Sulfate Groups Research Articles

Structural Analysis and Anticoagulant Activity of Fucosylated Glycosaminoglycan from Sea Cucumber Phyllophorus proteus.

Phyllophorus proteus is a low-value sea cucumber from Indonesia and other tropical peripheral waters. In this study, a fucosylated glycosaminoglycan (FG) was extracted from P. proteus. It consists of GlcA, GalNAc, and Fuc, with a molecular weight of 67.1 kDa. The degraded FG (dFG) was prepared by β-elimination. Structural analysis revealed that the main chain of dFG was composed of GalNAc and GlcA, linked alternately by β1,3 and β1,4 glycosidic bonds. The sulfate group was located at the 4 and 6 positions of GalNAc. Fuc was attached to the 3 position of GlcA by an α1,3 glycosidic bond, and the side chain of Fuc exhibited various sulfate substitutions. FG significantly prolonged the coagulation time of APTT, PT, TT, and FIB, surpassing the effect of LMWH, thereby demonstrating its ability to exert anticoagulant effects in both the endogenous and exogenous coagulation pathways. Conversely, dFG had no significant effect on the clotting time of PT, suggesting its lack of impact on the intrinsic coagulation pathway. This study elucidates the structural properties and potent anticoagulant activities of fucosylated glycosaminoglycan from P. proteus.

α,β-Dehydrogenation Adjacent to Sulfur- and Phosphorus- Containing Compounds.

Here, we report a robust nickel-catalyzed α,β-dehydrogenation process designed for substrates that contain electron-withdrawing sulfur and phosphorus groups. Leveraging the formation of organozinc intermediates and the utilization of a mild oxidant, allyl methyl carbonate, this methodology exhibits remarkable efficiency and outstanding diastereoselectivities across a diverse array of substrates, achieving E:Z ratios exceeding 20:1. Investigation through deuterium incorporation studies and an analysis of the reaction sequence leading to the formation of the dehydrogenative allylation side product, provide useful insights into reaction optimization.

Instant Controlled Pressure Drop (DIC) as an innovative pre-treatment for extraction of natural compounds from the brown seaweed Sargassum muticum (Yendo) Fensholt 1955 (Ochrophytina, Fucales)

The effects of the Instant Controlled Pressure Drop (DIC) technology on the recovery of natural compounds from the brown seaweed Sargassum muticum (Yendo) Fensholt 1955 (Ochrophytina, Fucales) were investigated. Fresh biomass of S. muticum was collected on the Brittany Coast, France. Both fresh and Air Impingement-Dried (AID) thalli of 3 and 10 cm length were submitted to DIC during 20 s or 90 s of processing time under 100 or 800 kPa of saturated steam pressure. DIC treatment significantly improved the extraction of sulphate groups at 90 s, and carotene at 20 s under 100 kPa in thalli of 10 cm. While, coupling AID to DIC, the content of neutral sugars, proteins and antioxidants were higher in AID + DIC treatments. Further, a significant increase of 20 % in fucose-containing sulfated polysaccharides and 30 % in sodium alginate under 100 kPa during 90 s, compared to oven-dried, was observed. The biomass of the invasive S. muticum treated by DIC and AID + DIC represented a valuable contribution for extraction of natural compounds. Advantages for industrial integration of DIC were discussed.

Synthesis of carbon dots with tailored heteroatomic structure for achieving ultrahigh effectiveness in persulfate activation

Carbon dots (CDs) are normally feature with zero-dimensional structure, excellent solubility, good biosafety, and exceptional photoelectronic properties, thus, awakening the homogeneous-like photocatalytic potency of CDs in peroxymonosulfate (PMS) activation can afford new idea for water body remediation. Herein, we presented a facile nitrogen and sulfur co-doping strategy for the development of high-performance CDs-based photocatalysts. Through the deep investigation on the structure-activity relationship, we proposed that the incorporated pyridinic N within CDs structure could serve as efficient Lewis basic sites for PMS confinement. Importantly, the co-existence of oxidized sulfur groups and specific nitrogen speciation (pyridine N and pyrrolic N) induced unique “push-pull” effect on the photogenerated carriers within the surface state of S,N co-doped CDs. The unique synergy sites and surface hydrophilic nature conferred the CDs exceptional photocatalytic effectiveness, presenting a remarkable PMS consumption ratio of 7.62 per gram of the CDs photocatalyst within just 20 min. Profited from the improved kinetics of interfacial reactions, the CDs-photocatalyzed oxidation system that consisted largely of sulfate radicals can completely degrade rhodamine B within 12.5 min, and hold great potential in long-term operation without needing to regenerate CDs catalyst.

Preparation of sulfated arabinogalactan-loaded hydrogel for wound healing in mouse burn model

Sulfation of polysaccharides can affect their biological activity by introducing sulfate groups. Skin burns occur regularly and have a great impact on normal survival. In this study, sulfated arabinogalactan (SAG) was prepared by sulfation, and polyvinyl alcohol (PVA) was used to prepare hydrogels for the treatment of scalded skin in mouse. The results show that the main chain of SAG consists of →3-β-D-Galactose (Gal)-(1, →3, 6)-β-D-Gal-(1 and →4)-β-d-Glucose (Glc)-(1. The chain is a neutral polysaccharide composed of T-β-L-Arabinose (Araf)-(1→, with a molecular weight of 17.9 kDa. At the same time, PVA + SAG hydrogel can promote the scald repair of mouse skin by promoting collagen deposition and angiogenesis, and regulating the TLR4/MyD88/NF-κB signaling pathway. Interestingly, the effect of SAG on promoting the repair of scald wounds is enhanced after AG is derivatized by sulfation. Therefore, the preparation of SAG by sulfation can promote scald repair, and has great application potential in the field of food and medicine.

Developing and Benchmarking Sulfate and Sulfamate Force Field Parameters via Ab Initio Molecular Dynamics Simulations To Accurately Model Glycosaminoglycan Electrostatic Interactions.

Glycosaminoglycans (GAGs) are negatively charged polysaccharides found on cell surfaces, where they regulate transport pathways of foreign molecules toward the cell. The structural and functional diversity of GAGs is largely attributed to varied sulfation patterns along the polymer chains, which makes understanding their molecular recognition mechanisms crucial. Molecular dynamics (MD) simulations, thanks to their unmatched microscopic resolution, have the potential to be a reference tool for exploring the patterns responsible for biologically relevant interactions. However, the capability of molecular dynamics force fields used in biosimulations to accurately capture sulfation-specific interactions is not well established, partly due to the intrinsic properties of GAGs that pose challenges for most experimental techniques. In this work, we evaluate the performance of molecular dynamics force fields for sulfated GAGs by studying ion pairing of Ca2+ to sulfated moieties─N-methylsulfamate and methylsulfate─that resemble N- and O-sulfation found in GAGs, respectively. We tested available nonpolarizable (CHARMM36 and GLYCAM06) and explicitly polarizable (Drude and AMOEBA) force fields, and derived new implicitly polarizable models through charge scaling (prosECCo75 and GLYCAM-ECC75) that are consistent with our developed "charge-scaling" framework. The calcium-sulfamate/sulfate interaction free energy profiles obtained with the tested force fields were compared against reference ab initio molecular dynamics (AIMD) simulations, which serve as a robust alternative to experiments. AIMD simulations indicate that the preferential Ca2+ binding mode to sulfated GAG groups is solvent-shared pairing. Only our scaled-charge models agree satisfactorily with the AIMD data, while all other force fields exhibit poorer agreement, sometimes even qualitatively. Surprisingly, even explicitly polarizable force fields display a notable disagreement with the AIMD data, likely attributed to difficulties in their optimization and possible inherent limitations in depicting high-charge-density ion interactions accurately. Finally, the underperforming force fields lead to unrealistic aggregation of sulfated saccharides, which qualitatively disagrees with our understanding of the soft glycocalyx environment. Our results highlight the importance of accurately treating electronic polarization in MD simulations of sulfated GAGs and caution against over-reliance on currently available models without thorough validation and optimization.

Synthesis and Reactivity of Masked Organic Sulfates.

Nature offers a variety of structurally unique, sulfated endobiotics including sulfated glycosaminoglycans, sulfated tyrosine peptides, sulfated steroids/bile acids/catecholamines. Sulfated molecules display a large number of biological activities including antithrombotic, antimicrobial, anticancer, anti-inflammatory, and others, which arise from modulation of intracellular signaling and enhanced in vivo retention of certain hormones. These characteristics position sulfated molecules very favorably as drug-like agents. However, few have reached the clinic. Major hurdles exist in realizing sulfated molecules as drugs. This state-of-the-art has been transformed through recent works on the development of sulfate masking technologies for both alkyl (sulfated carbohydrates, sulfated steroids) and aryl (sTyr-bearing peptides/proteins, sulfated flavonoids) sulfates. This review compiles the literature on different strategies implemented for different types of sulfate groups. Starting from early efforts in protection of sulfate groups to the design of newer SuFEx, trichloroethyl, and gem-dimethyl-based protection technologies, this review presents the evolution and application of concepts in realizing highly diverse, sulfated molecules as candidate drugs and/or prodrugs. Overall, the newer strategies for sulfate masking and demasking are likely to greatly enhance the design and development of sulfated molecules as non-toxic drugs of the future.

Comparison of Transforaminal Magnesium Sulfate with Steroid Injection in the Management of ‎Radicular Back Pain: A Randomized Double-Blinded Clinical Trial Study

Background: This study compares the effects of transforaminal magnesium sulfate injection versus other methods for managing radicular back pain, highlighting its potential for improved pain relief and functional outcomes. Methods: This randomized, double-blind clinical trial involved 30 patients with radicular back pain who were randomly assigned to receive either transforaminal magnesium sulfate or triamcinolone injection. Primary outcomes were pain intensity and functional disability, assessed using the Visual Analogue Scale (VAS) and Oswestry Disability Index (ODI), respectively. These were evaluated at five time points: Before the injection, 2 weeks, 1 month, 3 months, and 6 months after the injection. Secondary outcomes included drug-related adverse events within the six-month follow-up period. Results: Baseline characteristics were not significantly different between the two study groups. Compared to pre-injection measures, post-injection pain intensity and functional disability were significantly reduced in both groups at all time points (P < 0.001). At all postoperative evaluations, pain intensity and functional disability were lower in the magnesium sulfate group compared to the steroid group (P < 0.001). No drug-related side effects were recorded in either group. Conclusions: For patients with radicular back pain, transforaminal magnesium sulfate injection appears to be an effective and safe alternative to transforaminal steroid injection.

Preparation and activity evaluation of zinc ion delivery system based on fucoidan-zinc complex.

Zinc is a critical trace element in the human body, playing a key role in regulating various protein functions and cellular metabolism. Thus, maintaining zinc homeostasis is essential for human health, as zinc deficiency can directly contribute to the onset of numerous diseases. Effective supplementation with zinc ions offers a viable treatment for zinc deficiency. Polysaccharides, particularly natural polysaccharides, exhibit extensive physiological activities and serve as efficient systems for delivering zinc ions. Fucoidan (F) is an affordable, widely available polysaccharide with significant bioactivity and safety, attracting growing research interest. However, most studies focus on its physiological functions, while few explore the structure and effects of fucoidan-metal complexes. In this study, fucoidan (F) was chosen to complex with Zn2+ to form the fucoidan-zinc (F-Zn) complex, whose structure was characterized. The zinc ion content reached 9.15%, with zinc (II) predominantly complexed with sulfate groups in the F-Zn (II) complex. Evaluation demonstrated that the prepared fucoidan-zinc system, at a concentration of 110 μg/ml, exhibited no significant cytotoxicity toward HT22 cells. Furthermore, both F and F-Zn exhibited significant neuroprotective effects in an HT22 cell model induced by cisplatin. Additional investigations revealed that F and F-Zn could mitigate cisplatin-induced increases in reactive oxygen species levels and alleviate mitochondrial damage. The fucoidan-zinc complex presents itself as a promising zinc ion delivery system for treating zinc deficiency.

Zeolite functionalized with macroalgae as novel material for Fe and Mn removal from real acid mine drainage

The treatment of heavy metals such as Fe and manganese Mn remains a critical global issue, necessitating solutions that are not only effective and efficient but also cost- effective and easy to implement. Adsorption has been identified as one of the most efficient techniques for removing heavy metals. This study investigates adsorption method applied to real AMD, characterized by high levels of heavy metal contamination and low pH. Key parameters analyzed include adsorption performance, isotherm and kinetic models, thermodynamic properties, and adsorption characteristics. The adsorbent used was zeolite functionalized with carboxyl, hydroxyl, and sulfate groups derived from macroalgae. Material characterization was conducted using SEM, XRD, and FTIR. The results indicate that zeolite functionalized with carboxyl, hydroxyl, and sulfate groups from macroalgae effectively reduced Fe and Mn concentrations by up to 99 % within just five minutes. Furthermore, the adsorption process followed a pseudo-second-order kinetic model and conformed to the Langmuir isotherm model.

Sulfated polysaccharide from Apostichopus japonicus viscera exhibits anti-inflammatory properties in vitro and in vivo

Polysaccharides from sea cucumbers are known for their biological activities, but little is known about those from sea cucumber viscera. The present study isolated a sulfated polysaccharide (SCVP-2) from the viscera of Apostichopus japonicas, which had a molecular weight of 209.1 kDa. SCVP-2 comprised 66.3 % total sugars, 2.1 % uronic acid, 4.5 % proteins, and 25.5 % sulfate groups, containing glucosamine, galactosamine, glucose, galactose, and fucose. FT-IR and NMR analyses identified SCVP-2 as a fucoidan sulfate with sulfation patterns of the fucose branches as Fuc2S, Fuc4S, and Fuc0S. SEM and AFM analyses showed irregular clusters and linear conformations. SCVP-2 demonstrated strong anti-inflammatory properties both in vitro and in vivo. In lipopolysaccharide (LPS)-induced inflammation in macrophage RAW264.7 cells, SCVP-2 significantly reduced nitric oxide (NO) and cytokine secretion (IL-1β, IL-6, TNF-α). Additionally, it downregulated the expression of these cytokine genes. Furthermore, the anti-inflammatory mechanism of SCVP-2 was related to the inhibition of the MAPKs and NF-κB pathways. SCVP-2's anti-inflammatory capacity was confirmed in acute inflammation models, including xylene-induced ear swelling and acetic acid-induced peritoneal capillary permeability, and in high-fat diet-induced systemic low-grade chronic inflammation. In conclusion, SCVP-2 exhibits significant anti-inflammatory activity, suggesting its potential for development as a functional food ingredient or therapeutic agent for inflammation-related diseases.

Functionalized cellulose nanofiber films as potential substitutes for Japanese paper

Japanese papers (JPs) are among the most common materials used for the restoration of historical papers. However, they have low transparency and may structure the paper surface. To overcome the limitations of JPs, in the present work, films of cellulose nanofibers with and without lignin (LCNFs and CNFs, respectively) were explored. For this, chemically different LCNFs (carboxylated by TEMPO-mediated oxidation using variable oxidant amount and sulfated with deep eutectic solvent) and two reference CNFs were produced from Eucalyptus kraft pulps. Lignin hindered slightly the introduction of carboxyl groups into the cellulose structure, but did not affect the incorporation of sulfate groups. (L)CNFs gave films with better mechanical properties than those determined for three types of JP (tensile strength of 79–142 MPa (±11) vs 3.5–13.0 MPa (±0.4) and Young's modulus of 4900–5900 MPa (±300) vs 200–1800 MPa (±70)). Additionally, the (L)CNF films exhibited lower water vapor transmission rates (132–312 g.m−2.day−1) compared to the JPs (685–719 g.m−2.day−1), and a higher transparency (up to 89% and ≤82% for JPs). Besides thermal stability, all properties studied favored (L)CNF films over JPs, indicating their strong potential for restoration/conservation applications. This systematic comparison between the properties of (L)CNF films and JPs has never been conducted before.

Functionalization of MXene using iota-carrageenan, maleic anhydride, and N,N′-methylene bis-acrylamide for high-performance removal of thorium (IV), uranium (IV), sulfamethoxazole, and levofloxacin

An increasing quantity of pollutants has been discharged into the aquatic media, posing a serious hazard to public health. To address this issue, a new sorbent material, MXene@i.Carr@MaMb, was developed through the functionalization of the MXene surface using iota-carrageenan (i.Carr), maleic anhydride, and N, N′-methylene bis-acrylamide. This sorbent material was designed to remove thorium (Th (IV)) effectively, uranium (U (IV)), sulfamethoxazole (SMX), and levofloxacin (LEV) from wastewater. The MXene@i.Carr@MaMb composite incorporated significant functional groups, including OH, F, and O from MXene, oxygen and ester sulfate groups from iota-carrageenan (i.Carr), and OH, NH, and CO groups from N, N′-methylene bis-acrylamide, and maleic anhydride, which interacted with the UV (IV), Th (IV), SMX, and LEV pollutants through electrostatic interaction, complexation, and hydrogen bonding. MXene@i.Carr@MaMb composite exhibited excellent sorption capacities for Th (IV) (3.6 ± 0.03 mmol g−1), U (IV) (3.7 ± 0.09 mmol g−1), SMX (5.8 ± 0.03 mmol g−1), and LEV (5.9 ± 0.05 mmol g−1) at 323.15 K. The sorption kinetics and isotherms of radioactive metals and antibiotics can be well-described using pseudo-first-order kinetic models and Langmuir and Sips isothermal equations. This study presented a novel sorbent material for efficiently removing radioactive metals and antibiotics from wastewater.

Facilitating charge transport by phenyl-substitution and sulfate-intercalation on carbon nitride tubes for highly efficient photocatalytic hydrogen evolution

Despite challenges still remain, simultaneous regulation of light absorption, carrier separation and efficient exposed active sites of carbon nitride for the photocatalytic production of hydrogen (H2) are essential to help alleviate the energy crisis and achieve carbon neutrality. Using in-plane phenyl groups doping and interlayer sulfate groups modification, we demonstrated an eco-friendly and facile method for excogitating porous tubular graphitic carbon nitride (PhSO-TCN2.5). The PhSO-TCN2.5 has hollow tubular morphology with ultrathin pore walls, which offers more exposed active sites, shortened charge diffusion path and readily available diffusion channels. More importantly, the in-plane phenyl groups doping and interlayer sulfate groups modification enabled significant intense the visible light absorption, accelerated carrier transfer due to the electron transport channel between the interlayers. Meanwhile, PhSO-TCN2.5 possesses exceptionally adjusted band gap structure and more negative conduction band potential. Accordingly, the above synergistic effects contribute to the efficient photocatalytic efficiency in H2 evolution to 8709.29 μmol g−1 h−1. In addition to the apparent quantum yield of 12.0% at 420 nm, that far exceeds the reported tubular and functional group-modified carbon nitride photocatalysts. This document offers guidance on designing and producing photocatalysts with high efficiency.

Injectable and self-healing sulfated hyaluronic acid/gelatin hydrogel as dual drug delivery system for circumferential tracheal repair

Stem cell-based therapies show promise for clinically addressing circumferential tracheal defects (CTD) through tissue engineering. However, creating a tissue-engineered tracheal tube possesses a healthy cartilage matrix and intact tube structure remains a challenge. A solution lies in the use of an injectable hydrogel with shape adaptability and chondrogenic capacity, serving as a practical and dependable platform for tubular tracheal cartilage regeneration. In this study, we developed an injectable hydrogel using modified natural polymers-hydrazide-grafted gelatin (Gelatin-ADH) and aldehyde-modified hyaluronic acid with sulfated groups (HA-CHO-SO3) via Schiff Base interaction. Additionally, aldehyde-modified β-cyclodextrin (β-CD-CHO) was introduced into the network during hydrogel formation. The negative sulfated groups and hydrophobic cavities of β-cyclodextrin facilitated the efficient encapsulation and sustained release of transforming growth factor-β1 (TGF-β1) and kartogenin (KGN) within our hydrogel. This synergistically promoted the chondrogenesis of loaded bone marrow stem cells (BMSCs). Subsequently, we employed this TGF-β1, KGN, and BMSCs loaded hydrogel to form a cartilage ring. This ring was then assembled into an engineered tracheal cartilage tube using our previously reported ring-to-tube strategy. Our results demonstrated that the engineered tracheal cartilage tube effectively repaired CTD in a rabbit model. Hence, this study introduces a novel hydrogel with significant clinical application potential for tracheal tissue engineering.

Effect of branch length of cluster dextrin on the textural and rheological properties of κ-carrageenan emulsion gels

In this paper, a range of novel cluster dextrins (CDs) with high molecular weight (∼105 g/mol) and narrow molecular weight distribution were fabricated by α-amylase and branching enzyme (BE, EC 2.4.1.18). The influence of CDs on the physicochemical properties of κ-carrageenan (KC) emulsion gels was investigated. The average particle size of the composite emulsion gels containing CD was decreased by 7.85–12.66 μm, and the gel network was more uniform and denser, owing to stronger non-covalent interactions in the composite sample system. Textural results demonstrated that the composite emulsion gels exhibited higher hardness and springiness, but lower cohesiveness. CDs hindered the formation and aggregation of KC double helices, as evidenced by reducing the intensity of the sulfate group peak at 1223 cm−1. Furthermore, CDs increased the apparent viscosity, storage modulus (G'), and melting temperature (Tm) of emulsion gels, based on rheological results. CDs with longer branch lengths were more prone to entangle with KC chains to optimize the gel structure, exhibiting a more significant effect on the physicochemical properties of emulsion gels. The present study provided a new insight for constructing a new energy delivery system.

The effect of oral zinc sulfate supplementation on hospitalized infants with hyperbilirubinemia: a double-blind randomized clinical trial.

Previous investigations on the impact of oral zinc sulfate treatment on newborns' serum bilirubin levels have produced conflicting results. As a result, the goal of this clinical study was to evaluate how oral zinc sulfate affected the levels of serum bilirubin in term infants who were admitted to the neonatal intensive care unit. The study was conducted at the Neonatal Care Unit of Besat Hospital in Sanandaj, Kurdistan Province, as a double-blind randomized controlled trial. The participants included term infants (37-42weeks of gestation) who required phototherapy and were admitted to the neonatal intensive care unit. A total of 290 infants were enrolled and randomly divided into two groups. The intervention group received oral zinc sulfate supplementation at a dosage of 1mg/kg per day in addition to phototherapy, while the placebo group received an equivalent amount of placebo daily. Bilirubin measurements were obtained at the initiation of the intervention and subsequently every 24h until discharge. The collected data were analyzed using STATA software version 17. After the infants were randomly allocated to the zinc-sulfate and placebo groups, the study outcomes, including the average changes in bilirubin levels after intervention, the hours of phototherapy, and the number of days of hospitalization, were analyzed and compared for a total of 160 infants in the zinc sulfate group and 130 infants in the placebo group. The reduction in bilirubin levels in infants receiving zinc sulfate was (- 3.75 ± 0.19 CI 95% - 4.12, - 3.37) and for placebo group was (- 1.81 ± 0.15 CI 95% - 2.12, - 1.50) 24h after the intervention. Furthermore, 48 and 72h following the intervention, bilirubin levels in the intervention group demonstrated a more substantial decline. The zinc sulfate group had a shorter hospital stay (2.13 ± 0.04 vs. 2.83 ± 1.42) and required less phototherapy hours than the placebo group (6.21 ± 2.16 vs. 8.78 ± 1.40). Conclusions: Oral zinc sulfate supplementation in term neonates with hyperbilirubinemia decreased the level of bilirubin levels, duration of phototherapy, and hospital stay. Trial registration: IRCT, IRCT20220806055625N1. Study Registered 25 December 2022, http://irct.ir/trial/66,722 .

A fluorescent turn-on nanosensor for selective detection of L-morphine using D-cysteine-functionalized graphene quantum dots

Here, L- and D-cysteine-functionalized graphene quantum dots (L-/D-cys-GQDs) were designed with the aim of obtaining a selective fluorescent nanosensor to detect L-morphine. Citric acid was pyrolyzed to synthesize the GQDs, which were then functionalized with chiral L- and D-cys species using a thiol-ene click reaction between sulfur group of cysteine species and CC double bonds of GQDs. Energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopies (XPS) provides elemental analysis data which approved the presence of sulfur and nitrogen elements of L- and D-cysteine species on the surface of GQDs. Transmission electron microscopy (TEM) showed that the particle size of the modified GQDs ranges from 2 to 4.2 nm. The results of fluorescence spectroscopy showed that upon functionalization of GQDs with L-/D-cys the fluorescence intensity decreases as a result of Forster resonance energy transfer (FRET) mechanism. Interestingly, in the presence of L-morphine, the fluorescence intensity of D-cys-GQDs was selectively turned on as the FRET mechanism is ceased between the cysteine species and GQDs. Additional tests demonstrated that this nanosensor cannot interact with other drugs like methamphetamine or ibuprofen. As a result, it can serve as a cheap and precise nanosensor for identifying low quantities of L-morphine.

Single-Component Cellulose Acetate Sulfate Hydrogels for Direct Ink Writing 3D Printing.

Hydrogels, typically favored for 3D printing due to their viscoelasticity, are now trending toward ecofriendly alternatives amid growing environmental concerns. In this study, we crafted cellulose-based hydrogels, specifically employing cellulose acetate sulfate (CAS). By keeping the acetyl group substitution degree (DSacetyl = 1.8) and CAS molecular weight constant, we varied rheological properties by adjusting sulfate group substitution (DSsulfate = 0.4, 0.7, and 1.0) and CAS concentration (2-5 wt %). Rheological characterizations, including shear-thinning, yield stress, and thixotropy, were performed to identify optimal conditions for formulating CAS hydrogel ink in direct ink writing for 3D printing under selected experimental conditions. Based on rheological findings, CAS hydrogels with DSsulfate 0.7 and concentration of 4 wt % was used for 3D printing, with subsequent evaluation of printing metrics. Additionally, the effect of ionic cross-linking using Ca2+ ions on the structural integrity of 3D-printed structures was evaluated, demonstrating effective preservation through reinforced polymer networks. The shrinking and swelling behaviors of the 3D-printed structures were also significantly affected by this ionic cross-linking. Building on these findings, this work could broaden the range of cellulose derivatives available for the preparation of cellulose-based hydrogels for 3D printing.

Combined experimental and density functional theory approaches to address different mechanisms of nitrogen and sulfur doping on the enhancement of capacitive performance of hierarchical porous biochars

Activated carbon derived from biomass as hierarchical porous biochars (HPB) has been developed as electrode materials for supercapacitors. Nitrogen is known as the doping element that enhances quantum capacitance, but the mechanisms of sulfur doping on the quantum capacitance enhancement remain ambiguous. In this study, conventional approaches to assess the characteristics and capacitive performance of biochars were combined with density functional theory (DFT) calculations to assess different mechanisms of nitrogen and sulfur doping. The Bbiochar samples were prepared from the pyrolyzed fish bone powder at 800 °C without additional doping possessed a specific capacitance of 240 F g−1 at 1 A/g within 1 M H2SO4. Interestingly, additional nitrogen doping through urea mixing and additional sulfur doping through thiosulfate mixing prior to the pyrolysis enhanced the specific capacitance of biochar samples to exceed 400 F g−1 under the same condition. The urea mixed sample possessed low porosity but high charge transfer resistance, while the thiosulfate mixed sample possessed high porosity but low charge transfer resistance. The different underlying mechanisms were discussed through DFT calculations on graphene models designed based on the x-ray photoelectron spectroscopy (XPS) results. Nitrogen-doped configurations with topological defects mainly stored charge at the dangling atoms and possessed a relatively high quantum capacitance. Meanwhile, doped configurations of oxidized sulfur groups required relatively low formation energy and possessed large bond dipoles, corresponding to larger pore size and surface area of the thiosulfate mixed biochars. Understanding the contrary between effects of nitrogen and sulfur doping could resolve the bottleneck on enhancing the performance of electronic double layer supercapacitors.