Beyond nimodipine: advanced neuroprotection strategies for aneurysmal subarachnoid hemorrhage vasospasm and delayed cerebral ischemia.

The clinical management of aneurysmal subarachnoid hemorrhage (SAH)-associated vasospasm remains a challenge in neurosurgical practice, with its prevention and treatment having a major impact on neurological outcome. While considered a mainstay, nimodipine is burdened by some non-negligible limitations that make it still a suboptimal candidate of pharmacotherapy for SAH. This narrative review aims to provide an update on the pharmacodynamics, pharmacokinetics, overall evidence, and strength of recommendation of nimodipine alternative drugs for aneurysmal SAH-associated vasospasm and delayed cerebral ischemia. A PRISMA literature search was performed in the PubMed/Medline, Web of Science, ClinicalTrials.gov, and PubChem databases using a combination of the MeSH terms "medical therapy," "management," "cerebral vasospasm," "subarachnoid hemorrhage," and "delayed cerebral ischemia." Collected articles were reviewed for typology and relevance prior to final inclusion. A total of 346 articles were initially collected. The identification, screening, eligibility, and inclusion process resulted in the selection of 59 studies. Nicardipine and cilostazol, which have longer half-lives than nimodipine, had robust evidence of efficacy and safety. Eicosapentaenoic acid, dapsone and clazosentan showed a good balance between effectiveness and favorable pharmacokinetics. Combinations between different drug classes have been studied to a very limited extent. Nicardipine, cilostazol, Rho-kinase inhibitors, and clazosentan proved their better pharmacokinetic profiles compared with nimodipine without prejudice with effective and safe neuroprotective role. However, the number of trials conducted is significantly lower than for nimodipine. Aneurysmal SAH-associated vasospasm remains an area of ongoing preclinical and clinical research where the search for new drugs or associations is critical.

Fabrication of Curcumin-Based Electrochemical Nanosensors for the Detection of Environmental Pollutants: 1,4-Dioxane and Hydrazine.

This work reports the development of novel curcuminoid-based electrochemical sensors for the detection of environmental pollutants from water. In this study, the first set of electrochemical experiments was carried out using curcumin-conjugated multi-walled carbon nanotubes (MWCNT-CM) for 1,4-dioxane detection. The MWCNT-CM/GCE showed good sensitivity (103.25 nA nM-1 cm-2 in the linear range 1 nM to 1 µM), with LOD of 35.71 pM and LOQ of 108.21 pM. The second set of electrochemical experiments was carried out with bisdemethoxy curcumin analog quantum dots (BDMCAQD) for hydrazine detection. The BDMCAQD/GCE exhibited good sensitivity (74.96 nA nM-1 cm-2 in the linear range 100 nM to 1 µM), with LOD of 10 nM and LOQ of 44.93 nM. Thus, this work will serve as a reference for the fabrication of metal-free electrochemical sensors using curcuminoids as the redox mediator for the enhanced detection of environmental pollutants.

CO2-Based Polycarbonates through Ring-Opening Polymerization of Cyclic Carbonates Promoted by a NHC-Based Zinc Complex.

A backbone-substituted N-heterocyclic carbene (NHC) zinc complex, in combination with alcohol initiators, has been shown to be an effective catalyst for the ring-opening polymerization (ROP) of trimethylene carbonate (TMC) to poly(trimethylene carbonate) (PTMC) devoid of oxetane linkages. The ROP of TMC proceeded in solution to give PTMC, possessing controlled molecular mass (2500 < Mn < 10000) and low dispersity (D ∼ 1.2). Changing the alcohol initiators, PTMCs with different end-groups were obtained, included a telechelic polymer. The results of MALDI-ToF and NMR analysis confirmed the controlled/living nature of the present ROP catalytic system, where side reactions, such as inter- and intramolecular transesterifications, were minimized during the polymerization. Solution studies in different solvents demonstrated the polymerization reaction to proceed via a mechanism first order in monomer and in catalyst. The zinc complex was also able to convert substituted cyclic carbonates, which were purposely synthesized from renewable feedstocks such as CO2 and 1,3-diols. For the asymmetric 2-Me TMC monomer, good regioselectivity was observed (Xreg up to 0.92). The excellent control of the polymerization process was finally brought to light through the preparation of polycarbonate/polyether triblock copolymers by using polyethylene glycol (PEG) as a macroinitiator and of well-defined di- and triblock polycarbonate/polylactide copolymers by sequential ROP of TMC and L-LA.

QSRR modeling of lipophilicity of new spirohydantoin derivatives determined with various TLC systems.

A Quantitative structure-retention relationship (QSRR) analysis has been carried out on the chromatography parameters of lipophilicity of selected spirohydantoins. Multiple linear regression (MLR) was applied for construct the QSRR models. The chromatographic parameters of lipophilicity were determined by reversed-phase thin-layer chromatography. Chromatographic analyses were performed on C-18 modified silica gel with a two-component mobile phase consisting of water and protic organic solvent (ethanol, n-propanol, i-propanol, or t-butanol) in different ratios. QSRR models were built and for additional four aqueous mobile phases: acetone-water, acetonitrile-water, tetrahydrofuran-water, and 1,4-dioxane-water (results published before). In total, chromatographic lipophilicity parameters obtained for two types of organic solvents was subject of the QSRR. The predictive ability of each model was defined by an internal validation coefficient. The best QSRR model for predicting the chromatographic parameter of lipophilicity was obtained for tetrahydrofuran as an organic solvent.

The differential effects of blocking retinal orexin receptors on the expression of retinal c-fos and hypothalamic Vip, PACAP, Bmal1, and c-fos in Male Wistar Rats.

Orexin A and B (OXA and OXB) and their receptors are expressed in the majority of retinal neurons in humans, rats, and mice. Orexins modulate signal transmission between the different layers of the retina. The suprachiasmatic nucleus (SCN) and the retina are central and peripheral components of the body's biological clocks; respectively. The SCN receives photic information from the retina through the retinohypothalamic tract (RHT) to synchronize bodily functions with environmental changes. In present study, we aimed to investigate the impact of inhibiting retinal orexin receptors on the expression of retinal Bmal1 and c-fos, as well as hypothalamic c-fos, Bmal1, Vip, and PACAP at four different time-points (Zeitgeber time; ZT 3, 6, 11, and ZT-0). The intravitreal injection (IVI) of OX1R antagonist (SB-334867) and OX2R antagonist (JNJ-10397049) significantly up-regulated c-fos expression in the retina. Additionally, compared to the control group, the combined injection of SB-334867 and JNJ-10397049 showed a greater increase in retinal expression of this gene. Moreover, the expression of hypothalamic Vip and PACAP was significantly up-regulated in both the SB-334867 and JNJ-10397049 groups. In contrast, the expression of Bmal1 was down-regulated. Furthermore, the expression of hypothalamic c-fos was down-regulated in all groups treated with SB-334867 and JNJ-10397049. Additionally, the study demonstrated that blocking these receptors in the retina resulted in alterations in circadian rhythm parameters such as mesor, amplitude, and acrophase. Finally, it affected the phase of gene expression rhythms in both the retina and hypothalamus, as identified through cosinor analysis and the zero-amplitude test. This study represents the initial exploration of how retinal orexin receptors influence expression of rhythmic genes in the retina and hypothalamus. These findings could provide new insights into how the retina regulates the circadian rhythm in both regions and illuminate the role of the orexinergic system expression within the retina.

Isolation and characterization of pure cultures for metabolizing 1,4-dioxane in oligotrophic environments.

1,4-Dioxane concentration in most contaminated water is much less than 1 mg/L, which cannot sustain the growth of most reported 1,4-dioxane-metabolizing pure cultures. These pure cultures were isolated following enrichment of mixed cultures at high concentrations (20 to 1,000 mg/L). This study is based on a different strategy: 1,4-dioxane-metabolizing mixed cultures were enriched by periodically spiking 1,4-dioxane at low concentrations (≤1 mg/L). Five 1,4-dioxane-metabolizing pure strains LCD6B, LCD6D, WC10G, WCD6H, and WD4H were isolated and characterized. The partial 16S rRNA gene sequencing showed that the five bacterial strains were related to Dokdonella sp. (98.3%), Acinetobacter sp. (99.0%), Afipia sp. (99.2%), Nitrobacter sp. (97.9%), and Pseudonocardia sp. (99.4%), respectively. Nitrobacter sp. WCD6H is the first reported 1,4-dioxane-metabolizing bacterium in the genus of Nitrobacter. The net specific growth rates of these five cultures are consistently higher than those reported in the literature at 1,4-dioxane concentrations <0.5 mg/L. Compared to the literature, our newly discovered strains have lower half-maximum-rate concentrations (1.8 to 8.2 mg-dioxane/L), lower maximum specific 1,4-dioxane utilization rates (0.24 to 0.47 mg-dioxane/(mg-protein ⋅ d)), higher biomass yields (0.29 to 0.38 mg-protein/mg-dioxane), and lower decay coefficients (0.01 to 0.02 d-1). These are characteristics of microorganisms living in oligotrophic environments.

Engineering Biodegradable Polyurethanes with Precisely Controlled Hierarchical Structures to Access Shape Memory Effect and Enhanced Bioactivities.

Biodegradable polymers with shape memory effects (SMEs) offer promising solutions for short-term medical interventions, facilitating minimally invasive procedures and subsequent degradation without requiring secondary surgeries. However, achieving a good balance among desirable SMEs, mechanical performance, degradation rate, and bioactivities remains a significant challenge. To address this issue, we established a strategy to develop a versatile biodegradable polyurethane (PPDO-PLC) with tunable hierarchical structures via precise chain segment control. Initial copolymerization of l-lactide and ε-caprolactone sets a tunable Tg close to body temperature, followed by block copolymerization with poly(p-dioxanone) to form a hard domain. This yields a uniform microphase-separation morphology, ensuring robust SME and facilitating the development of roughly porous surface structures in alkaline environments. Cell experiments indicate that these rough surfaces significantly enhance cellular activities, such as adhesion, proliferation, and osteogenic differentiation. Our approach provides a methodology for balancing biodegradability, SMEs, three-dimensional (3D) printability, and bioactivity in materials through hierarchical structure regulation.

Convenient Preparation, Thermal Properties and X-ray Structure Determination of 2,3-Dihydro-5,6,7,8-tetranitro-1,4-benzodioxine (TNBD): A Promising High-Energy-Density Material.

2,3-dihydro-5,6,7,8-tetranitro-1,4-benzodioxine (TNBD), molecular formula = C8H4N4O10, is a completely nitrated aromatic ring 1,4-benzodioxane derivative. The convenient method of TNBD synthesis was developed (yield = 81%). The detailed structure of this compound was investigated by X-ray crystallography. The results of the thermal analysis (TG) obtained with twice re-crystallized material revealed the onset at 240 °C (partial sublimation started) and melting at 286 °C. The investigated material degraded completely at 290-329 °C. The experimental density of 1.85 g/cm3 of TNBD was determined by X-ray crystallography. The spectral properties of TNBD (NMR, FT-IR and Raman) were explored. The detonation properties of TNBD calculated by the EXPLO 5 code were slightly superior in comparison to standard high-energy material-tetryl (detonation velocity of TNBD-7727 m/s; detonation pressure-278 kbar; and tetryl-7570 m/s and 226.4 kbar at 1.614 g/cm3, or 260 kbar at higher density at 1.71 g/cm3. The obtained preliminary results might suggest TNBD can be a potential thermostable high-energy and -density material (HEDM).

Biomimicking covalent organic frameworks nanocomposite coating for integrated enhanced anticorrosion and antifouling properties of a biodegradable magnesium stent.

The utilization of biodegradable magnesium (Mg) alloys in the fabrication of temporary non-vascular stents is an innovative trend in biomedical engineering. However, the heterogeneous degradation profiles of these biomaterials, together with potential bacterial colonization that could precipitate infectious or stenotic complications, are critical obstacles precluding their widespread clinical application. In pursuit of overcoming these limitations, this study applies the principles of biomimicry, particularly the hydrophobic and anti-fouling characteristics of lotus leaves, to pioneer the creation of nanocomposite coatings. These coatings integrate poly-trimethylene carbonate (PTMC) with covalent organic frameworks (COFs), to modify the stent's surface property. The strategic design of the coating's topography, porosity, and self-polishing capabilities collectively aims to decelerate degradation processes and minimize biological adhesion. The protective qualities of the coatings were substantiated through rigorous testing in both in vitro dynamic bile tests and in vivo New Zealand rabbit choledochal models. Empirical findings from these trials confirmed that the implementation of COF-based nanocomposite coatings robustly fortifies Mg implantations, conferring heightened resistance to both biocorrosion and biofouling as well as improved biocompatibility within bodily environments. The outcomes of this research elucidate a comprehensive framework for the multifaceted strategies against stent corrosion and fouling, thereby charting a visionary pathway toward the systematic conception of a new class of reliable COF-derived surface modifications poised to amplify the efficacy of Mg-based stents. STATEMENT OF SIGNIFICANCE: Biodegradable magnesium (Mg) alloys are widely utilized in temporary stents, though their rapid degradation and susceptibility to bacterial infection pose significant challenges. Our research has developed a nanocomposite coating inspired by the lotus, integrating poly-trimethylene carbonate with covalent organic frameworks (COF). The coating achieved self-polishing property and optimal surface energy on the Mg substrate, which decelerates stent degradation and reduces biofilm formation. Comprehensive evaluations utilizing dynamic bile simulations and implantation in New Zealand rabbit choledochal models reveal that the coating improves the durability and longevity of the stent. The implications of these findings suggest the potential COF-based Mg alloy stent surface treatments and a leap forward in advancing stent performance and endurance in clinical applications.

Effect of 1,4-Dioxane Solvent on ß-Glucuronidation Using Methyl 1,2,3,4-Tetra-O-acetyl-ß-D-glucuronate as the Glycosyl Donor.

A facile and selective ß-D-glucuronidation of alcohols, such as (-)-menthol, cholestanol, (+)- and (-)-borneols, and 2-adamantanol, using commercially available methyl 1,2,3,4-tetra-O-acetyl-ß-D-glucuronate as the glycosyl donor and trimethylsilyl bis(trifluoromethanesulfonyl)imide (Tf2NTMS) (0.5 equivalent) as the activator in 1,4-dioxane at 60 °C gave products in moderate yields. The addition of MS4A increased the ß : α ratios of D-glucuronides when cholestanol, (+)-borneol, and 2-adamantanol were used as the acceptor substrate.

Meniscal repair with additive manufacture of bioresorbable polymer: From physicochemical characterization to implantation of 3D printed poly (L-co-D, L lactide-co-trimethylene carbonate) with autologous stem cells in rabbits.

Three-dimensional (3D) structures are actually the state-of-the-art technique to create porous scaffolds for tissue engineering. Since regeneration in cartilage tissue is limited due to intrinsic cellular properties this study aims to develop and characterize three-dimensional porous scaffolds of poly (L-co-D, L lactide-co-trimethylene carbonate), PLDLA-TMC, obtained by 3D fiber deposition technique. The PLDLA-TMC terpolymer scaffolds (70:30), were obtained and characterized by scanning electron microscopy, gel permeation chromatography, differential scanning calorimetry, thermal gravimetric analysis, compression mechanical testing and study on in vitro degradation, which showed its amorphous characteristics, cylindrical geometry, and interconnected pores. The in vitro degradation study showed significant loss of mechanical properties compatible with a decrease in molar mass, accompanied by changes in morphology. The histocompatibility association of mesenchymal stem cells from rabbit's bone marrow, and PLDLA-TMC scaffolds, were evaluated in the meniscus regeneration, proving the potential of cell culture at in vivo tissue regeneration. Nine New Zealand rabbits underwent total medial meniscectomy, yielding three treatments: implantation of the seeded PLDLA-TMC scaffold, implantation of the unseeded PLDLA-TMC and negative control (defect without any implant). After 24 weeks, the results revealed the presence of fibrocartilage in the animals treated with polymer. However, the regeneration obtained with the seeded PLDLA-TMC scaffolds with mesenchymal stem cells had become intimal to mature fibrocartilaginous tissue of normal meniscus both macroscopically and histologically. This study demonstrated the effectiveness of the PLDLA-TMC scaffold in meniscus regeneration and the potential of mesenchymal stem cells in tissue engineering, without the use of growth factors. It is concluded that bioresorbable polymers represent a promising alternative for tissue regeneration.

Comparison of efficacy between clazosentan and fasudil hydrochloride-based management of vasospasm after subarachnoid hemorrhage focusing on older and WFNS grade V patients: a single-center experience in Japan.

Subarachnoid hemorrhage often leads to poor outcomes owing to vasospasm, even after successful aneurysm treatment. Clazosentan, an endothelin receptor inhibitor, has been proven to be an effective treatment for vasospasms in a Japanese randomized controlled trial. However, its efficacy in older patients (≥ 75 years old) and those with World Federation of Neurosurgical Societies (WFNS) grade V has not been demonstrated. We retrospectively evaluated the efficacy of clazosentan in older patients and those with WFNS grade V, using real-world data. Patients with subarachnoid hemorrhage treated before and after the introduction of clazosentan were retrospectively evaluated. The patients were categorized into two groups (clazosentan era versus pre-clazosentan era), in which vasospasm management and outcomes were compared. Vasospasms were managed with fasudil hydrochloride-based (pre-clazosentan era) or clazosentan-based treatment (clazosentan era). Seventy-eight patients were included in this study: the clazosentan era (n = 32) and pre-clazosentan era (n = 46). Overall, clazosentan significantly reduced clinical vasospasms (clazosentan era: 31.3% versus pre-clazosentan era: 60.9%, p = 0.01), delayed cerebral ischemia (DCI) (9.4% versus 39.1%, p = 0.004), and vasospasm-related morbidity and mortality (M/M) (3.1% versus 19.6%, p = 0.03). In subgroup analysis of older patients or those with WFNS grade V, no significant difference was observed in clinical outcomes, although both DCI and vasospasm-related M/M were lower in the clazosentan era. Clazosentan was more effective than fasudil-based management in preventing DCI and reducing vasospasm-related M/M. Clazosentan could be used safely in older patients and those with WFNS grade V, although clinical outcomes in these patients were comparable to those of conventional treatment.

Factors Influencing Discontinuation of Clazosentan Therapy in Elderly Patients with Aneurysmal Subarachnoid Hemorrhage: A Retrospective Study from a Japanese Single Center.

BACKGROUND Clazosentan is an endothelin receptor antagonist approved in Japan for preventing cerebral vasospasm and vasospasm-associated cerebral ischemia and infarction. This study included elderly patients aged ≥75 years with aneurysmal subarachnoid hemorrhage (SAH) and aimed to evaluate the factors associated with discontinuing anti-vasospasm therapy with clazosentan. MATERIAL AND METHODS In this single-center retrospective observational study, we extracted diagnostic and therapeutic work-up data of consecutive 40 patients with SAH treated with clazosentan infusion (10 mg/h) as first-line anti-vasospasm therapy between May 2022 and August 2023. Patient data were compared between the discontinued and completed groups, and related factors for the discontinuation were further analyzed. RESULTS Clazosentan was discontinued in 22% (n=9) of patients due to intolerable dyspnea accompanied by hypoxemia at 5±3 days after therapy initiation, in which 44% (n=4) were elderly (≥75 years). Patients who discontinued clazosentan therapy showed significantly lower urine volumes compared with those who completed the therapy (P<0.05). Multivariate regression analysis revealed that day-to-day urine volume variance and older age were independent risk factors for drug cessation (P<0.05). The cut-off value for predicting clazosentan discontinuation was -0.7 mL/kg/h with sensitivity of 86% and specificity of 75% (area under the curve: 0.76±0.10; 95% confidence interval: 0.56-0.96; P=0.035). CONCLUSIONS Our results suggest that approximately 20% of SAH patients suffered from intolerable respiratory symptoms attributable to hypoxemia. We found that both reduced day-to-day urine volume variation and older age are independent risk factors for drug discontinuation.

Fabrication and characterization of poly(lactic acid-trimethylene carbonate) based biodegradable composite films.

Two biobased composite films have been prepared with poly (lactic acid-trimethylene carbonate), polylactic acid and Laponite by solvent evaporation method. The 1H NMR and FTIR spectrums illustrate that P (LA-TMC) polymer is successfully synthesized and designed composite films are produced. Morphometric analyses demonstrate that the roughnesses of the film's surface and cross-section are on the increase with higher PLA and Laponite content. Mechanical performances reveal that the rise in tensile strength and modulus while maintaining excellent elongation at break is mainly due to the increase in the content of polylactic acid and Laponite. By utilizing the nano effect of Laponite, the maximum tensile strength of the composite film reaches 34.59 MPa. Thermal property results illustrate that the Tg and initial decomposition temperature are on the growth with the increase of PLA content. However, it is not significant on the effect of Laponite on the initial decomposition temperature. The water vapor permeability measurements prove that the barrier property of P(LA-TMC)/PLA/Laponite composite film is on the ascent with the Laponite addition. Hydrolytic degradation tests indicate that PLA and Laponite play avital part in accelerating the degradation rate of composite films and alkaline media is superior acidic and neutral conditions.

A natural butter glyceride as a plasticizer for improving thermal, mechanical, and biodegradable properties of poly(lactide acid).

Polylactic acid (PLA) is a biobased and biodegradable thermoplastic polyester with great potential to replace petroleum-based plastics. However, its poor toughness and slow biodegradation rate affect broad applications of PLA in many areas. In this study, a glycerol triester existing in natural butter, glycerol tributyrate, was creatively explored and compared with previously investigated triacetin and tributyl citrate, as potential plasticizers of PLA for achieving improved mechanical and biodegradation performances. The compatibilities of these agents with PLA were assessed quantitively via the Hansen solubility parameter (HSP) and measured by using different testing methods. The incorporation of these compounds with varied contents ranging from 1 to 30 % in PLA altered thermal, mechanical, and biodegradation properties consistently, and the relationship and impacts of chemical structures and properties of these agents were systematically investigated. The results demonstrated that glycerol tributyrate is a novel excellent plasticizer for PLA and the addition of this triester not only effectively reduced the glass transition, cold crystallization, and melting temperatures and Young's modulus, but also led to a significant improvement in the enzymatic degradation rate of the plasticized PLA. This study paves a way for the development of sustainable and eco-friendly food grade plasticized PLA products.

Occurrence of Rhodococcus sp. RR1 prmA and Rhodococcus jostii RHA1 prmA across microbial communities and their enumeration during 1,4-dioxane biodegradation.

1,4-Dioxane, a likely human carcinogen, is a co-contaminant at many chlorinated solvent contaminated sites. Conventional treatment technologies, such as carbon sorption or air stripping, are largely ineffective, and so many researchers have explored bioremediation for site clean-up. An important step towards this involves examining the occurrence of the functional genes associated with 1,4-dioxane biodegradation. The current research explored potential biomarkers for 1,4-dioxane in three mixed microbial communities (wetland sediment, agricultural soil, impacted site sediment) using monooxygenase targeted amplicon sequencing, followed by quantitative PCR (qPCR). A BLAST analysis of the sequencing data detected only two of the genes previously associated with 1,4-dioxane metabolism or co-metabolism, namely propane monooxygenase (prmA) from Rhodococcus jostii RHA1 and Rhodococcus sp. RR1. To investigate this further, qPCR primers and probes were designed, and the assays were used to enumerate prmA gene copies in the three communities. Gene copies of Rhodococcus RR1 prmA were detected in all three, while gene copies of Rhodococcus jostii RHA1 prmA were detected in two of the three sample types (except impacted site sediment). Further, there was a statistically significant increase in RR1 prmA gene copies in the microcosms inoculated with impacted site sediment following 1,4-dioxane biodegradation compared to the control microcosms (no 1,4-dioxane) or to the initial copy numbers before incubation. Overall, the results indicate the importance of Rhodococcus associated prmA, compared to other 1,4-dioxane degrading associated biomarkers, in three different microbial communities. Also, the newly designed qPCR assays provide a platform for others to investigate 1,4-dioxane biodegradation potential in mixed communities and should be of particular interest to those considering bioremediation as a potential 1,4-dioxane remediation approach.

Ubiquitous occurrence of 1,4-dioxane in drinking water of China and its ecological and human health risk.

The occurrence and distribution of 1,4-dioxane was investigated in 280 source and finished drinking water samples from 31 Chinese cities, based on which its ecological and health risks were systematically evaluated. The findings demonstrated that 1,4-dioxane was detected in about 80.0 % samples with values ranging from n.d. to 7757 ng/L in source water and n.d. to 2918 ng/L in drinking water. 1,4-Dioxane showed limited removal efficiency using conventional coagulation-sedimentation-filtration processes (14 % ± 48 %), and a removal efficiency of 35 % ± 44 % using ozonation-biological activated carbon advanced treatment processes. Relatively higher concentrations, detection frequency and environmental risk were observed in Taihu Lake, Yellow River, Yangtze River, Zhujiang River, and Huaihe River mainly in the eastern and southern regions, where there are considerable industrial activities and comparatively high population densities. The widespread presence as by-products during manufacturing consumer products e.g., ethoxylated surfactants, suggested municipal wastewater discharges were the dominant source for the ubiquitous occurrence of 1,4-dioxane, while industrial activities, e.g. resin manufacturing, also contribute considerably to the elevated concentrations of 1,4-dioxane. The estimated risk quotients were in the range of <1.5 × 10-4 for ecological risk, <5.0 × 10-3 by oral exposure and < 5.0 × 10-2 by inhalation exposure for health risk, illustrating limited ecological harm to water environment or chronic toxicity to human health. For carcinogenic risk, 1,4-Dioxane presented a mean risk of 1.8 × 10-6 by oral exposure, which slightly surpassed the recommended acceptable levels of U.S. EPA (<10-6), and risk from inhalation exposure could be negligible. The pervasiveness in drinking water, low removal efficiencies during water treatment processes, and suspected health impacts, highlighted the necessity to set related water quality standards of 1,4-dioxane in order to improve water environment in China.

Effect of stereo-complexation on crystallization behavior and barrier properties of poly-lactide.

The unique stere-complex crystal formed by poly(ʟ-lactide)/poly(ᴅ-lactide) (PLLA/PDLA) has a significant impact on properties of poly-lactide materials and is considered an effective means to improve the barrier properties of poly-lactide (PLA). In this work, poly-lactide films with different aggregate structures were prepared and the relationship of aggregate structure and barrier properties were explored. The results show that the crystal structure including crystallinity and crystal forms can be controlled by adjusting the isothermal crystallization time and crystallization temperature during the molding process. PLLA/PDLA composite films contain both homochiral crystallites and stereo-complex crystallites, and there is a synergistic crystallization effect between the two of them, which provides the composite films with high crystallinity and excellent barrier properties. Compared to the PLLA with homochiral crystallites, the PLLA/PDLA composite film with only stereo-complex crystallites exhibits higher barrier properties. The linear correlation between the crystallinity and the barrier properties is weak due to the changes in crystallization behavior and then the structure of poly-lactide caused by stereo-complexation. The linear correlation between the crystallinity and the barrier properties of the blend film is strong in the low crystallinity but weak at high crystallinity. Compared to homochiral crystallites, stereo-complex crystallites exhibits lower crystallinity dependence. It has been proven that different crystal forms have different design ideas for preparing high-barrier films, but the stereo-complexation resulting from the intermolecular forces between PLLA and PDLA having complementary chemical structure, is an effective method for enhancing the barrier performances of poly-lactide sustainably.

Fe-ZSM-5 zeolite catalyst for heterogeneous Fenton oxidation of 1,4-dioxane: effect of Si/Al ratios and contributions of reactive oxygen species.

Heterogeneous Fenton oxidation using traditional catalysts with H2O2 for the degradation of 1,4-dioxane (1,4-DX) still presents challenge. In this study, we explored the potential of Fe-ZSM-5 zeolites (Fe-zeolite) with three Si/Al ratios (25, 100, 300) as heterogeneous Fenton catalysts for the removal of 1,4-DX from aqueous solution. Fe2O3 or ZSM-5 alone provided ineffective in degrading 1,4-DX when combined with H2O2. However, the efficient removal of 1,4-DX using H2O2 was observed when Fe2O3 was loaded on ZSM-5. Notably, the Brønsted acid sites of Fe-zeolite played a crucial role during the degradation of 1,4-DX. Fe-zeolites, in combination with H2O2, effectively removed 1,4-DX via a combination of adsorption and oxidation. Initially, Fe-zeolites demonstrated excellent affinity for 1,4-DX, achieving adsorption equilibrium rapidly in about 10 min, followed by effective catalytic oxidative degradation. Among the Fe-ZSM-5 catalysts, Fe-ZSM-5 (25) exhibited the highest catalytic activity and degraded 1,4-DX the fastest. We identified hydroxyl radicals (·OH) and singlet oxygen (1O2) as the primary reactive oxygen species (ROS) responsible for 1,4-DX degradation, with superoxide anions (HO2·/O2·-) mainly converting into 1O2 and ·OH. The degradation primarily occurred at the Fe-zeolite interface, with the degradation rate constants proportional to the amount of Brønsted acid sites on the Fe-zeolite. Fe-zeolites were effective over a wide working pH range, with alkaline pH conditions favoring 1,4-DX degradation. Overall, our study provides valuable insights into the selection of suitable catalysts for effective removal of 1,4-DX using a heterogeneous Fenton technology.

Experimental evidence for immiscibility of enantiomeric polymers: Phase separation of high-molecular-weight poly(ʟ-lactide)/poly(ᴠ-lactide) blends and its impact on hindering stereocomplex crystallization.

Although polymers tend not to mix, it remains challenging to characterize the immiscibility of enantiomeric poly(ʟ-lactide) (PLLA) and poly(ᴅ-lactide) (PDLA), particularly with equivalent and high molecular weight (high MW), which frustratingly disfavors the exclusive stereocomplexation. By introducing a random copolymer (PLC) of ʟ-lactide and caprolactone to form binary blends with PLLA and PDLA, the phase behavior of high-MW PLLA/PDLA blends was investigated mainly by using differential scanning calorimetry (DSC) and atomic force microscopy (AFM). DSC results showed that PLLA/PLC blends exhibited a single glass transition temperature (Tg), which depended on the blending ratio and precisely corresponded with the theoretical values calculated from the Fox equation. In comparison, PDLA/PLC blends showed composition-dependent heat-capacity increment at two unchanged Tg values of pure PLC and PDLA. AFM observation revealed that PLC is completely miscible with PLLA at high MW but is immiscible with PDLA, logically suggesting immiscibility of high-MW PLLA and PDLA. Moreover, AFM results demonstrated that high-MW PLLA/PDLA blends exhibited spherical droplets in asymmetric blends and bicontinuous interpenetrating worm-like patterns in symmetric counterparts, showing distinct and well-defined interfaces, confirming the microphase separation. Additionally, different MWs fundamentally led to significant differences in miscibility, which consequently affected the crystallization behaviors of PLLA/PDLA blends. This work provides evidence for (im)miscibility and its crucial impact on the crystallization of PLLA/PDLA blends and has important implications for understanding the stereocomplexation of polymers.