A review: Hydrochar as potential adsorbents for wastewater treatment and CO2 adsorption.

To valorize the biomass and organic waste, hydrothermal carbonization (HTC) stands out as a highly efficient and promising pathway given its intrinsic advantages over other thermochemical processes. Hydrochar, as the main product obtained from HTC, is widely applied as a fuel source and soil conditioner. Aside from these applications, hydrochar can be either directly used or modified as bio-adsorbents for environmental remediation. This potential arises from its tunable surface chemistry and its suitability to act as a precursor for activated or engineered carbon. In view of the importance of this topic, this review offers a thorough examination of the research progress for using hydrochar and its modified forms to remove organic dyes (cationic and anionic dyes), heavy metals, herbicides/pesticides, pharmaceuticals, and CO2. The review also sheds light on the fundamental chemistry involved in HTC of biomass and the major analytical techniques applied for understanding surface chemistry of hydrochar and modified hydrochar. The knowledge gaps and potential hurdles are identified to highlight the challenges and prospects of this research field with a summary of the key findings from this review. Overall, this article provides valuable insights and directives and pinpoints the areas meriting further investigation in the application potential of hydrochar in wastewater management and CO2 capture.

Chemical extraction of chitin from American lobster (Homarus americanus) shells optimized through response surface methodology.

Chitin extraction from the shells of American lobsters (Homarus americanus) was optimized through the use of response surface methodology (RSM). The demineralization step was optimized to minimize the ash content of shell samples and the deproteination step was optimized to minimize the protein content of the chitin product. At a laboratory scale, one set of optimized conditions for the demineralization step was 7.35 % w/w acetic acid at a 40 mL/g of powdered lobster shell ratio for 15 min; this lowered the ash content from 39.62 % to 0.41 ± 0.08 %. A set of optimized conditions for the deproteination step at a similar scale was 4 % w/w sodium hydroxide at a 43 mL/g demineralized shell ratio heated to 95 °C for 83 min. These conditions were indicated to entirely remove protein from the resultant chitin. Average yields under optimized conditions were 23.43 ± 1.75 % for demineralization and 30.33 ± 0.02 % for deproteination, though a demineralization reaction with larger biomass input had a higher yield at 40.31 %.

Chitin, Chitosan, and Nanochitin: Extraction, Synthesis, and Applications.

Crustacean shells are a sustainable source of chitin. Extracting chitin from crustacean shells is ongoing research, much of which is devoted to devising a sustainable process that yields high-quality chitin with minimal waste. Chemical and biological methods have been used extensively for this purpose; more recently, methods based on ionic liquids and deep eutectic solvents have been explored. Extracted chitin can be converted into chitosan or nanochitin. Once chitin is obtained and modified into the desired form, it can be used in a wide array of applications, including as a filler material, in adsorbents, and as a component in biomaterials, among others. Describing the extraction of chitin, synthesis of chitosan and nanochitin, and applications of these materials is the aim of this review. The first section of this review summarizes and compares common chitin extraction methods, highlighting the benefits and shortcomings of each, followed by descriptions of methods to convert chitin into chitosan and nanochitin. The second section of this review discusses some of the wide range of applications of chitin and its derivatives.

Aspirin-Based Organoiron Dendrimers as Promising Anti-Inflammatory, Anticancer, and Antimicrobial Drugs.

Designing nanocarriers with actions directed at a specific organ or tissue is a very promising strategy since it can significantly reduce the toxicity of a bioactive drug. In this study, an organometallic dendrimer was used to synthesize a biocompatible drug delivery system by attaching aspirin to the periphery of the dendrimer. Our goal is to enhance the bioavailability and anticancer activity of aspirin and reduce its toxicity through successive generations of organoiron dendrimers. The biological activity of aspirin-based dendrimer complexes was evaluated. The result of antimicrobial activity of the synthesized dendrimers also demonstrated an increase in their antimicrobial activity with increased generation of the dendrimers for most types of microorganisms. This study reveals for the first time that organoiron dendrimers linked with aspirin exhibit an excellent Gram-negative activity comparable to the reference drug Gentamicin. All synthesized dendrimers were tested for their anticancer activity against breast cancer cell lines (MCF-7), hepatocellular cell lines (Hep-G2), and a non-cancer cell line, Human Embryonic Kidney (HEK293), using the MTT cell viability assay and compared against a standard anticancer drug, Doxorubicin. Compounds G3-D9-Asp and G4-D12-Asp exhibited noticeable activity against both cell lines, both of which were more effective than aspirin itself. In addition, the in vivo anti-inflammatory activity and histopathology of swollen paws showed that the designed aspirin-based dendrimers displayed significant anti-inflammatory activity; however, G2-D6-Asp showed the best anti-inflammatory activity, which was more potent than the reference drug aspirin during the same period. Moreover, the coupling of aspirin to the periphery of organoiron dendrimers showed a significant reduction in the toxicity of aspirin on the stomach.

Development of Ferromagnetic Materials Containing Co2P, Fe2P Phases from Organometallic Dendrimers Precursors.

The development of synthesis methods to access advanced materials, such as magnetic materials that combine multimetallic phosphide phases, remains a worthy research challenge. The most widely used strategies for the synthesis of magnetic transition metal phosphides (TMPs) are organometallic approaches. In this study, Fe-containing homometallic dendrimers and Fe/Co-containing heterometallic dendrimers were used to synthesize magnetic materials containing multimetallic phosphide phases. The crystalline nature of the nearly aggregated particles was indicated for both designed magnetic samples. In contrast to heterometallic samples, homometallic samples showed dendritic effects on their magnetic properties. Specifically, saturation magnetization (Ms) and coercivity (Hc) decrease as dendritic generation increases. Incorporating cobalt into the homometallic dendrimers to prepare the heterometallic dendrimers markedly increases the magnetic properties of the magnetic materials from 60 to 75 emu/g. Ferromagnetism in homometallic and heterometallic particles shows different responses to temperature changes. For example, heterometallic samples were less sensitive to temperature changes due to the presence of Co2P in contrast to the homometallic ones, which show an abrupt change in their slopes at a temperature close to 209 K, which appears to be related to the Fe2P ratios. This study presents dendrimers as a new type of precursor for the assembly of magnetic materials containing a mixture of iron- and cobalt-phosphides phases with tunable magnetism, and provides an opportunity to understand magnetism in such materials.

Polylactic Acid Cellulose Nanocomposite Films Comprised of Wood and Tunicate CNCs Modified with Tannic Acid and Octadecylamine.

Herein, a one-pot strategy was used to prepare hydrophobic cellulose nanocrystals (CNCs) surface-modified with tannic acid and octadecylamine. By this strategy, CNCs derived from wood (W-CNC) and tunicates (T-CNC) were modified in situ and incorporated into a polylactic acid (PLA) matrix using two methods, without first drying the CNCs. Films of PLA-CNC nanocomposites were prepared both by solution casting and by wet compounding in a thermo-kinetic mixer, followed by melt extrusion. Various properties of these PLA nanocomposites were evaluated herein, along with an assessment of how these properties vary with the type of CNC reinforcement. Cast films with a hybrid mixture of wood and tunicate CNCs displayed improved mechanical properties compared to either wood or tunicate CNCs, but extruded films did not show this hybrid effect. The water vapor permeability of the extruded nanocomposite films with 1% CNCs was reduced by as much as 60% compared to the PLA films. The composite films also showed enhanced biodegradation compared to neat PLA films. These results demonstrate that wet compounded PLA composites produced with wood or tunicate CNCs modified using a one-pot, water-based route have improved barrier and biodegradation properties, indicating a potential for packaging applications without having to dry the CNCs.

Towards the scalable isolation of cellulose nanocrystals from tunicates.

In order for sustainable nanomaterials such as cellulose nanocrystals (CNCs) to be utilized in industrial applications, a large-scale production capacity for CNCs must exist. Currently the only CNCs available commercially in kilogram scale are obtained from wood pulp (W-CNCs). Scaling the production capacity of W-CNCs isolation has led to their use in broader applications and captured the interest of researchers, industries and governments alike. Another source of CNCs with potential for commercial scale production are tunicates, a species of marine animal. Tunicate derived CNCs (T-CNCs) are a high aspect ratio CNC, which can complement commercially available W-CNCs in the growing global CNC market. Herein we report the isolation and characterization of T-CNCs from the tunicate Styela clava, an invasive species currently causing significant harm to local aquaculture communities. The reported procedure utilizes scalable CNC processing techniques and is based on our experiences from laboratory scale T-CNC isolation and pilot scale W-CNC isolation. To our best knowledge, this study represents the largest scale where T-CNCs have been isolated from any tunicate species, under any reaction conditions. Demonstrating a significant step towards commercial scale isolation of T-CNCs, and offering a potential solution to the numerous challenges which invasive tunicates pose to global aquaculture communities.

Effect of magnetic field alignment of cellulose nanocrystals in starch nanocomposites: Physicochemical and mechanical properties.

The magnetic field (MF) induced alignment of cellulose nanocrystals (CNC) within a starch matrix is investigated and its effect on the physicochemical and mechanical properties of the nanocomposites are discussed in the paper. Two different kinds of CNC i.e. plant-CNC and tunicate-CNC and its hybrid combination are studied to understand the effect of aspect ratio of CNC on the properties of nanocomposite. Nanocomposites with tunicate sourced CNC showed higher tensile strength and modulus, and lower water vapor permeability as compared to plant sourced CNC. These properties are higher for nanocomposites prepared under MF. The modulus of starch nanocomposites increased from 0.26 GPa and 0.32 GPa to 0.38 GPa and 0.44 GPa, respectively for plant-CNC and tunicate-CNC when exposed to MF. The improved orientation and alignment of CNC in presence of MF is further supported by Raman and scanning electron micrographs studies.

Diatoms embedded, self-assembled carriers for dual delivery of chemotherapeutics in cancer cell lines.

The concept of dual drug delivery to treat relapsing tumors is a well-studied approach to improve the antitumor efficacies and to reduce the side effects of single drug chemotherapeutic treatments. One of the major issues with dual drug delivery to treat drug resistant tumors is the concentration and ratio dependent antagonistic behavior of two drugs, which may reverse the anticancer efficacies of individual chemotherapeutics and stimulate the growth of tumor cells. In this paper, we address this issue by developing diatomaceous earth embedded core shell materials, which are capable of encapsulating two chemotherapeutic drugs at constant molar ratios, in different compartments of a single drug delivery carrier. The encapsulation of each drug in different compartments of delivery carrier (core of diatoms versus shell of cyclodextrin) then controls the release rate of both drugs in situ, and maintains the optimal molar ratios required for their synergistic outcomes in vitro.

Advances in Light-Emitting Dendrimers.

The design of dendrimers with various chromophores has attracted significant attention in light of the dual effect of the luminescence of the chromophores and the morphology of the synthesized dendrimers. Recent developments in this field stem from their wide potential applications, including organic light-emitting diodes, photonic switches and upconversion lasers, as well as sensors and electronic devices. The focus of this comprehensive review is on the design and properties of various classes of light-harvesting dendrimeric materials.

Polymeric Composites with Embedded Nanocrystalline Cellulose for the Removal of Iron(II) from Contaminated Water.

The exponential increase in heavy metal usage for industrial applications has led to the limited supply of clean water for human needs. Iron is one of the examples of heavy metals, which is responsible for an unpleasant taste of water and its discoloration, and is also associated with elevated health risks if it persists in drinking water for a prolonged period of time. The adsorption of a soluble form of iron (Fe2+) from water resources is generally accomplished in the presence of natural or synthetic polymers or nanoparticles, followed by their filtration from treated water. The self-assembly of these colloidal carriers into macroarchitectures can help in achieving the facile removal of metal-chelated materials from treated water and hence can reduce the cost and improve the efficiency of the water purification process. In this study, we aim to develop a facile one-pot strategy for the synthesis of polymeric composites with embedded nanocrystalline cellulose (NCC) for the chelation of iron(II) from contaminated water. The synthesis of the polymeric composites with embedded nanoparticles was achieved by the facile coating of ionic monomers on the surface of NCC, followed by their polymerization, crosslinking, and self-assembly in the form of three-dimensional architectures at room temperature. The composites prepared were analyzed for their physiochemical properties, antifouling properties, and for their iron(II)-chelation efficacies in vitro. The results indicate that the embedded-NCC polymeric composites have antifouling properties and exhibit superior iron(II)-chelation properties at both acidic and basic conditions.

Water recycling efficacies of extremely hygroscopic, antifouling hydrogels.

Water harvesting, reusable, and antifouling hydrogels have found various applications in the fields of nanotechnology, biomedicine, food production and agriculture. These water-releasing materials are generally comprised of hygroscopic natural polymers, such as alginate blended with ionic salts or thermo-responsive moieties, to aid the release of water from a network of hydrogels. In this report, we propose a simple strategy to develop novel, synthetic, hygroscopic hydrogels (in the absence of ionic salts or thermo-responsive moieties), capable of absorbing copious amount of water and allow the facile release of water at ambient temperatures, as a function of crosslinking density of the polymer chains. The first step in the development of hygroscopic hydrogels is the development of hygroscopic vitamin B5 analogous or pantothenic acid analogous monomer (B5AMA), by ring opening chemistry. The hygroscopic hydrogels are then prepared from B5AMA monomer at different cross-linker densities by free radical polymerization approach and are evaluated for their antifouling properties and for their water absorbing and release efficacies, as a function of temperature. The release of significant amount of water by B5AMA hydrogels at physiological temperature (37 °C), their repeated water absorption and desorption behavior and excellent antifouling properties, suggest their potential usage as water harvesting materials in arid regions.

Quaternized and Thiazole-Functionalized Free Radical-Generating Organometallic Dendrimers as Antimicrobial Platform against Multidrug-Resistant Microorganisms.

New macromolecules such as dendrimers are increasingly needed to drive breakthroughs in diverse areas, for example, healthcare. Here, the authors report hybrid antimicrobial dendrimers synthesized by functionalizing organometallic dendrimers with quaternary ammonium groups or 2-mercaptobenzothiazole. The functionalization tunes the glass transition temperature and antimicrobial activities of the dendrimers. Electron paramagnetic resonance spectroscopy reveals that the dendrimers form free radicals, which have significant implications for catalysis and biology. In vitro antimicrobial assays indicate that the dendrimers are potent antimicrobial agents with activity against multidrug-resistant pathogens such as methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus faecium as well as other microorganisms. The functionalization increases the activity, especially in the quaternary ammonium group-functionalized dendrimers. Importantly, the activities are selective because human epidermal keratinocytes cells and BJ fibroblast cells exposed to the dendrimers are viable after 24 h.

Encapsulation of polyanilines into graphite oxide.

Herein we report on the intercalation of polyaniline, poly(2-ethylaniline), and poly(2-propylaniline) into graphite oxide. This was achieved by taking advantage of the exfoliation/reconstruction properties of the layered host. The resulting intercalates were characterized by powder X-ray diffraction and thermogravimetric analysis.