ray fluorescence and photoelectron spectroscopies. A binary system of β‐TiO2 and anatase phases is obtained for low Au content while only anatase form is favored when the initial Au rate rises. This investigation also suggests the inclusion of gold in the TiO2 structure. Although the optical bandgap of the different nanocomposites remains around 3 eV, the increase of Au content induces a shift of both valence and conduction edge bands to lower energy levels. The photocatalytic activity of TiO2/Au nanocomposites is assessed through the decolorization of different cationic and anionic dyes as model compounds. Regarding rhodamine and methylene blue dyes, the sample TiO2 modified with 3.5 wt% of Au presents the best performance. The relation between the structure of the nanocomposites and their capacity to degrade pollutants is discussed.

Transport of polyethylene and polypropylene microplastics under the action of agricultural chemicals: Role of pesticide adjuvants and neonicotinoid active ingredients

Understanding the impact of various agricultural chemical components on the fate and transport of microplastics (MPs) in the subsurface is essential. In this study, column experiments on saturated porous media were conducted to explore the influence of the coexistence environment of pesticide adjuvants (surfactants) and active ingredients (neonicotinoids) on the transport of polyethylene (PE) and polypropylene (PP) MPs. An anionic surfactant (sodium dodecyl sulfate (SDS)), a nonionic surfactant (nonylphenol ethoxylate (NP-40)), and three neonicotinoid insecticides (acetamiprid, dinotefuran, and nitenpyram) could independently increase MP migration by 9.31%–61.01% by improving the hydrophilicity. Acetamiprid or dinotefuran reduced the adhesion work of the binary system by competing with SDS for adsorption sites, thereby inhibiting PE mobility. However, nitenpyram in the mixture was not easily adsorbed on the surface of PE MPs together with SDS because of nitenpyram's high hydrophilicity. Neonicotinoid molecules could not reduce the hydrophilic modification of SDS on PP MPs by competing for adsorption sites. Owing to their weak charge and adhesion work of nonionic surfactants (−4.80 mV and 28.45 kT for PE and −8.21 mV and 17.64 kT for PP), neonicotinoids tended to occupy the adsorption sites originally belonging to NP-40. The long molecular chain of NP-40 made it difficult for high-concentration neonicotinoids to affect the adhesion on MPs. In addition, NP-40 was harder to peel off from the MP surface than SDS, leading to a larger MP transport ability in the sand column.

Effect of intestinal nitrate on growth of Klebsiella pneumoniae and its regulatory mechanism

To explore the effect of intestinal nitrates on the growth of Klebsiella pneumoniae and its regulatory mechanisms. K. pneumoniae strains with nitrate reductase narG and narZ single or double gene knockout or with NarXL gene knockout were constructed and observed for both aerobic and anaerobic growth in the presence of KNO3 using an automated bacterial growth analyzer and a spectrophotometer, respectively. The mRNA expressions of narG and narZ in K. pneumoniae in anaerobic cultures in the presence of KNO3 and the effect of the binary regulatory system NarXL on their expresisons were detected using qRT-PCR. Electrophoretic mobility shift assays (EMSA) and MST analysis were performed to explore the specific regulatory mechanisms of NarXL in sensing and utilizing nitrates. Competitive experiments were conducted to examine anaerobic growth advantages of narG and narZ gene knockout strains of K. pneumoniae in the presence of KNO3. The presence of KNO3 in anaerobic conditions, but not in aerobic conditions, promoted bacterial growth more effectively in the wild-type K. pneumoniae strain than in the narXL gene knockout strain. In anaerobic conditions, the narXL gene knockout strain showed significantly lowered mRNA expressions of narG and narZ (P < 0.0001). EMSA and MST experiments demonstrated that the NarXL regulator could directly bind to narG and narZ promoter regions. The wild-type K. pneumoniae strain in anaerobic cultures showed significantly increased expressions of narG and narZ mRNAs in the presence of KNO3 (P < 0.01), and narG gene knockout resulted in significantly attenuated anaerobic growth and competitive growth abilities of K. pneumoniae in the presence of KNO3 (P < 0.01). The binary regulatory system NarXL of K. pneumoniae can sense changes in intestinal nitrate concentration and directly regulate the expression of nitrate reductase genes narG and narZ to promote bacterial growth.

Multi-objective optimization of sequential simulated moving bed for multi-component separation based on multi-parameter modeling and its determination

This study investigates optimum solution for difficult multi-component separation and purification process based on sequential simulated moving bed (SSMB) technology. Xylo-oligosaccharides (XOS), containing XOS with polymerization degree 2–6, xylose and arabinose, was chosen as the main system due to its complex composition and low degree resolution. Multi-objective optimization (MOO) was carried out for three cases with different combinations of objective functions, decision variables and constraints. Multi-component system studied in this work is not simplified as a binary mixture while all the kinetics and isotherm parameters are considered in the SSMB modeling process. Several groups of SSMB experiments were conducted to verify the accuracy of parameter determination and to prove further the necessity and superiority of application of multi-parameter simulation. Furthermore, the MOO based on multi-parameter simulation were done, which shows that better Pareto optimal curves could be obtained when product purity, recovery, water consumption and unit throughput are simultaneously optimized with meaningful constraints. The corresponding trends of flow rate ratios, operating conditions, and internal concentration profiles for both multi-parameter and binary systems were compared and analyzed to determine a reasonable strategy for multi-component separation.

The improved component masses and parallaxes for the two close binary stars: HD 80671 and HD 97038

We present the fundamental stellar parameters, including the individual component masses, as well as the orbital parameters, and dynamical parallaxes of the two close binary stars; HD80671, and HD97038. The stellar parameters are spectrophotometrically estimated via Al-Wardat’s method for analyzing binary and multiple stellar systems, which is having a combination of the spectroscopic analysis and the photometric analysis to build the combined and individual synthetic spectral energy distributions of the individual components of the systems and so to estimate their fundamental parameters, metallicities, and ages. It employs Kurucz’s model atmospheres of single stars, while the orbital parameters are estimated using Tokovinin’s method. The individual spectrophotometric component masses are inferred with good accuracy, and found to be MSphA = 1.47±0.10M⊙ and MSphB=1.29±0.09M⊙ with an age of 1.0±0.09 Gyr for HD80671, and MSphA=1.17±0.09M⊙ and MSphB=1.12±0.08M⊙ with an age of 3.981±0.35 Gyr for HD97038. The improved dynamical parallaxes are given as πdyn=28.305±0.45 mas for HD80671, and πdyn=16.26±0.30 mas for HD97038. The evolutionary status of two binaries is discussed depending on the positions of the components on the isochrones and evolutionary tracks.

Organocatalytic ring-opening polymerization of lactide by bis(thiourea) H-bonding donating cocatalysts with binaphthyl-amine framework

Development of H-bonding organo-catalysts with high catalytic activity and high degree of control is significantly important for the metal-free polyesters that are potentially suitable for biomedical usage. The concomitant use of base and commercially available thiourea generally suffered from prolonged reaction time and resulted in incomplete monomer conversion in some cases. Introducing one or more (thio)urea H-bonding donating arms to the parent thiourea has been proved to be an effective method for substantially increasing the activity of thiourea H-bonding donors. Consequently, we synthesized bis-thioureas derived from binaphthyl-amine bearing different substituents and investigated their catalytic performance in ROPs of lactide in this work. The density functional theory (DFT) calculations suggested that the “activated-thiourea” mode is more preferred for the bis(thiourea) containing binaphthyl-amine framework. The bis(thiourea)/base binary systems could effectively promote the LA polymerization using benzyl alcohol as initiator. The polymerization rates and the degree of control over the polymerization are highly dependent on the structures of the bis(thiourea) and base. Bis(thiourea)/1,5,7-triazabicyclo[4.4.0]dec‑5-ene pairs exhibited highest catalytic activity compared to other bis(thiourea)/base pairs, and the turnover frequency is high up to 1980 h–1 at 75 °C. In addition, the bulky hindrance and axial chirality of the binaphthyl-amine framework could enable stereoselective ROP of rac-LA to produce isotactic-rich and crystalline PLAs at relatively low temperature (0 °C). Mechanistic studies indicated that both enantiomorphic site control (ESC) and chain end control (CEC) concurrently occurred in the rac-LA polymerization catalyzed by bis(thiourea)/base binary systems. This work will inspire future design of H-bonding donors with high catalytic performance.

Minimally Invasive Delivery of Percutaneous Ablation Agent via Magnetic Colloidal Hydrogel Injection for Treatment of Hepatocellular Carcinoma.

Percutaneous thermotherapy, a minimally invasive operational procedure, is employed in the ablation of deep tumor lesions by means of target-delivering heat. Conventional thermal ablation methods, such as radiofrequency or microwave ablation, to a certain extent, are subjected to extended ablation time as well as biosafety risks of unwanted overheating. Given its effectiveness and safety, percutaneous thermotherapy gains a fresh perspective, thanks to magnetic hyperthermia. In this respect, an injectable- and magnetic-hydrogel-construct-based thermal ablation agent is likely to be a candidate for the aforementioned clinical translation. Adopting a simple and environment-friendly strategy, a magnetic colloidal hydrogel injection is introduced by a binary system comprising super-paramagnetic Fe3O4 nanoparticles and gelatin nanoparticles. The colloidal hydrogel constructs, unlike conventional bulk hydrogel, can be easily extruded through a percutaneous needle and then self-heal in a reversible manner owing to the unique electrostatic cross-linking. The introduction of magnetic building blocks is exhibited with a rapid magnetothermal response to an alternating magnetic field. Such hydrogel injection is capable of generating heat without limitation of deep penetration. The materials achieve outstanding therapeutic results in mouse and rabbit models. These findings constitute a new class of locoregional interventional thermal therapies with minimal collateral damages.