Engineering the surface of Nbn+1CnTx MXenes to versatile bio-activity towards microorganisms.

Two-dimensional (2D) transition metal carbides/nitrides (MXenes) are potential antibacterial agents. However, their activity against microorganisms is not fully understood. It could relate to MXenes' surface which further influences their biocidal action. Herein, we report no continuous biocidal activity for delaminated 2D niobium-based MXenes (Nbn+1XnTx) such as Nb2CTx and Nb4C3Tx prepared with HF/TMAOH protocol. Biocidal activity towards Bacillus subtilis and Staphylococcus aureus microorganisms was achieved by surface-functionalization with lysozyme macromolecule. MXenes' engineering with lysozyme changed MXene's surface charge from negative into positive thus enabling the elimination of bacteria cells during 48 h of incubation. In contrast, Nb4C3Tx functionalized with collagen stimulated the growth of Bacillus subtilis by 225 %, showing MXene's biocompatibility towards this particular strain. Altogether, our results show that MXenes are incredibly bio-tunable. Opposing bio-effects such as antimicrobial or growth-stimulating can be achieved towards various microorganisms with rational surface engineering.

Waste iron as a robust and ecological catalyst for decomposition industrial dyes under UV irradiation.

In an era of increasing environmental awareness, it is very important to work towards eliminating or at least reducing as many harmful industrial substances as possible. However, the implementation of green chemistry methods for wastewater treatment can be difficult especially due to complexity, the high cost of reagents, and the required long process time. This paper focuses on using waste iron (WI) to remove two kinds of amaranth dye commonly used in industry. To enhance the process, UV irradiation and hydrogen peroxide were used. The novelty of the research was the use of efficient and reusable WI as a heterogeneous catalyst in the process. WI material characteristics was done before and after the process using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray fluorescence (XRF). Zeta potential, size characterization, circularity, and direct band gap were also determined. As a result of treatment complete decolorization of both dyes was achieved, as well as 99% absorbance removal after 15-min process time. The total organic carbon (TOC) decrease after 60-min process time was in the range from 86.6 to 89.8%. Modified pseudo-second-order reaction reflects obtained results of treatment efficiency. Treatment results, confirmed by WI material characterization, indicate satisfactory stability of the catalyst and good oxidation capacity.

Photocatalytic Activity of the Oxidation Stabilized Ti3 C2 Tx MXene in Decomposing Methylene Blue, Bromocresol Green and Commercial Textile Dye.

Two-dimensional MXenes are excellent photocatalysts. However, their low oxidation stability makes controlling photocatalytic processes challenging. For the first time, this work elucidates the influence of the oxidation stabilization of model 2D Ti3 C2 Tx MXene on its optical and photocatalytic properties. The delaminated MXene is synthesized via two well-established approaches: hydrofluoric acid/tetramethylammonium hydroxide (TMAOH-MXene) and minimum intensive layer delamination with hydrochloric acid/lithium fluoride (MILD-MXene) and then stabilized by L-ascorbic acid. Both MXenes at a minimal concentration of 32 mg L-1 show almost 100% effectiveness in the 180-min photocatalytic decomposition of 25 mg L-1 model methylene blue and bromocresol green dyes. Industrial viability is achieved by decomposing a commercial textile dye having 100 times higher concentration than that of model dyes. In such conditions, MILD-MXene is the most efficient due to less wide optical band gap than TMAOH-MXene. The MILD-MXene required only few seconds of UV light, simulated white light, or 500 nm (cyan) light irradiation to fully decompose the dye. The photocatalytic mechanism of action is associated with the interplay between surface dye adsorption and the reactive oxygen species generated by MXene under light irradiation. Importantly, both MXenes are successfully reused and retained approximately 70% of their activity.

Application of Micron-Sized Zero-Valent Iron (ZVI) for Decomposition of Industrial Amaranth Dyes.

Dyes are highly toxic and persistent in the environment. Their presence in water causes environmental and social problems. Dyes must be effectively removed from the water. A UV/ZVI/H2O2 process was applied to decompose two organic dyes, AM E123 and AM ACID. A commercial ZVI product, Ferox Flow, was used, and its properties were determined using SEM and XRF. The zeta potential, surface area, and optical properties of ZVI were also determined. The efficiency of dye removal in optimal conditions was 85.5% and 80.85% for AM E123 and AM ACID, respectively. Complete decolorization was observed in all samples. The decomposition of both dyes occurred according to a modified pseudo-second-order reaction and there was a statistically significant correlation between the TOC decrease, pH, and process time. The catalyst was observed to have high stability, and this was not affected by the performance of the treatment process even after the third cycle, as confirmed by the results of the catalyst surface analysis and iron diffusion test. Slight differences in process efficiency were observed after each cycle. The need for only a small amount of catalyst to decompose AM E123 and AM ACID, coupled with the ability to reuse the catalyst without the need for prior preparation, may reduce catalyst purchase costs.

Understanding the mechanism of Nb-MXene bioremediation with green microalgae.

Rapidly developing nanotechnologies and their integration in daily applications may threaten the natural environment. While green methods of decomposing organic pollutants have reached maturity, remediation of inorganic crystalline contaminants is major problem due to their low biotransformation susceptibility and the lack of understanding of material surface-organism interactions. Herein, we have used model inorganic 2D Nb-based MXenes coupled with a facile shape parameters analysis approach to track the mechanism of bioremediating 2D ceramic nanomaterials with green microalgae Raphidocelis subcapitata. We have found that microalgae decomposed the Nb-based MXenes due to surface-related physicochemical interactions. Initially, single and few-layered MXene nanoflakes attached to microalgae surfaces, which slightly reduced algal growth. But with prolonged surface interaction, the microalgae oxidized MXene nanoflakes and further decomposed them into NbO and Nb2O5. Since these oxides were nontoxic to microalgal cells, they consumed Nb-oxide nanoparticles by an uptake mechanism thus enabling further microalgae recovery after 72 h of water treatment. The uptake-associated nutritional effects were also reflected by cells' increased size, smoothed shape and changed growth rates. Based on these findings, we conclude that short- and long-term presence of Nb-based MXenes in freshwater ecosystems might cause only negligible environmental effects. Notably, by using 2D nanomaterials as a model system, we show evidence of the possibility of tracking even fine material shape transformations. In general, this study answers an important fundamental question about the surface interaction-associated processes that drive the mechanism of 2D nanomaterials' bioremediation as well as provides the fundamental basis for further short- and long-term investigations on the environmental effects of inorganic crystalline nanomaterials.

2D MBenes: A Novel Member in the Flatland.

2D MBenes, early transition metal borides, are a very recent derivative of ternary or quaternary transition metal boride (MAB) phases and represent a new member in the flatland. Although holding great potential toward various applications, mainly theoretical knowledge about their potential properties is available. Theoretical calculations and preliminary experimental attempts demonstrate their rich chemistry, excellent reactivity, mechanical strength/stability, electrical conductivity, transition properties, and energy harvesting possibility. Compared to MXenes, MBenes' structure appears to be more complex due to multiple crystallographic arrangements, polymorphism, and structural transformations. This makes their synthesis and subsequent delamination into single flakes challenging. Overcoming this bottleneck will enable a rational control over MBenes' material-structure-property relationship. Innovations in MBenes' postprocessing approaches will allow for the design of new functional systems and devices with multipurpose functionalities thus opening a promising paradigm for the conscious design of high-performance 2D materials.

The 10th anniversary of MXenes: Challenges and prospects for their surface modification toward future biotechnological applications.

A broad family of two-dimensional (2D) materials - carbides, nitrides, and carbonitrides of early transition metals, called MXenes, became a newcomer in the flatland at the turn of 2010 and 2011 (over ten years ago). Their unique physicochemical properties made them attractive for many applications, highly boosting the development of various fields, including biotechnological. However, MXenes' functional features that impact their bioactivity and toxicity are still not fully well understood. This study discusses the essentials for MXenes's surface modifications toward their application in modern biotechnology and nanomedicine. We survey modification strategies in context of cytotoxicity, biocompatibility, and most prospective applications ready to implement in medical practice. We put the discussion on the material-structure-chemistry-property relationship into perspective and concentrate on overarching challenges regarding incorporating MXenes into nanostructured organic/inorganic bioactive architectures. It is another emerging group of materials that are interesting from the biomedical point of view as well. Finally, we present an influential outlook on the growing demand for future research in this field.

Biological and Corrosion Evaluation of In Situ Alloyed NiTi Fabricated through Laser Powder Bed Fusion (LPBF).

In this work, NiTi alloy parts were fabricated using laser powder bed fusion (LBPF) from pre-alloyed NiTi powder and in situ alloyed pure Ni and Ti powders. Comparative research on the corrosive and biological properties of both studied materials was performed. Electrochemical corrosion tests were carried out in phosphate buffered saline at 37 °C, and the degradation rate of the materials was described based on Ni ion release measurements. Cytotoxicity, bacterial growth, and adhesion to the surface of the fabricated coupons were evaluated using L929 cells and spherical Escherichia coli (E. coli) bacteria, respectively. The in situ alloyed NiTi parts exhibit slightly lower corrosion resistance in phosphate buffered saline solution than pre-alloyed NiTi. Moreover, the passive layer formed on in situ alloyed NiTi is weaker than the one formed on the NiTi fabricated from pre-alloyed NiTi powder. Furthermore, in situ alloyed NiTi and NiTi made from pre-alloyed powders have comparable cytotoxicity and biological properties. Overall, the research has shown that nitinol sintered using in situ alloyed pure Ni and Ti is potentially useful for biomedical applications.

A Review on Development of Ceramic-Graphene Based Nanohybrid Composite Systems in Biological Applications.

Graphene-based nanocomposites constitute an interesting and promising material for various applications. Intensive progress in the development of this group of materials offers an opportunity to create new systems useful for drinking water decontamination or other biotechnological applications. Nanohybrid structures of graphene-ceramic systems can be obtained using covalent graphene surface modification with nanoparticles (NPs) of ceramic and/or co-deposition of metals with selected morphology and chemistry. The present paper systematizes the associated bio-related knowledge and inspires future development of graphene/NPs systems. Emerging knowledge and unique research techniques are reviewed within designing the required nanocomposite structure and chemical composition, development and optimization of new methods of covalent surface modification of graphene with NPs as well as analysis of mechanisms governing the formation of covalent bonding. Further, innovative research tools and methodologies are presented regarding the adjustment of functionalities of materials used for the application in drinking water decontamination or biocidal composites. This study provides a comprehensive base for rational development of more complex, hybrid graphene-based nanomaterials with various bio-functionalities that can be further applied in industrial practice.

Filtration Materials Modified with 2D Nanocomposites-A New Perspective for Point-of-Use Water Treatment.

Point-of-use (POU) water treatment systems and devices play an essential role in limited access to sanitary safe water resources. The filtering materials applied in POU systems must effectively eliminate contaminants, be readily produced and stable, and avoid secondary contamination of the treated water. We report an innovative, 2D Ti3C2/Al2O3/Ag/Cu nanocomposite-modified filtration material with the application potential for POU water treatment. The material is characterized by improved filtration velocity relative to an unmodified reference material, effective elimination of microorganisms, and self-disinfecting potential, which afforded the collection of 99.6% of bacteria in the filter. The effect was obtained with nanocomposite levels as low as 1%. Surface oxidation of the modified material increased its antimicrobial efficiency. No secondary release of the nanocomposites into the filtrate was observed and confirmed the stability of the material and its suitability for practical application in water treatment.

Multifunctional carbon-supported bioactive hybrid nanocomposite (C/GO/NCP) bed for superior water decontamination from waterborne microorganisms.

Achieving both effective and sustainable water decontamination technology requires development of a universal filtration solution. However, effective removal of natural waterborne microorganisms still remains a challenge. The use of nanoparticles in water filters is promising but also leads to problems with their efficiency and safety. To cross these bottlenecks, we have designed a novel multifunctional carbon-supported bioactive hybrid nanocomposite filtration bed. For this purpose, we took advantage of granular activated carbon (C), graphene oxide (GO) and bioactive Al2O3/Ag nanocomposite particles (NCP). These components were assembled into a hybrid nanocomposite structure using facile in situ surface decoration via a sol-gel approach. This obtained C/GO/NCP filtration bed was thoroughly characterized in terms of morphology, structure and surface properties as well as further evaluated for tap water filtration efficiency. Analysis of the preferential sites for bacteria adsorption and biological tests under close-to-real static and dynamic filtration conditions has proved C/GO/NCP's efficiency in eliminating model and natural strains of waterborne microorganisms. At the same time, nanoparticles were not released into the filtrate, which confirmed material stability and safety. We have also revealed that C/GO/NCP nanofiltration bed was self-sterilizing which means that it entirely eliminated up to 100% of the filtered bacteria cells within short periods of contact time. What is more, the low-temperature thermal regeneration allowed recovering the assumed properties. In general, the obtained results indicate a breakthrough in designing hybrid-structured filtration beds that can be easily synthesized and safely used for drinking water decontamination.

Generalized Additive Mixed Modeling of Longitudinal Tumor Growth Reduces Bias and Improves Decision Making in Translational Oncology.

Scientists working in translational oncology regularly conduct multigroup studies of mice with serially measured tumors. Longitudinal data collected can feature mid-study dropouts and complex nonlinear temporal response patterns. Parametric statistical models such as ones assuming exponential growth are useful for summarizing tumor volume over ranges for which the growth model holds, with the advantage that the model's parameter estimates can be used to summarize between-group differences in tumor volume growth with statistical measures of uncertainty. However, these same assumed growth models are too rigid to recapitulate patterns observed in many experiments, which in turn diminishes the effectiveness of their parameter estimates as summary statistics. To address this problem, we generalized such models by adopting a nonparametric approach in which group-level response trends for logarithmically scaled tumor volume are estimated as regression splines in a generalized additive mixed model. We also describe a novel summary statistic for group level splines over user-defined, experimentally relevant time ranges. This statistic reduces to the log-linear growth rate for data well described by exponential growth and also has a sampling distribution across groups that is well approximated by a multivariate Gaussian, thus facilitating downstream analysis. Real-data examples show that this nonparametric approach not only enhances fidelity in describing nonlinear growth scenarios but also improves statistical power to detect interregimen differences when compared with the simple exponential model so that it generalizes the linear mixed effects paradigm for analysis of log-linear growth to nonlinear scenarios in a useful way. SIGNIFICANCE: This work generalizes the statistical linear mixed modeling paradigm for summarizing longitudinally measured preclinical tumor volume studies to encompass studies with nonlinear and nonmonotonic group response patterns in a statistically rigorous manner.

Structural elucidation of specific noncovalent association of folic acid with native cyclodextrins using an ion mobility mass spectrometry and theoretical approach.

The combination of ion mobility mass spectrometry studies and theoretical calculations including docking studies permitted a detailed structural description of noncovalent complexes of folic acid (FA) and native cyclodextrins (α-CD, ß-CD, and γ-CD). The mode of noncovalent association depended on the cavity size of the cyclodextrin. The structure of FA/α-CD represented the exclusion complex in which the aminobenzoic moiety and the aromatic pteridine ring of folic acid remain outside the cyclodextrin cavity, while the glutamate residue is anchored in the interior of the α-cyclodextrin. A rotaxane-type structure was proposed for the FA/ß-CD complex with the aminobenzoic part of FA being trapped in the central cavity of ß-CD. The glutamate residue and the aromatic pteridine ring interact with the primary and secondary rim hydroxyl residues, respectively, enhancing complex stability. Two possible structures of FA/γ-CD were suggested, the first one being analogous to the FA/ß-CD complex and the second one being more stable-in which the aromatic pteridine ring penetrates into the CD cavity while the glutamate residue with the aminobenzoic part of FA is exposed to the cone exterior of CD at its wider edge. Further insight into the association behavior of the folic acid toward cyclodextrins evaluated by thermodynamic calculations indicates that the process is highly exothermic. The complex stability increased in the order FA/α-CD < FA/ß-CD < FA/γ-CD. This order is consistent with the previously determined relative gas-phase stability established based on the dissociation efficiency curves of the FA/CD complexes.