Search Results (15)

We study the microstructural properties and state of hydration of aqueous low-molecular-weight poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) solutions and their dependence on polymer concentration and pH by means of detailed atomistic Molecular Dynamics (MD) simulations and experiments. For infinitely dilute solutions with a degree of polymerization of N = 30 at basic pH conditions, no temperature dependence is observed on the overall shape and state of hydration of the polyelectrolyte. This is supported by the experimental component of our work according to which the hydrodynamic radius, R_h, does not change dramatically with temperature. Small, but not drastic, changes are observed for solutions with longer PDMAEMA chains (N = 50, 70, and 110). Although the MD simulations demonstrate that temperature and salt do affect the strength of hydrophobic interactions between PDMAEMA and water, apparently these effects are not strong enough to cause drastic changes to the overall shape of the polymer. MD simulations also reveal that Na⁺ salt ions strongly interact with the oxygen atoms located at the side chain of the polyelectrolyte. While no significant changes in the global shape or state of hydration of the PDMAEMA chain are found, a strong dependence is revealed for the aggregation behavior of the polymer on temperature and salt in slightly more concentrated solutions. A structural transition from a collapsed coil to a stretched conformation is also observed as we move from basic to acidic pH conditions, which is strongly correlated with the degree of chain rigidity as a function of pH. Full article

The present study used the adult earthworm Aporrectodea trapezoides as a bioindicator species to look into the possible dangers of ammonium sulfate (AS) fertilizer. Two complementary toxicity tests were conducted to determine the LC50values, growth rate inhibition, morphological alterations, and histopathological texture of worms. The lethality test included four increasing concentrations of AS fertilizer (ranging from 2500 to 7500 mg/kg of dry soil weight (d.w.)), while sub-lethal concentrations were based on 10%, 30%, 40%, and 50% of the 14-day median lethal concentration (LC50), with a control group included for both tests. The LC₍₅₀₎ values for AS fertilizer were significantly higher at 7 days (4831.13 mg/kg d.w.) than at 14 days (2698.67 mg/kg d.w.) of exposure. Notably, earthworms exhibited significant growth rate inhibition under exposure to various concentrations and time durations (14/28 exposure days). Morphological alterations such as clitellar swelling, bloody lesions, whole body coiling and constriction, body strangulation, and fragmentation were accentuated steadily, with higher concentrations. Histopathological manifestations included severe injuries to the circular and longitudinal muscular layers, vacuolation, muscle layer atrophy, degradation of the chloragogenous tissue in the intestine, collapsed digestive epithelium of the pharynx with weak reserve inclusion, and fibrosis of blood vessels. These effects were primarily influenced by increasing concentrations of fertilizer and time exposure. The study highlights the strong relationship between concentration and exposure time responses and underscores the potential of A. trapezoides earthworms as valuable biological control agents against acidic ammonium sulfate fertilizer. Importantly, this research contributes to the use of such biomarkers in evaluating soil toxicity and the biological control of environmental risk assessment associated with chemical fertilizers. Full article

In this work, the two-dimensional fluid models for two types of inductively coupled plasma, Ar/O₂ and Ar/SF₆, are numerically solved by the finite element method. Four interesting phenomena revealed by the simulations are reported: (1) comet-shaped and semi-circle-shaped structures in Ar/O₂ and Ar/SF₆ plasmas, respectively; (2) blue sheaths that surround the two structures; (3) the collapse and dispersion of semi-circle-shaped structures of certain Ar/SF₆ plasma cations and anions when they are observed separately; and (4) the rebuilding of coagulated structures by minor cations in the Ar/SF₆ plasma at the discharge center. From the simulation detail, it was found that the cooperation of free diffusion and negative chemical sources creates the coagulated structure of anions, and the self-coagulation theory is therefore built. The advective and ambipolar types of self-coagulation are put forth to explain the co-existence of blue sheath and internal neutral plasma, among which the advective type of self-coagulation extends the Bohm’s sheath theory of cations to anions, and the ambipolar type of self-coagulation originates from the idea of the ambipolar diffusion process, and it updates the recognition of people about the plasma collective interaction. During the ambipolar self-coagulation, each type of Ar/SF₆ plasma cations and anions is self-coagulated, and the coagulated plasma species are then modeled as mass-point type (or point-charge type, more precisely). When the charge amounts of two point-charge models of plasma species with the same charge type are equal, the expelling effect caused by the Coulomb’s force of them leads to the collapse or dispersal of heavily coagulated species. The simulation shows that the lighter the species is, the easier it self-coagulates and the more difficult its coagulation is broken, which implies the inertia effect of density quantity. Moreover, the collapse of cation coagulation creates the spatially dispersed charge cloud that is not shielded into the Debye’s length, which indicates the anti-collective behavior of electronegative plasmas when they are self-coagulated. The rebuilt coagulated structure of minor Ar/SF₆ plasma species at the discharge center and the weak coagulation of electrons in the periphery of the main coagulated structure that is under the coil are caused by the monopolar and spontaneous (non-advective) type of self-coagulation. The analysis predicts an intensity order of physically driven coagulation force, chemical self-coagulation force, and ambipolar self-coagulation force. The popular coagulated structure of the electronegative ICP sources is urgently needed to validate the experiment. Full article

Random walks (RWs) have been important in statistical physics and can describe the statistical properties of various processes in physical, chemical, and biological systems. In this study, we have proposed a self-interacting random walk model in a continuous three-dimensional space, where the walker and its previous visits interact according to a realistic Lennard-Jones (LJ) potential $u_{LJ}\left(r\right)=\epsilon \left[{\left(r_0/r\right)}^{12}-2{\left(r_0/r\right)}^6\right]$. It is revealed that the model shows a novel globule-to-helix transition in addition to the well-known coil-to-globule collapse in its trajectory when the temperature decreases. The dependence of the structural transitions on the equilibrium distance $r_0$ of the LJ potential and the temperature T were extensively investigated. The system showed many different structural properties, including globule–coil, helix–globule–coil, and line–coil transitions depending on the equilibrium distance $r_0$ when the temperature T increases from low to high. We also obtained a correlation form of k_BT_c = λε for the relationship between the transition temperature T_c and the well depth $\epsilon$, which is consistent with our numerical simulations. The implications of the random walk model on protein folding are also discussed. The present model provides a new way towards understanding the mechanism of helix formation in polymers like proteins. Full article

Coil-to-globule transition and dynamics of inhomogeneities in aqueous solutions of graft copolymers of NIPAM with different content of oligolactide groups were studied using spin probe continuous wave EPR spectroscopy. The technique of the suppressing of TEMPO as spin probe by spin exchange with Cu²⁺ ions was applied. This approach allowed us to detect individual EPR spectra of the probe in collapsed globules and estimate its magnetic and dynamic parameters reliably. The formation of inhomogeneities at temperatures lower than the volume phase transition temperature measured via transmission, and differential scanning calorimetry was fixed. An increase in oligolactide content in copolymers leads to the formation of looser globules, allowing for the exchange of the probe molecules between the globules and the external solution. Full article

This paper studies the effect of extreme cooling and traditional cooling on the microstructure of high-strength steel during hot rolling by adjusting the cooling process, combining the theoretical calculation and the thermal simulation experiment, and using metallographic microscope, scanning electron microscope (SEM), and electron backscattered diffraction (EBSD) analysis methods in order to solve the problem of coil collapse in the production process of high-strength steel. The research results show that compared with the traditional cooling method, the front-section fast cooling mode can rapidly cool the hot-rolled sheet to the “nose tip” temperature of the ferrite transformation of the time-temperature-phase-transition (TTT) curve, which can promote the transformation of the material to ferrite, increase the proportion of ferrite, and make the grain size of the organization finer. It helps to improve the overall mechanical properties of the material and reduce coil collapse defects. The front-section fast cooling mode achieves good results in industrial application, the proportion of coil collapse reduces from 9.363% to 0.533%, and the problem of coil collapse is significantly improved. Full article

Elastin-like polypeptides (ELPs) are soluble in water at low temperature, but, on increasing the temperature, they undergo a reversible and cooperative, coil-to-globule collapse transition. It has been shown that the addition to water of either trimethylamine N-oxide (TMAO), glycine, or betaine causes a significant decrease of T(collapse) in the case of a specific ELP. Traditional rationalizations of these phenomena do not work in the present case. We show that an alternative approach, grounded in the magnitude of the solvent-excluded volume effect and its temperature dependence (strictly linked to the translational entropy of solvent and co-solute molecules), is able to rationalize the occurrence of ELP collapse in water on raising the temperature, as well as the T(collapse) lowering caused by the addition to water of either TMAO, glycine, or betaine. Full article

Coil to globule transition in poly(N-isopropylacrylamide) aqueous solutions was studied using spin probe continuous-wave electronic paramagnetic resonance (CW EPR) spectroscopy with an amphiphilic TEMPO radical as a guest molecule. Using Cu(II) ions as the “quencher” for fast-moving radicals in the liquid phase allowed obtaining the individual spectra of TEMPO radicals in polymer globule and observing inhomogeneities in solutions before globule collapsing. EPR spectra simulations confirm the formation of molten globules at the first step with further collapsing and water molecules coming out of the globule, making it denser. Full article

Fast kinetic experiments with dramatically improved time resolution have contributed significantly to understanding the fundamental processes in protein folding pathways involving the formation of a-helices and b-hairpin, contact formation, and overall collapse of the peptide chain. Interpretation of experimental results through application of a simple statistical mechanical model was key to this understanding. Atomistic description of all events observed in the experimental findings was challenging. Recent advancements in theory, more sophisticated algorithms, and a true long-term trajectory made way for an atomically detailed description of kinetics, examining folding pathways, validating experimental results, and reporting new findings for a wide range of molecular processes in biophysical chemistry. This review describes how optimum dimensionality reduction theory can construct a simplified coarse-grained model with low dimensionality involving a kinetic matrix that captures novel insights into folding pathways. A set of metastable states derived from molecular dynamics analysis generate an optimally reduced dimensionality rate matrix following transition pathway analysis. Analysis of the actual long-term simulation trajectory extracts a relaxation time directly comparable to the experimental results and confirms the validity of the combined approach. The application of the theory is discussed and illustrated using several examples of helix <==> coil transition pathways. This paper focuses primarily on a combined approach of time-resolved experiments and long-term molecular dynamics simulation from our ongoing work. Full article

With the recent proliferation of mobile and wearable devices, wireless power transfer (WPT) has gained attention as an up-and-coming technology to charge these devices. In particular, WPT via magnetic resonance coupling has attracted considerable interest for day-to-day applications since it is harmless to the human body and has relatively long transmission distance. However, it was difficult to be installed into environment (e.g., utensils and furniture) and flexible objects in the living space since the use of flexible coils leads to the decrease in transmission efficiency due to the collapse of the resonance caused by coil deformation. Therefore, this study proposes an automatic resonance compensation system that automatically compensates the inductance variation caused by coil deformation using a circuit that can electronically control the equivalent capacitance (a capacity control circuit), and thereby maintains the resonant state. An experiment was conducted to verify whether the efficiency was maintained when the coil deformed. The results indicated a transmission efficiency nearly as high as that of the ideal resonant state as well as a highly responsive control, and therefore, the proposed system has a good potential for use in real-world applications. Full article

We employ the recently introduced generalized microcanonical inflection point method for the statistical analysis of phase transitions in flexible and semiflexible polymers and study the impact of the bending stiffness upon the character and order of transitions between random-coil, globules, and pseudocrystalline conformations. The high-accuracy estimates of the microcanonical entropy and its derivatives required for this study were obtained by extensive replica-exchange Monte Carlo simulations. We observe that the transition behavior into the compact phases changes qualitatively with increasing bending stiffness. Whereas the $\Theta$ collapse transition is less affected, the first-order liquid-solid transition characteristic for flexible polymers ceases to exist once bending effects dominate over attractive monomer-monomer interactions. Full article

Endovascular Embolization (EVE) of aneurysms is a very effective and efficient treatment modality. Nevertheless, a few complications have been reported after EVE of aneurysms. Our study therefore evaluated the safety and efficacy of Low-profile Visible Intraluminal Support (LVIS) stentassisted EVE for intracranial Dissecting Aneurysms (DAs). We conducted a retrospective study to identify patients with DAs who were treated with LVIS stent from July 2015 to September 2018. The DAs were categoried into ruptured and unruptured. The arteries harbouring the aneurysm were identified in all cases. LVIS device stent assisted coil EVE treatment modality was utilized to treat all the patients. Surgical safety, immediate surgery outcome, recurrence rate and imaging follow-up results of all patients were analysed. The Glasgow Outcome Scale (GOS) score of all patients where assessed during discharge. Cerebral angiography of all patients were reevaluated on scheduled visits from three months up to one year after their operations. A total of Six DA patients were identified during our analysis. Four of the cases were ruptured DAs while two cases were unruptured. The DAs originated from the Internal Carotid Artery (ICA) in two cases, while in the remaining four cases, the DAs originated from vertebral artery (VA). Stents and coils were successfully implanted in all six patients. The DAs were embolized satisfactorily and the parent arteries were patent immediately after the operations. We obsereved 5 points GOS score in four cases and 4 points in two cases. No aneurysmal recurrece, no stent collapse or displacement was obsereved in all cases during follow-ups. Our study suggests that, LVIS stent-assisted EVE is simple, safe and effective in the treatment of DAs. Full article

Among a variety of inorganic-based nanomaterials, mesoporous silica nanoparticles (MSNs) have several attractive features for application as a delivery system, due to their high surface areas, large pore volumes, uniform and tunable pore sizes, high mechanical stability, and a great diversity of surface functionalization options. We developed novel hybrid MSNs composed of a mesoporous silica nanostructure core and a pH-responsive polymer shell. The polymer shell was prepared by RAFT polymerization of 2-(diisopropylamino)ethyl methacrylate (pKa ~6.5), using a hybrid grafting approach. The hybrid nanoparticles have diameters of ca. 100 nm at pH < 6.5 and ca. 60 nm at pH > 6.5. An excellent control of cargo release is achieved by the combined effect of electrostatic interaction of the cargo with the charged silica and the extended cationic polymer chains at low pH, and the reduction of electrostatic attraction with a simultaneous collapse of the polymer chains to a globular conformation at higher pH. The system presents a very low (almost null) release rate at acidic pH values and a large release rate at basic pH, resulting from the squeezing-out effect of the coil-to-globule transition in the polymer shell. Full article

We study collapsed homo-polymeric molecules under linear shear flow conditions using hydrodynamic Brownian dynamics simulations. Tensile force profiles and the shear-rate-dependent globular-coil transition for grafted and non-grafted chains are investigated to shine light on the different unfolding mechanisms. The scaling of the critical shear rate, at which the globular-coil transition takes place, with the monomer number is inverse for the grafted and non-grafted scenarios. This implicates that for the grafted scenario, larger chains have a decreased critical shear rate, while for the non-grafted scenario higher shear rates are needed in order to unfold larger chains. Protrusions govern the unfolding transition of non-grafted polymers, while for grafted polymers, the maximal tension appears at the grafted end. Full article

Nonionic-zwitterionic diblock copolymers are designed to feature a coil-to-globule collapse transition with an upper critical solution temperature (UCST) in aqueous media, including physiological saline solution. The block copolymers that combine presumably highly biocompatible blocks are synthesized by chain extension of a poly(ethylene glycol) (PEG) macroinitiator via atom transfer radical polymerization (ATRP) of sulfobetaine and sulfabetaine methacrylates. Their thermoresponsive behavior is studied by variable temperature turbidimetry and ¹H NMR spectroscopy. While the polymers with polysulfobetaine blocks exhibit phase transitions in the physiologically interesting window of 30–50 °C only in pure aqueous solution, the polymers bearing polysulfabetaine blocks enabled phase transitions only in physiological saline solution. By copolymerizing a pair of structurally closely related sulfo- and sulfabetaine monomers, thermoresponsive behavior can be implemented in aqueous solutions of both low and high salinity. Surprisingly, the presence of the PEG blocks can affect the UCST-transitions of the polyzwitterions notably. In specific cases, this results in “schizophrenic” thermoresponsive behavior displaying simultaneously an UCST and an LCST (lower critical solution temperature) transition. Exploratory experiments on the UCST-transition triggered the encapsulation and release of various solvatochromic fluorescent dyes as model “cargos” failed, apparently due to the poor affinity even of charged organic compounds to the collapsed state of the polyzwitterions. Full article