The temperature dependence of the Hildebrand solubility parameters of selected hydrocarbon polymers and hydrocarbon solvents: a molecular dynamics investigation.

CONTEXT: To determine the miscibility of liquids at high temperatures using the concept of Hildebrand solubility parameter δ , the current practice is to examine the difference in δ between two liquids at room temperature, assuming that δ is not sensitive to temperature. However, such an assumption may not be valid for certain polymer blends and solutions. Therefore, a knowledge of the δ values of the liquids of interest at high temperatures is desirable. The determination of δ at high temperatures, especially for high-molecular-weight polymers, is impossible, as polymers have vapor pressures of zero. To this end, molecular dynamics (MD) simulations provide a practical means for determining δ over a wide range of temperatures. In this work, we study the temperature dependence of δ of five hydrocarbon polymers: polyethylene (PE), isotactic and atactic polypropylene (i-PP and a-PP), polyisobutylene (PIB), and polyisoprene (PI) in five hydrocarbon solvents: n-pentane, n-hexane, n-dodecane, isobutene, and cyclohexane. The polymers are modeled as monodisperse chains with 100 repeat units. The average δ values of PE, i-PP, a-PP, PIB, and PI at 300 K are determined as 18.6, 14.9, 14.6, 14.3, and 16.4 MPa1/2, respectively, in a good agreement with experimental data. The δ values of these polymers at various temperatures are also determined. The temperature dependence of δ is fitted to two linear equations, one above and the other below the polymer's glass transition temperature Tg. The δ values are more sensitive to temperature at T ≥ Tg. The Tg values of the polymers, determined based upon their specific volumes and δ values agree with the experiment qualitatively. The determination of the temperature dependence of δ has a great potential for industrial applications, such as determining miscibility, developing polymeric organogelators as flocculants and oil spill treating agents, and identifying potential solvents and ideal processing temperatures. METHODS: The MD simulations are performed using the GROMACS 2022.3 package with optimized potential for liquid simulations-all atom (OPLS-AA) force field parameters. All polymers are built as extended chains using CHARMM-GUI Polymer Builder.

Optimal CT perfusion thresholds for core and penumbra in acute posterior circulation infarction.

Background: At least 20% of strokes involve the posterior circulation (PC). Compared to the anterior circulation, posterior circulation infarction (POCI) are frequently misdiagnosed. CT perfusion (CTP) has advanced stroke care by improving diagnostic accuracy and expanding eligibility for acute therapies. Clinical decisions are predicated upon precise estimates of the ischaemic penumbra and infarct core. Current thresholds for defining core and penumbra are based upon studies of anterior circulation stroke. We aimed to define the optimal CTP thresholds for core and penumbra in POCI. Methods: Data were analyzed from 331-patients diagnosed with acute POCI enrolled in the International-stroke-perfusion-registry (INSPIRE). Thirty-nine patients with baseline multimodal-CT with occlusion of a large PC-artery and follow up diffusion weighted MRI at 24-48 h were included. Patients were divided into two-groups based on artery-recanalization on follow-up imaging. Patients with no or complete recanalisation were used for penumbral and infarct-core analysis, respectively. A Receiver operating curve (ROC) analysis was used for voxel-based analysis. Optimality was defined as the CTP parameter and threshold which maximized the area-under-the-curve. Linear regression was used for volume based analysis determining the CTP threshold which resulted in the smallest mean volume difference between the acute perfusion lesion and follow up MRI. Subanalysis of PC-regions was performed. Results: Mean transit time (MTT) and delay time (DT) were the best CTP parameters to characterize ischaemic penumbra (AUC = 0.73). Optimal thresholds for penumbra were a DT >1 s and MTT>145%. Delay time (DT) best estimated the infarct core (AUC = 0.74). The optimal core threshold was a DT >1.5 s. The voxel-based analyses indicated CTP was most accurate in the calcarine (Penumbra-AUC = 0.75, Core-AUC = 0.79) and cerebellar regions (Penumbra-AUC = 0.65, Core-AUC = 0.79). For the volume-based analyses, MTT >160% demonstrated best correlation and smallest mean-volume difference between the penumbral estimate and follow-up MRI (R 2 = 0.71). MTT >170% resulted in the smallest mean-volume difference between the core estimate and follow-up MRI, but with poor correlation (R 2 = 0.11). Conclusion: CTP has promising diagnostic utility in POCI. Accuracy of CTP varies by brain region. Optimal thresholds to define penumbra were DT >1 s and MTT >145%. The optimal threshold for core was a DT >1.5 s. However, CTP core volume estimates should be interpreted with caution.

Origins of covalent linkages within the lignin-carbohydrate network of biomass.

Covalent linkages between lignin and the surrounding carbohydrate network, often referred to as lignin-carbohydrate complexes (LCCs), have been proposed to affect the organization of the biomass microstructure and directly correlate with the recalcitrant nature of biomass. However, the existence and frequency of these LCC linkages remain controversial and largely unknown, primarily due to the harsh experimental techniques available to characterize them. During the predominant lignin polymerization pathway a reactive intermediate is formed. Though this intermediate can covalently bind to the surrounding cellulose/hemicellulose matrix, it has been traditionally assumed to react exclusively with water, leading to purely physical interactions between lignin and cellulose/hemicellulose in the cell wall. This work, for the first time, provides direct evidence of the molecular mechanism of the formation of benzyl ether and benzyl ester LCC linkages via the speculated lignin polymerization pathway. The formation of these LCC linkages showed thermodynamic favorability, while remaining kinetically facile, compared to the previously assumed mechanism of the lignin intermediate reacting with water. The present work suggests that the surrounding carbohydrate matrix could play a role in the organization of lignin deposition and these covalent linkages could be a key factor in biomass recalcitrance.

The role of endoscopic endonasal surgery in the management of prolactinomas based on their invasiveness into the cavernous sinus.

PURPOSE: To review our institutional experience with the surgical management of prolactinomas through the endoscopic endonasal approach with specific focus on cavernous sinus invasion. METHODS: Clinical and radiographic data were collected retrospectively from the electronic medical record of 78 consecutive patients with prolactinomas undergoing endoscopic endonasal resection from 2002 to 2019. Immediate and late post-operative remission were defined as prolactin < 20 ng/mL within 14 days and 1-year of surgery without adjuvant therapy, respectively. Cavernous sinus invasion was quantified by Knosp score. RESULTS: A total of 78 patients with prolactinoma, 59% being male, underwent surgical resection with a mean age of 37 ± 13 years. Indications for surgery were medication resistance in 38 patients (48.7%), medication intolerance in 11 (14.1%), and patient preference in 29 (37.2%). Patients with Knosp 0-2 achieved higher immediate remission rates (83.8%) compared to patients with Knosp 3 (58.8%) and Knosp 4 (41.7%) patients (p = 0.003). Long-term remission rates were 48.7% and increased to 71.8% when combined with adjuvant treatments. Knosp 4 prolactinomas had significantly higher tumor volumes, higher preoperative prolactin levels, higher recurrence rates, higher rates of adjuvant therapy utilization, and were more likely to have failed dopamine agonist therapy compared to other tumor grades (p < 0.05). We encountered 18 complications in our series, and no cerebrospinal fluid leaks. CONCLUSION: The endoscopic endonasal approach is a safe and effective modality that can be employed in properly selected patients with invasive prolactinomas. It is associated with improved control and remission rates despite cavernous sinus invasion, though at a lower rate than without invasion.

Meta-analysis on the treatment options and outcomes of carotid blood blister aneurysms.

OBJECTIVE: Carotid blister aneurysms remain a formidable surgical challenge with varied surgical options. There have been significant advancements in the endovascular management of these aneurysms with the introduction of flow diverters. The comparative risk profiles for different endovascular options compared to surgical management of these lesions is not completely understood. METHODS: The study is a comprehensive systematic review and meta-analysis on the treatment of carotid blood blister aneurysms. Pubmed searches were used to identify relevant articles and patient level data was extracted. Two and three group analyses were conducted comparing surgical and endovascular strategies and surgical, stent coil and flow diversion techniques respectively. Patient outcomes were graded on the modified Rankin Scale with a score of 2 or less defined as favorable. RESULTS: In total, 83 studies (41 and 42 studies on surgical and endovascular interventions, respectively) with 1119 patients met our inclusion criteria. A statistically significant difference (at the 5% level of significance) in the effect among three different interventions was not found (Q = 3.41, p = 0.1815) under the random-effect model. Our results did show summary proportions of favorable outcomes were higher in the stent coil (0.87, 95% CI: 0.79 - 0.94) and flow diversion (0.87, 95% CI: 0.75 - 0.96) than that of surgery (0.76, 95% CI: 0.71 - 0.83). CONCLUSIONS: Our results suggest a trend towards improved patient outcomes with endovascular techniques compared to surgical strategies but statistical significance was not achieved. We also found that endovascular techniques compare favorably. Increasing retreatments were found to negatively affect patient outcomes.

COVID-19 vaccination in haematology patients: an Australian and New Zealand consensus position statement.

Australia and New Zealand have achieved excellent community control of COVID-19 infection. In light of the imminent COVID-19 vaccination roll out in both countries, representatives from the Haematology Society of Australia and New Zealand and infectious diseases specialists have collaborated on this consensus position statement regarding COVID-19 vaccination in patients with haematological disorders. It is our recommendation that patients with haematological malignancies, and some benign haematological disorders, should have expedited access to high-efficacy COVID-19 vaccines, given that these patients are at high risk of morbidity and mortality from COVID-19 infection. Vaccination should not replace other public health measures in these patients, given that the effectiveness of COVID-19 vaccination, specifically in patients with haematological malignancies, is not known. Given the limited available data, prospective collection of safety and efficacy data of COVID-19 vaccination in this patient group is a priority.

Case studies of clinical hemodialysis membranes: influences of membrane morphology and biocompatibility on uremic blood-membrane interactions and inflammatory biomarkers.

End stage renal disease (ESRD) patients depend on hemodialysis (HD) as a life-sustaining treatment, but HD membrane properties play a critical role in blood activation during HD and can lead to severe patient outcomes. This study reports on a series of investigations on the common clinical HD membranes available in Canadian hospitals to explore the key reasons behind their susceptibility to blood activation and unstable cytokine. Clinical HD membranes composed of cellulose triacetate (CTA) and polyvinylpyrrolidone: polyarylethersulfone (PAES: PVP) were thoroughly characterized in terms of morphology and chemical composition. Membrane-surface interactions with uremic blood samples after HD treatment were probed using Fourier Transform Infra-Red (FTIR) and Raman spectroscopic techniques in order to understand changes in chemistry on membrane fibers. In addition, as part of this innovative study, we utilized Molecular Modeling Docking to examine the interactions of human blood proteins and membrane models to gain an in-depth understanding of functional group types responsible for perceived interactions. In-vitro adsorption of fibrinogen on different clinical HD membranes was compared at similar clinical operating conditions. Samples were collected from dialysis patients to ascertain the extent of inflammatory biomarkers released, before, during (30 and 90 min) and after dialysis (4 h). Collected blood samples were analyzed using Luminex assays for the inflammatory biomarkers of Serpin/Antithrombin-III, Properdin, C5a, 1L-1α, 1L-1ß, TNF-α, IL6, and vWF. We have likewise incubated uremic blood in vitro with the two membrane materials to determine the impact that membrane materials pose in favor of activation away from the hydrodynamics influences. The results of our morphological, chemical, spectroscopic, and in vitro incubation analyses indicate that CTA membranes have a smoother surface and higher biocompatibility than PAES: PVP membranes, however, it has smaller pore size distribution, which results in poor clearance of a broad spectrum of uremic toxins. However, the rougher surface and greater hydrophilicity of PAES: PVP membranes increases red blood cell rupture at the membrane surface, which promotes protein adsorption and biochemical cascade reactions. Molecular docking studies indicate sulfone functional groups play an important role in the adsorption of proteins and receptors. PAES: PVP membranes result in slower but greater adsorption of fibrinogen, but are more likely to experience reversible and irreversible fouling as well as backfiltration. Our major finding is that a single dialysis session, even with a more biocompatible membrane such as CTA, increases the levels of complement and inflammation factors, but to a milder extent than dialysis with a PAES membrane.

Biocompatibility enhancement of hemodialysis membranes using a novel zwitterionic copolymer: Experimental, in situ synchrotron imaging, molecular docking, and clinical inflammatory biomarkers investigations.

The aim of the current research study is to conduct a comparative assessment of biocompatibility of zwitterionic-coated polyether sulfone (PES) clinical hemodialysis (HD) membranes using both theoretical and experimental methods. Fibrinogen plays a key role in assessing membrane hemocompatibility since its membrane-surface adsorption triggers several biological reactions, complete thrombosis and embolism. As a result, adsorption of fibrinogen on the untreated PES surface and novel synthesized PES coated with poly 3-((3-(3-carboxy-2,5-dimethyltridecanamido) propyl) dimethylammonio) propane-1-sulfonate as a zwitterion (ZW) was compared. Specifically, the comparison was conducted using in situ synchrotron based micro computed tomography imaging (SR-µCT), Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy, and Scanning Electron Microscopy (SEM). The in situ SR-µCT showed that fibrinogen adsorption and membrane fouling were intense on PES membrane surface. However, there was insignificant fouling in the middle layer of zwitterion coated PES membrane (PES-ZW). Moderate shifting of peaks was observed in ATR-FTIR spectra of the adsorbed fibrinogen when compared to the bulk protein spectra, which may be due to the conformational transformations occurring during the adsorption process. The spectral features indicate that PES-ZW surface has a lower adsorption affinity for fibrinogen than that for the PES surface. In this innovative study, the use of molecular modeling docking to evaluate the interaction of fibrinogen active pose with PES-ZW and PES models with the aim of gaining an in depth understanding of the functional group responsible for the interactions was explored. The PES and PES/zwitterion hemodialysis membrane models indicated minimum binding energies with fibrinogen by -6.00 and -6.70 kcal/mol, respectively. Docking studies thus suggest that the membrane's sulfone functional groups play an essential key role during the fibrinogen interaction and adsorption. The HD patients' uremic samples were incubated in vitro with PES and PES-ZW membranes for the inflammatory biomarkers released of Serpin/Antithrombin-III, Properdin, C5a, IL-1α, IL-1ß, TNF-α, and IL6. This study's results emphasize that even though a neutral charge of synthesized novel zwitterion PES, which enhances biocompatibility, the sulfone group still significantly affected the interactions with fibrinogen.

Prediction of crossover in the molecular weight dependence of polyethylene viscosity using a polymer free volume theory.

Based upon the Doolittle concept that viscosity and free volume are inversely related, we used the Boltzmann equation along with a polymer free volume theory to calculate the viscosity (η) of polyethylene with three different molecular structures - linear, ring and four-arm symmetrical star - over a molecular weight (M) range of 420-14 000 g mol-1. Free volume parameters were estimated using the Polymer Reference Interaction Site Model (PRISM) and generic van der Waals (GvdW) equation. The polymer free volume theory was able to describe the crossovers in the molecular weight dependence of the viscosity of the aforementioned molecular structures. In particular, the crossover for the linear structure was predicted at about 3000 g mole-1 with η ∼ M1.5 in the unentangled regime and η ∼ M3.3 in the entangled regime that agree reasonably well with experiment. The predictions for the other two structures also agree with the available simulation data. We also demonstrated that the accuracy of the viscosity prediction was sensitive to the difference between two free volume parameters (i.e., (φ+ - F)). Here, F signifies the probability of a bead finding free volume greater than the critical free volume while the fraction of such beads (φ+) can be used to calculate the activation energy. The theory also reproduced the temperature dependence of η for the linear structure at different M, giving apparent activation energy (Eappa) values in the range of 5.30-7.70 kcal mole-1 that are in good agreement with experimental values of 5.50-6.75 kcal mole-1. This work demonstrates for the first time that viscosity of polymer melts can be determined from the polymer free volume theory.

Embolization of carotid-cavernous fistulas: A technical note on simultaneous balloon protection of the internal carotid artery.

A carotid-cavernous fistula (CCF) is an abnormal connection between the carotid circulation and the cavernous sinus. Treatment of CCFs often consists of obliteration of the fistula by a transarterial or transvenous endovascular approach using embolic agents. However, fistula embolization is often halted due to the potential embolic complications that may arise from the retrograde flow of the embolic agents into the arterial circulation, which often leads to the development of fistula recurrence. Moreover, retreatment of a CCF recurrence is challenging and more complex approaches may be required. In this technical note, we describe our experience with CCF embolization in 25 patients treated at a single center. We utilized a transvenous approach for CCF embolization with simultaneous balloon occlusion of the internal carotid artery during the infusion of the embolic material into the fistula. In our series, this simultaneous protection of the internal carotid artery showed to be a safe technique to prevent embolic complications and to achieve successful obliteration of the fistula. On follow-up, 2 cases presented a recurrence, one due to technical difficulties and the other related to an undetected vascular injury. In conclusion, this technique provides a safe approach in the treatment of CCFs by decreasing the risk of embolic complications and increasing the effectiveness of the embolic agents in accomplishing the obliteration of the CCF.

A theory for the temperature effect on the chain length dependence of the diffusivity of oligomers.

The effect of temperature on the chain length (N) dependence of the diffusivity of oligomers (with N = 10-60 carbon atoms) was theoretically studied using the free volume theory of Wong and Choi [Soft Matter, 2019, 15, 9300-9309] along with the experimental data of von Meerwall et al. [J. Chem. Phys., 1998, 108, 4299-4304]. Experimental data showed that Dcm∼Nv and that becomes less negative as temperature increases but is always stronger than -1 as obtained in the Rouse model. The theory successfully predicts the exponent v as a function of temperature.

Management of Venous Sinus-Related Epidural Hematomas.

BACKGROUND: Epidural hematomas (EDHs) involving the venous sinuses are uncommon and carry the risk of hemorrhage or venous infarction. We report the largest case series for superior sagittal sinus- and transverse sinus-related EDHs including surgical and nonsurgical management. We compare our findings to the relevant literature. METHODS: A retrospective review of the EDH cases at our center was performed from 2013-2018. Patients were analyzed by surgical versus conservative management, outcomes, and complications. RESULTS: Of the 268 EDH patients identified, 32 involved the venous sinuses (23 supratentorial and 9 infratentorial). Ten of the patients had surgery, and 22 were managed conservatively. No surgical complications occurred, and all had a Glasgow Outcome Scale score of 5 at follow-up. All of the nonsurgical patients had a Glasgow Outcome Scale score of 4 or 5 at follow-up except for 1 patient with prior disability. The literature search resulted in 39 infratentorial and 47 supratentorial EDHs involving venous sinuses. CONCLUSIONS: Surgical and nonsurgical management of EDHs involving the venous sinuses are both viable options with good outcomes. Surgical intervention is based on location, size, neurologic examination, expansion on serial imaging, and vascular imaging findings. Surgery has the potential for significant complications, but all surgical patients in our series had good outcomes at follow-up. Similarly, nonsurgically managed patients had good outcomes and our overall series demonstrates better outcomes with fewer complications than other similar series in the literature.

On the diffusivity of ring polymers.

A free volume theory of linear polyethylene (PE) melts [Soft Matter, 2019, 15, 9300-9309] was used to describe the crossover in the size dependence of the center-of-mass diffusion coefficients of ring PE melts from Dcm ∼ N-1.03±0.15 to Dcm ∼ N-1.88±0.14 at Nc ≈ 100. Parameters in the theory were determined theoretically by either the polymer reference interaction site model (PRISM) theory or molecular dynamics (MD) simulation data. The former method is computationally less expensive, whereas the latter gives more accurate results in calculating the temperature dependence of Dcm as different intermolecular and intramolecular potentials were explicitly included in the equation of motion. Both approaches were able to describe the dynamics below and above the crossover in the size dependence of Dcm.

Thickness Dependence of the Diffusivity and Solubility of Cyclohexane in Nanoscale Bitumen Films.

Diffusivity and solubility of cyclohexane in nanoscale bitumen films coated on hydrophilic substrates at ambient conditions were studied using a gravimetric analyzer. Three substrates were used, and they are as follows: sample A, monodisperse spherical glass beads; sample B, polydisperse spherical glass beads mixed with polydisperse irregular-shape kaolin clay particles; and sample C, irregular-shape residual solids generated from a solvent extraction process of an oil sand ore. All of the above samples had a mean diameter of 150 µm. Diffusion coefficients were determined based upon the initial rates of cyclohexane absorption when bitumen-coated samples at various amounts (thicknesses) were exposed to a carrier gas with cyclohexane vapors at two levels of relative saturations (RSs), and they were found to be in the range of 10-18 to 10-16 m2/s. A double-first-order kinetics model fits well to the absorption data, suggesting that there exists a concentration gradient of polar (or nonpolar) bitumen molecules in the nanoscale films. This is because the hydrophilic substrates attract the relatively polar fraction of bitumen molecules to the region close to the substrates and the nonpolar fraction resides in the region near the free surface. As a result, the measured diffusion coefficients exhibited positive thickness dependence when the thickness of the bitumen films was at the nanoscale. The molecules near the substrates tended to diffuse slower than those in the free surface region. However, diffusivity was insensitive to the cyclohexane RS. On the other hand, the measured solubility of cyclohexane in the nanoscale bitumen films exhibited no thickness dependence but strong cyclohexane RS dependence. These results suggest that solubility is not affected by the inhomogeneous distribution of bitumen molecules in the nanoscale films and that it follows more or less Henry's law.

A free volume theory on the chain length dependence of the diffusivity of linear polymers.

A free volume theory was developed to account for the crossover of the chain length dependence of the center-of-mass self-diffusion coefficient of linear polymers from unentangled to entangled regimes. Similar to the original free volume theory of Cohen and Turnbull, this theory requires information about the free volume overlapping factor (α), critical free volume per bead (v), and mean free volume per bead (〈vf,i〉). However, one additional parameter is needed and it is the critical fraction of beads having free volume greater than or equal to αv termed as φ+. Here, α and v can be readily determined from the intermolecular and intramolecular radial distribution functions (i.e., g(r) and gintra(r)) obtained from molecular dynamics (MD) simulation and they were found to be 0.5 and 0.0257 nm3, respectively, for polyethylene melts and it is not dependent on N. 〈vf,i〉 was determined using the generic van der Waals (GvdW) equation of state and it had a value of 0.01 nm3 and the volume available to each bead can also be determined by Voronoi tessellation (VT) on the corresponding MD simulation trajectories. VT yielded exact probability of finding a certain amount of free volume and the free volume distribution was found in the form of the gamma distribution that is consistent with the positron annihilation lifetime spectroscopy observation. Finally, φ+ was calculated using the experimentally measured activation energies for diffusion per polyethylene molecule with different chain lengths and was found to be approximately 0.22 that was in line with what was found from MD simulations.

Applications of Highly Stretchable and Tough Hydrogels.

Stretchable and tough hydrogels have drawn a lot of attention recently. Due to their unique properties, they have great potential in the application in areas such as mechanical sensing, wound healing, and drug delivery. In this review, we will summarize recent developments of stretchable and tough hydrogels in these areas.

Effect of confinement on the adsorption behavior of inorganic and organic ions at aqueous-cyclohexane interfaces: a molecular dynamics study.

Molecular dynamics simulation was used to study the adsorption behavior of inorganic and organic ions at aqueous-cyclohexane interfaces, and that with such systems confined in a kaolinite nanopore. Four aqueous solutions were used, each containing one of the four solutes (NaCl, NaOH, CaCl2 and Ca(OH)2) at the concentration of 1.0 M. At the interface of each of the solutions with neat cyclohexane, there existed an ion depletion zone. The more strongly hydrated ions, such as calcium and hydroxide, were more intensely depleted from the interface as compared to sodium and chloride. Such surface exclusion led to interfacial tension increases, with greater increments for solutions containing calcium or hydroxide. Upon addition of sodium decanoate to the cyclohexane phase, they partly migrated to the aqueous-organic interface, and the remaining formed inverted micelle complexes. Also, a small fraction of the solvated cations in the aqueous phase drifted to the depletion zone to interact with the organic anions, with their affinity towards the interface still being controlled by their hydration-strength. When such systems were confined in a kaolinite nanopore, behavior of decanoate anions - which were found to be prone to strong adsorption to solid surfaces in the absence of any aqueous solution - was determined by the nature of the solvated ions in water. In these systems, the more weakly-hydrated ionic species exhibited preferential adsorption to the solid surface, while affinity of the more strongly-hydrated ones was towards remaining within the water layers or to the aqueous-organic interface. With the calcium chloride solution, almost all of the organic ions were detached from the surface and adsorbed at the aqueous-cyclohexane interface. This was caused by the release of double amount of inorganic anions by this 1 : 2 salt, the inner-sphere adsorption of majority of chloride anions to the octahedral surface, and the higher charge density of calcium cations.

Reliability of the Acutely Estimated Premorbid Modified Rankin Scale for Stroke Treatment Decision Making.

BACKGROUND: Premorbid functional status is an important factor in acute stroke treatment decision making. Determining the modified Rankin Score (mRS) accurately may be difficult due to deficits from stroke and lack of collateral information in the acute setting. Data on the reliability of the premorbid mRS in "real-world" practice outside of clinical trial or registry settings are limited. METHODS: A retrospective study at a high volume academic primary stroke center. For patients with acute ischemic stroke treated with alteplase between July 2012 and July 2016, hospital electronic records were reviewed for detailed inpatient occupational therapist (OT) assessment of premorbid functional status to determine mRS (OT-mRS). This was compared with premorbid mRS determined at acute emergency department assessment (Acute-mRS). Kappa statistic and Lin's concordance correlation coefficient was used to calculate agreement between Acute-mRS and OT-mRS. RESULTS: Among stroke patients treated with alteplase over the 4 years period, OT-mRS was available for 312 patients (79.0%), the mean age was 75.5 years (male 51.9%). 82.4%, 11.9%, and 5.8% of patients had Acute-mRS of 0-1, 2, and ≥3; while 84.9%, 8.0%, and 6.7% had OT-mRS of 0-1, 2, and ≥3, respectively. The agreement between Acute-mRS and OT-mRS was 83.3%, with κ = .64 and correlation coefficient r = .87 (95% CI .841-.896, P < .05). CONCLUSIONS: There was at least moderate agreement between Acute-mRS prior to thrombolysis and OT-mRS obtained by detailed assessment later. The number of patients with premorbid disability was small and may have positively influenced the agreement between the 2 scores.

Contributions of van der Waals Interactions and Hydrophobic Attraction to Molecular Adhesions on a Hydrophobic MoS2 Surface in Water.

Pushing the boundaries of the investigation of hydrophobic attraction (HA) to the molecular scale readily ensures the collection of experimental results free of secondary effects, thereby facilitating the unraveling of the underlying mechanism by providing clean experimental results that truly reflect the hydrophobic attraction. Regardless of the feasibility of this approach, investigations using this promising method are stagnant due to the difficulties in determining the individual contributions of HA and van der Waals (vdW) interactions at the molecular scale. Here, a novel approach was proposed for the first time to determine the individual contributions of vdW interactions and HA by studying the single-molecule adhesion forces of a neutral oligo ethylene glycol methacrylate copolymer on a MoS2 crystal exposed to different water chemistry. The anisotropic surface properties of MoS2 enabled the partitioning of vdW interactions and hydrophobic attraction in total single-molecule adhesion forces and also enabled determining the contribution of electrostatic interaction (ESI). When the presence of ESI is excluded, the study of single-molecule adhesion forces using single-molecule force spectroscopy (SMFS) revealed that the contribution of vdW interactions to total molecular interactions was smaller than 9 pN. The strong single-molecule adhesion forces of oligo ethylene glycol copolymer on the hydrophobic basal surface of MoS2 demonstrated that HA plays a dominant role with contribution up to 89% to the total single-molecule adhesion force. By utilizing the derived theoretical model, we quantified the individual contribution of each fundamental interaction under a variety of conditions. This study proposed a facile approach to quantitatively clarify the roles of vdW interactions and HA at the molecular scale, which may help assist future experimental and theoretical investigations of hydrophobic (solvophobic) effects and vdW interactions in aqueous solutions.

Molecular Dynamics Study of Hydrophilic Sphalerite (110) Surface as Modified by Normal and Branched Butylthiols.

Molecular dynamics simulation was used to study the wettability of the hydrophilic sphalerite (110) surface chemically modified by butylthiols made up of normal and branched alkyl tails, referred to as n-butylthiol and i-butylthiol hereafter, at different adsorption site coverages. Butylthiol molecules were grafted onto the adsorption sites of the surface in two different distributions-ordered and random. The results showed that for a given butylthiol at a given site coverage, random surface distribution yielded a slightly larger contact angle. This observation was attributed to the fact that average distances between the first and second nearest neighbors of butylthiol molecules are shorter in the case of random surface distribution, resulting in smaller patches of bare surface exposed to water molecules compared to those of the ordered surface distribution. Regardless of the tail structure, the random surface distribution exhibited hydrophobic character (i.e., contact angle ≥ 90°) at a relatively low site coverage of about 25%. The test area method and the Kirkwood and Buff approach were adopted to estimate surface energies (γSV) of the bare sphalerite (110) surface and the collector monolayer, respectively. Using the obtained γSV values of these two pure states, the apparent surface energy as a function of surface coverage was determined based on Cassie's law. This allowed us to estimate the corresponding values of solid-liquid apparent interfacial tension (γSL). Both γSV and γSL exhibit a linear inverse dependence on surface coverage with a crossover point at 25% site coverage (about 50% surface coverage), above which γSV falls below γSL, leading to contact angles greater than 90°. The results also revealed that contact angles of the two butylthiols are comparable at site coverages below ∼85%, but above that, they are significantly lower for the branched thiols compared to their normal counterparts. Considering the Lennard-Jones interaction energies between the water cluster and the butylthiols, stronger attractive interactions were present in the case of i-butylthiol due to the presence of two methyl groups in its alkyl chain. This difference was the most intense at site coverages above ∼85%.