Transition of iPB-1 with low molecular weight crystallized from solutions.

The dimension or entanglement of polymer chains is crucial to chain dynamics, and the polymer chains can be diluted and disentangled in a solution by reducing the interaction with each other. This letter addresses the role of solution concentration in the crystal transition of isotactic polybutene-1 (iPB-1) with low molecular weight crystallized from solution. It turned out that the transition of iPB-1 obtained from the higher concentration of the solution is faster than that obtained from the lower one. In addition, the disparity in the transition between the early stage and later stage for samples prepared from solutions with and without stirring was characterized. DSC and X-ray experiments revealed that initial temperatures for the solution-crystallized iPB-1 to melt and crystallize into form II dominated the transition. The role of entropy in the transition was proposed as a primary factor influencing the iPB-1 transition. Increasing the concentration of the solution or stirring during crystallization increases the supersaturation for iPB-1 to crystalize from the solution and form less stable crystals. The less stable iPB-1 crystals cause the formation of form II at lower temperatures during heating. Therefore, the lower entropy in amorphous regions resulted in an enhanced propensity for the helical conformation with a lower entropy and consequently accelerated the crystal transition.

Form II to form I transition in solution-crystallized isotactic polybutene-1.

Different polymer chains in a solution or melt have different conformations with corresponding entropy at each moment, which would be confined after crystallization. Equilibrium concept-based conformation or conformational entropy depends on chain dynamics, which is related to the effect of energy on conformational changes in polymer chains. Herein, an isotactic polybutene-1 (iPB-1) crystal was crystallized from solution by adding a precipitant at various temperatures. The solution-crystallized iPB-1 crystal was heated to 100 °C to obtain form II at different heat rates and the transition of form II was characterized. It was found that the form II to form I transition was not only related to the precipitation temperature but also to the heating rate of the solution-crystallized iPB-1. Thus, both precipitation temperature and heating rate determine the formation temperature of form II, i.e., form II that crystallized at lower temperature would transform faster. The results indicate that the conformation or conformational entropy of the amorphous region in iPB-1 is important to understand crystal transition.

Melt memory in random ethylene-1-alkene copolymers.

Chain flexibility or stiffness based polymer conformation plays a crucial role in affecting the dynamics and kinetics of polymers, which is related to the hierarchical architecture of chains. A series of random copolymers of ethylene and 1-alkenes including 1-hexene, 1-octene, and 1-dodecene were synthesized with metallocene catalysts. The crystallization behavior and memory effect in random ethylene-1-alkene copolymers with different side groups were investigated via differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). Rheological tests were performed for understanding their dynamical behavior. The results show that the melting peak and the viscosity decrease but the orthorhombic crystal dimensions increase with co-unit contents increasing in the copolymers. It was found that the scaling relationship between the zero shear viscosity (η0) and molecular weight (Mn) of the copolymers containing ethylene-1-hexene and ethylene-1-octene is 3.6, which is higher than the classical scaling value of 3.4. The memory of crystals in the melt is enhanced with the increase of 1-alkene contents but is independent of the types of 1-alkenes. The enhanced melt memory effect in the copolymers was proposed due to the effect of the 1-alkene based side groups on the dynamics of polymer chains. The present work would be helpful to understand the chain stiffness based polymer dynamics and processing of polyolefins and copolymers prepared with the metallocene catalyst.

Crystallization and melting of unentangled poly(ε-caprolactone) cycles containing pendants.

The Rouse model provides a basic framework to understand the chain dynamics of polymers, which is confirmed to be more suitable for exploring the linear dynamics of unentangled polymers. The crystalline morphology governed by chain dynamics and crystallization kinetics is expected to differ in linear and cyclic polymers. Cyclic poly(ε-caprolactone)s (c-PCLs) containing two bi-anthracenyl group pendants with molecular weights close to the critical molecular weight (Mc) were synthesized to investigate the chain dynamics based crystallization and melting behavior by DSC, POM, and in situ simultaneous small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) investigations during heating of the isothermally crystallized samples. Double endothermic peaks were observed in the DSC curves with a low heating rate of c-PCLs without entanglement after isothermal crystallization, especially for c-PCLs with Mc. The structure evolution of the crystalline structures observed from the in situ investigations during the heating and double endothermic peaks in DSC heating curves of the c-PCLs indicate the role of pendants in the chain dynamics, which leads to the reorganization of the metastable structures. Banded spherulites of c-PCL without entanglement were observed for the first time, and the uneven growth of spherulites along the radial direction may be caused by the mismatch between chain dynamics and crystallization kinetics.

Effects of end groups and entanglements on crystallization and melting behaviors of poly(ε-caprolactone).

The topology including end groups, entanglement loops, and tie molecules has a significant impact on the rheological and crystallization behavior and consequently on the functionality of a polymer. Unentangled, weakly entangled, and strongly entangled poly(ε-caprolactone)s (PCLs) with end groups and various molecular weights were synthesized. POM and DSC were used to observe spherulite growth and characterize thermal properties during crystallization and melting. The viscosity and structure of the samples were probed by rheology and X-ray analysis, respectively. The crossover of the scaling relationship of viscosity vs molecular weight demonstrates that the samples cover a wide range of entanglement density, and the bulky end groups cause deviations from the classical scaling laws. In situ simultaneous SAXS/WAXS investigations showed that the crystal structure of PCLs did not change with end groups and heating. The results of POM and DSC imply that the end groups and entanglements affect the crystallization rate and the spherulite morphology. The melting of PCLs containing end groups was found to be a multi-step process involving various nanoscale crystalline structures. The evolution of nanoscale crystalline structures of isothermally crystallized PCLs during heating was analyzed by fitting 1D SAXS profiles, and the continuous structural evolution was found to be a process influenced by end groups and entanglements. The results show that end groups and entanglements affect the chain dynamics and lead to constrained crystallization behavior and the formation of metastable structures, ultimately affecting the structure evolution during melting.

Mpemba effect in crystallization of polybutene-1.

The Mpemba effect and its inverse can be understood as a result of nonequilibrium thermodynamics. In polymers, changes of state are generally non-equilibrium processes. However, the Mpemba effect has been rarely reported in the crystallization of polymers. In the melt, polybutene-1 (PB-1) has the lowest critical cooling rate in polyolefins and tends to maintain its original structure and properties with thermal history. A nascent PB-1 sample was prepared by using metallocene catalysis at low temperature, and the crystallization behavior and crystalline structure of the PB-1 were characterized by DSC and WAXS. Experimentally, a clear Mpemba effect is observed not only in the crystallization of the nascent PB-1 melt in form II but also in form I obtained from the nascent PB-1 at low melting temperature. It is proposed that this is due to the differences in the chain conformational entropy in the lattice which influence conformational relaxation times. The entropy and the relaxation time can be predicted using the Adam-Gibbs equations, whereas non-equilibrium thermodynamics is required to describe the crystallization with the Mpemba effect.

Evaluating the efficacy and timing of blood purification modalities in early-stage hyperlipidemic acute pancreatitis treatment.

Hypertriglyceridemia-induced acute pancreatitis (HTG-AP) is characterized by a violent cytokine storm-driven inflammation and is associated with a predisposition to severe disease. The treatment strategy for HTG-AP consists mainly of conventional symptomatic and lipid-lowering treatments. For early-stage HTG-AP, blood purification (BP) can rapidly and effectively reduce serum triglyceride and inflammatory cytokine levels, block the development of systemic inflammatory response syndrome, and improve patient outcomes. Currently, the primary modalities for BP in patients with HTG-AP include plasma exchange, hemoperfusion, and hemofiltration. When using BP to treat patients with HTG-AP, a comprehensive analysis incorporating the elevated lipid levels and severity of the patient's condition contributes to the selection of different treatment modes. Moreover, the timing of the treatment is also imperative. Early intervention is associated with a better prognosis for patients with HTG-AP requiring lipid-lowering treatment.

N-Heterocyclic Carbene-Catalyzed Atroposelective Annulation for Access to Thiazine Derivatives with C-N Axial Chirality.

A catalytic atroposelective cycloaddition reaction between thioureas and ynals is developed. This reaction features the first NHC-catalyzed addition of thioureas to acetylenic acylazolium intermediates to eventually set up C-N axial chirality with excellent optical purities. The obtained axially chiral thiazine derivative products bear multiple functional groups and are feasible for further transformations.

Carbene-Catalyzed Enantioselective Aromatic N-Nucleophilic Addition of Heteroarenes to Ketones.

The aromatic nitrogen atoms of heteroarylaldehydes are activated by carbene catalysts to react with ketone electrophiles. Multi-functionalized cyclic N,O-acetal products are afforded in good to excellent yields and optical purities. Our reaction involves the formation of an unprecedented aza-fulvene-type acylazolium intermediate. A broad range of N-heteroaromatic aldehydes and electron-deficient ketone substrates works effectively in this transformation. Several of the chiral N,O-acetal products afforded through this protocol exhibit excellent antibacterial activities against Ralstonia solanacearum (Rs) and are valuable in the development of novel agrichemicals for plant protection.

Photocontrollable Wrinkle Morphology Evolution on Azo-Based Multilayers for Hierarchical Surface Micropatterns Fabrication.

Inspired by nature, comprehensive understanding and ingenious utilization of the self-organized wrinkling behaviors of the sandwiched multilayer bonded on substrates are important for engineering and/or functional laminated devices design. Herein, we report a facile and effective strategy to regulate the wrinkles morphology evolution and the resultant hierarchical surface micropatterns on azobenzene-based laminated multilayers by visible-light irradiation. Revealed by systematic experiments, the photocontrolled dynamic wrinkle evolutions are triggered by the reversible photoisomerization of azobenzene in the top azopolymer film and are strongly dependent on the intermediate photoinert layers (e.g., polystyrene and oxygen plasma-induced SiO x layer) with the wrinkle-reinforcing effect or the stress relaxation acceleration effect. Interestingly, large-area well-defined hierarchical surface wrinkle patterns could be fabricated on the multilayers upon selective exposure. In the unexposed region, the wrinkles evolved into highly oriented patterns, whereas in the exposed region, they were fully erased or evolved into smaller-wavelength wrinkles. This study not only sheds light on the morphological evolution of the wrinkling laminated composites in engineering and nature but also paves a new avenue to conveniently and controllably realize the hierarchical stimulus-responsive surface patterns.

Design, Synthesis, and Biological Activity of Novel Myricetin Derivatives Containing Amide, Thioether, and 1,3,4-Thiadiazole Moieties.

A series of myricetin derivatives containing amide, thioether, and 1,3,4-thiadiazole moieties were designed and synthesized, and their antiviral and antibacterial activities were assessed. The bioassays showed that all the title compounds exhibited potent in vitro antibacterial activities against Xanthomonas citri (Xac), Ralstonia solanacearum (Rs), and Xanthomonas oryzae pv. Oryzae (Xoo). In particular, the compounds 5a, 5f, 5g, 5h, 5i, and 5l, with EC50 values of 11.5⁻27.3 µg/mL, showed potent antibacterial activity against Xac that was better than the commercial bactericides Bismerthiazol (34.7 µg/mL) and Thiodiazole copper (41.1% µg/mL). Moreover, the in vivo antiviral activities against tobacco mosaic virus (TMV) of the target compounds were also tested. Among these compounds, the curative, protection, and inactivation activities of 5g were 49.9, 52.9, and 73.3%, respectively, which were better than that of the commercial antiviral Ribavirin (40.6, 51.1, and 71.1%, respectively). This study demonstrates that myricetin derivatives bearing amide, thioether, and 1,3,4-thiadiazole moieties can serve as potential alternative templates for the development of novel, highly efficient inhibitors against plant pathogenic bacteria and viruses.

The influence of polymer architectures on the dewetting behavior of thin polymer films: from linear chains to ring chains.

The dewetting behavior of ring polystyrene (RPS) film and linear polystyrene (LPS) film on silanized Si substrates with different grafting densities and PDMS substrate was investigated. Results showed that polymer architectures greatly influenced the dewetting behavior of the thin polymer film. On the silanized Si substrate with 69% grafting density, RPS chains exhibited stronger adsorption compared with LPS chains, and as a result the wetting layer formed more easily. For LPS films, with a decreased annealing temperature, the stability of the polymer film changed from non-slip dewetting via apparent slip dewetting to apparently stable. However, for RPS films, the polymer film stability switched from apparent slip dewetting to apparently stable. On the silanized Si substrate with 94% grafting density, the chain adsorption became weaker and the dewetting processes were faster than that on the substrate with 69% grafting density at the same experimental temperature for both the LPS and RPS films. Moreover, on the PDMS substrate, LPS films always showed non-slip dewetting, while the dewetting kinetics of RPS films switched from non-slip dewetting to slip dewetting behaviour. Forming the wetting layer strongly influenced the stability and dewetting behavior of the thin polymer films.

Fluorescence turn-on detection of alkaline phosphatase activity based on controlled release of PEI-capped Cu nanoclusters from MnO2 nanosheets.

A fluorescence turn-on assay for alkaline phosphatase (ALP) activity is developed through the controlled release of polyethyleneimine-capped copper nanoclusters (PEI-capped CuNCs) from the MnO2 nanosheets. In an aqueous solution, the positively charged PEI-capped CuNCs could be adsorbed onto the surface of the negatively charged MnO2 nanosheets. Such adsorption through favorable electrostatic interactions could efficiently quench the nanocluster fluorescence emission via resonance energy transfer from the PEI-capped CuNCs to the MnO2 nanosheets. 2-Phospho-L-ascorbic acid (AAP) could be hydrolyzed to L-ascorbic acid (AA) in the presence of ALP. AA could reduce MnO2 into Mn2+ and trigger the disintegration of the MnO2 nanosheets. As a result, the CuNCs were released and the quenched fluorescence was recovered efficiently. The detection strategy is simple, inexpensive, sensitive, selective, with low toxicity, and has better biocompatibility. The newly fabricated biosensor for ALP activity will potentially make it a robust candidate for numerous biological and biomedical applications.

Patterning Surfaces on Azo-Based Multilayer Films via Surface Wrinkling Combined with Visible Light Irradiation.

Here, a simple combined strategy of surface wrinkling with visible light irradiation to fabricate well tunable hierarchical surface patterns on azo-containing multilayer films is reported. The key to tailor surface patterns is to introduce a photosensitive poly(disperse orange 3) intermediate layer into the film/substrate wrinkling system, in which the modulus decrease is induced by the reversible photoisomerization. The existence of a photoinert top layer prevents the photoisomerization-induced stress release in the intermediate layer to some extent. Consequently, the as-formed wrinkling patterns can be modulated over a large area by light irradiation. Interestingly, in the case of selective exposure, the wrinkle wavelength in the exposed region decreases, while the wrinkles in the unexposed region are evolved into highly oriented wrinkles with the orientation perpendicular to the exposed/unexposed boundary. Compared with traditional single layer-based film/substrate systems, the multilayer system consisting of the photosensitive intermediate layer offers unprecedented advantages in the patterning controllability/universality. As demonstrated here, this simple and versatile strategy can be conveniently extended to functional multilayer systems for the creation of prescribed hierarchical surface patterns with optically tailored microstructures.

Tuning and Erasing Surface Wrinkles by Reversible Visible-Light-Induced Photoisomerization.

Periodic wrinkling across different scales has received considerable attention because it not only represents structure failure but also finds wide applications. How to prevent wrinkling or create desired wrinkling patterns is non-trivial because the dynamic evolution of wrinkles is a highly nonlinear problem. Herein, we report a simple yet powerful method to dynamically tune and/or erase wrinkling patterns with visible light. The light-induced photoisomerization of azobenzene units in azopolymer films leads to stress release and consequently to the erasure of the wrinkles. The wrinkles in unexposed regions are also affected and oriented perpendicular to the exposed boundary during the stress reorganization. Theoretical models were developed to understand the dynamics of the reversible photoisomerization-induced wrinkle evolution. This method can be applied for designing functional materials/devices, for example, for the reversible optical writing/erasure of information as demonstrated here.

Melting processes of oligomeric α and ß isotactic polypropylene crystals at ultrafast heating rates.

The melting behaviors of α (stable) and ß (metastable) isotactic polypropylene (iPP) crystals at ultrafast heating rates are simulated with atomistic molecular dynamics method. Quantitative information about the melting processes of α- and ß-iPP crystals at atomistic level is achieved. The result shows that the melting process starts from the interfaces of lamellar crystal through random dislocation of iPP chains along the perpendicular direction of lamellar crystal structure. In the melting process, the lamellar crystal gradually expands but the corresponding thickness decreases. The analysis shows that the system expansion lags behind the crystallinity decreasing and the lagging extents for α- and ß-iPP are significantly different. The apparent melting points of α- and ß-iPP crystals rise with the increase of the heating rate and lamellar crystal thickness. The apparent melting point of α-iPP crystal is always higher than that of ß-iPP at differently heating rates. Applying the Gibbs-Thomson rule and the scaling property of the melting kinetics, the equilibrium melting points of perfect α- and ß-iPP crystals are finally predicted and it shows a good agreement with experimental result.

Discovery of novel piperidine-containing thymol derivatives as potent antifungal agents for crop protection.

BACKGROUND: Plant fungal diseases pose a significant threat to crop production. The extensive use of chemical pesticides has led to growing environmental safety risks and pesticide resistance of various plant pathogens. Therefore, it is an urgent task to explore novel eco-friendly fungicidal agents with high efficacy to combat fungal infection. RESULTS: In this study, we rationally designed a series of novel thymol derivatives by incorporation of the sulfonamide moiety and evaluated their biological activities against plant pathogenic fungi. The bioassay results underscored the remarkable in vitro antifungal activity of compounds 5m and 5t against Phytophthora capsici (P. capsici), with EC50 values of 8.420 and 8.414 µg/mL, respectively. Their efficacies were superior to that of widely used commercial fungicides azoxystrobin (AZO, 20.649 µg/mL) and cabendazim (CAB, 251.625 µg/mL). Furthermore, compound 5v exhibited excellent in vitro antifungal activity against Sclerotinia sclerotiorum (S. sclerotiorum), with an EC50 value of 12.829 µg/mL, significantly outperforming AZO (63.629 µg/mL). In vivo bioassays demonstrated the impactful activity of compound 5v against S. sclerotiorum, achieving over 98% curative and protective efficacies at the concentration of 200 µg/mL. Further mechanistic investigations unveiled that compound 5v induced mycelial shrinkage and collapse in S. sclerotiorum, resulting in organelle damage and the accumulation of antioxidant enzyme activity. CONCLUSION: The significant antifungal efficacy of the prepared thymol derivatives shall encourage further exploration of compound 5v as a promising candidate to develop novel fungicides for crop protection. © 2024 Society of Chemical Industry.

Controlled free edge effects in surface wrinkling via combination of external straining and selective O2 plasma exposure.

Herein the edge effect from the traction-free boundary condition is utilized to direct the spontaneous surface wrinkling. This boundary condition is attained by a simple combination of mechanical straining and selective exposure of polydimethylsiloxane (PDMS) substrate to O2 plasma (OP) through a copper grid. When the strained PDMS sheet is subjected to selective OP treatment, a patterned heterogeneous surface composed of the OP-exposed "hard" oxidized SiOx region (denoted as D1) and the OP-unexposed "soft" region (denoted as D2) is produced. The subsequent full release of the prestrain (ε(pre)) leads to the selective wrinkling in D1, rather than in D2. It is seen that even in D1, no wrinkling occurs in the vicinity of the D1 edge that is perpendicular to the wavevector. Furthermore, the average wrinkle wavelength in D1 (λ(D1)) is smaller than that of the exposed copper grid-free blank area (λ(blank)). This wavelength decrement between λ(D1) and λ(blank), which can be used to roughly estimate the edge-effect extent, increases with the applied mesh number of copper grids and exposure duration, while decreases with the increase of ε(pre). Meanwhile, there exists a decrease in the amplitude of the patterned wrinkles, when compared with that of the blank region. Additionally, hierarchical wrinkling is induced when the strain-free PDMS substrate is selectively exposed to OP, followed by uniaxial stretching and the subsequent blanket exposure. Consequently, oriented wrinkles perpendicular to the stretching direction are generated in D2. With respect to D1, no wrinkling happens or orthogonal wrinkles occur in this region depending on the applied mesh number, exposure duration, and ε(pre). In the above wrinkling process, the combinative edge effects in two perpendicular directions that are involved sequentially have been discussed.

Comparison of Ibuprofen with Ketorolac on the Control of Renal Colic Pain: A Meta-Analysis of Randomized Controlled Studies.

PURPOSE: The comparison of ibuprofen with ketorolac remains controversial for the pain control of renal colic. We therefore conduct this meta-analysis to compare the analgesic efficacy of ibuprofen with ketorolac for renal colic. METHODS: We have searched PubMed, EMbase, Web of science, EBSCO, and Cochrane library databases through December 2022 for randomized controlled trials (RCTs) assessing the analgesic efficacy of ibuprofen in comparison with ketorolac for renal colic. This meta-analysis was performed using the random-effect or fixed-effect model based on the heterogeneity. RESULTS: Four RCTs were included in the meta-analysis. In patients with renal colic pain, intravenous ibuprofen and ketorolac produced comparable pain scores at 15 min (MD = -0.46; 95% CI = -1.24 to 0.31; P = 0.24), 30 min (MD = -0.81; 95% CI = -1.75 to 0.31; P = 0.09), 60 min (MD=-0.63; 95% CI = -1.40 to 0.13; P = 0.10) and 120 min (MD = -0.74; 95% CI = -2.18 to 0.70; P = 0.31), as well as adverse events (OR = 0.95; 95% CI = 0.61 to 1.49; P = 0.83). CONCLUSION: Ibuprofen can obtain comparable analgesic efficacy to ketorolac for renal colic pain.

Comparison of clinical effectiveness of conbercept and ranibizumab for treating retinopathy of prematurity: a meta-analysis.

BACKGOUND: Conbercept and ranibizumab have been used to treat retinopathy of prematurity (ROP). However, the clinical effectiveness of conbercept and ranibizumab remains controversial. AIM: This meta-analysis aimed to compare the effectiveness of conbercept and ranibizumab for treating ROP. METHOD: We systematically searched Pubmed, Web of Science, Embase, the Cochrane Library, Ovid, Scopus, China National Knowledge Infrastructure, Wanfang Database, CQVIP, Duxiu Database, SinoMed, and X-MOL to screen relevant studies up to November 2022. Retrospective cohort studies and randomized controlled trials (RCTs) evaluating the effectiveness of conbercept and ranibizumab in treating patients with ROP were selected. The outcomes assessed were the rates of primary cure, ROP recurrence, and retreatment. Statistical analysis was performed using Stata. RESULTS: Seven studies (n = 989) were selected in the meta-analysis. There were 303 cases (594 eyes) treated with conbercept and 686 patients (1,318 eyes) treated with ranibizumab. Three studies reported the primary cure rate. Compared to ranibizumab, conbercept had a significantly higher primary cure rate (odds ratio [OR] 1.91, 95% confidence interval [CI] 1.05-3.49, P < 0.05). Five studies reported the rate of ROP recurrence, and there were no significant differences between conbercept and ranibizumab (OR 0.62, 95% CI 0.28-1.38, P > 0.05). Three studies reported the rate of retreatment, and the rates were not significantly different between conbercept and ranibizumab (OR 0.78, 95% CI 0.21-2.93, P > 0.05). CONCLUSION: Conbercept had a higher rate of primary cure in ROP patients. More RCTs are needed to compare the efficacy of conbercept and ranibizumab in treating ROP.