Wet Chemistry Research Articles

Preparation of Nonfouling Zwitterionic Coatings by Plasma-Enhanced Chemical Vapor Deposition under Ambient Pressure.

Nonspecific protein adsorption significantly impacts the performance of biomedical devices in both hemocompatibility and tissue compatibility. Polyzwitterionic coatings are a promising solution. However, conventional zwitterionic coatings always have to rely on sophisticated wet chemistry methods, leading to low controllability and high cost. In this work, zwitterionic coatings were prepared by nitrogen plasma-enhanced chemical vapor deposition (PECVD) of precursors for 90 s under ambient pressure followed by hydrolysis. The results showed that the PECVD-coated thermoplastic polyurethane (TPU), Tecoflex, effectively resists nonspecific protein adsorption, platelet adhesion, and bacterial adhesion without changing the mechanic properties of TPU. This approach simplified the zwitterionic coating process with highly controllability, showing a promising potential for the surface modification of biomedical devices.

Experimental investigation of pool boiling on Ti-Cu composite coated surfaces prepared using Electric Discharge Coating

Boiling heat transfer has become a very potent two-phase heat transfer mechanism for cooling high heat-producing devices such as microelectronic devices, fusion reactors or turbine blades. Increasing research has shown that micro/nano-structures on surfaces increase the number of nucleation sites for bubble formation, which ultimately results in a major improvement in boiling performance. This led to studies on developing various coated surfaces in order to generate micro/nano-structures on surfaces. In the current study, microstructured boiling surfaces were prepared using the Electric Discharge Coating (EDC) process. Titanium-copper (Ti-Cu) composite microparticles were coated on copper surface under reverse polarity in the Electric Discharge Machine. Four surfaces were prepared by using current settings of 3 A, 4 A, 5 A and 6 A. It was followed by characterisation of the surfaces which included, wettability analysis, porosity, pore size estimation, mean roughness measurement and elemental analysis, in order to better understand the boiling results on the surfaces. The surfaces formed were hydrophilic in nature, with contact angles varying from 47° to 65°. Pool boiling were performed with the developed surfaces and critical heat flux (CHF) and nucleate boiling heat transfer coefficient (NBHTC) improvement of 37.17 % and 172 % respectively were observed with the best performing surface compared to the bare surface. The best performing surface was also compared with relevant published literature to determine its standing against the present state of the art.

NIR spectroscopy prediction model for capsaicin content estimation in chilli: A rapid mining tool for trait-specific germplasm screening

Chilli is a widely produced crop, highly valued for its capsaicin content, a key economic trait. Traditional wet chemistry methods for estimating capsaicin are time-taking and laborious, while non-destructive methods like NIRS coupled with chemometrics, offer efficient alternatives, simplifying and accelerating biochemical assessments. This study is the first to develop and validate and tested for applicability of NIRS-based prediction model for capsaicin content in Indian chilli germplasm using MPLS regression. Various mathematical treatments were performed, and the most suited model was selected based on high RSQexternal, RPD and lower SEP values in the external validation set, indicating strong prediction accuracy and minimal error. The model achieved high RSQexternal value of 0.808, RPD value of 2.088 and low SEP value of 3.415 for capsaicin content, demonstrating excellent prediction performance. A paired sample t-test p-value of 0.757 (p > 0.05) showed non-significant difference between wet lab and predicted values, confirming the model’s accuracy. The applicability of the model was validated on fresh harvest germplasm the following year, showing a higher reliability score of 0.949, further confirming model’s reliability. This model would aid in high-throughput, accurate screening of chilli germplasm for capsaicin, accelerating chilli crop improvement programs and the development of new high-capsaicin varieties.

Techno-Economic Analysis of Near-Infrared (NIR) Systems at Feed Millsas a Low-Cost, High-Speed Alternative to Feed Ingredient Testing

Improperly balanced diets not only impact the quality of animal production but also the profits of a livestock operation. Typically, the nutrient and chemical content of feed ingredients and forages are determined using well-established wet chemistry tests. However, these tests can be expensive and time-consuming. Moreover, the increasing use of various by-products which are known to have large variations in chemical and nutrient content warrants a real-time on-site feed and forage testing system. Near infrared (NIR) spectroscopy systems are quick and effective on-site testing tools. While NIR systems are being adopted for on-farm or at feed mill ingredient and forage testing, little is known about the economic impacts of such an investment for a livestock or feed mill operator. This study developed a baseline model and an Excel based spreadsheet application for performing Return on Investment (ROI) analysis to determine the feasibility of using an on-farm or at feed mill NIR testing system. ROI was calculated based on the nutrient cost saved or spent determined from the difference of estimated nutrient content and actual calculated value. The findings from this study will promote low-cost alternatives for onfarm or at feed mill ingredient testing, positively impacting quality of animal products and minimizing costs.

High entropy alloys mediated formation of multi-oxide nanoparticles on carbon fiber cloths and their synergistic effects in electrochemical performance

A wet chemistry technique is developed to produce high entropy alloy nanoparticles on carbon fibers. Coatings display solution phase and can be aerially oxygenated into multi-oxides. Electrochemical measurements confirm the generation of high specific capacitance from multi-oxide coatings where individual components show redox reactions at different potentials thus producing large loops of charge–discharge. Comparative study confirms synergistic effects arising from individual oxides in coatings.

Thickness dependent crystallinity, hydrophilicity, and surface microtexture in CaF2 thin films deposited via thermal evaporation method

This study investigates the deposition and characterization of CaF₂ thin films with thicknesses ranging from 40 to 320 nm, fabricated via thermal evaporation onto glass substrates. X-ray diffractometry (XRD) revealed that increased film thickness leads to enhanced crystallinity, with larger crystallite sizes and reduced lattice strain. Wettability analysis demonstrated a transition from hydrophobic behavior (contact angle ∼70° for 40 nm) to hydrophilic behavior (contact angle ∼52° for 320 nm) as film thickness increased. Surface morphology, examined via atomic force microscopy (AFM), showed a significant reduction in surface roughness in thicker films, with smoother, more coalesced surfaces observed for films over 160 nm. Monofractal analysis further confirmed the evolution of surface microtexture, with thicker films exhibiting higher uniformity and reduced surface complexity. These findings provide critical insights into optimizing CaF₂ thin films for applications in optics, electronics, and surface coatings, where improved crystallinity and surface properties are essential.

Opal‐Inspired SiO2‐Mediated Carbon Dot Doping Enables the Synthesis of Monodisperse Multifunctional Afterglow Nanocomposites for Advanced Information Encryption

AbstractDespite recent advancements in inorganic and organic phosphors, creating monodisperse afterglow nanocomposites (NCs) remains challenging due to the complexities of wet chemistry synthesis. Inspired by nanoinclusions in opal, we introduce a novel SiO2‐mediated carbon dot (CD) doping method for fabricating monodisperse, multifunctional afterglow NCs. This method involves growing a SiO2 shell matrix on monodisperse nanoparticles (NPs) and doping CDs into the SiO2 shell under hydrothermal conditions. Our approach preserves the monodispersity of the parent NP@SiO2 NCs while activating a green afterglow in the doped CDs with an impressive lifetime of 1.26 s. Additionally, this method is highly versatile, allowing for various core and dopant combinations to finely tune the afterglow through core‐to‐CD or CD‐to‐dye energy transfer. Our findings significantly enhance the potential of SiO2 coatings, transforming them from merely enhancing the biocompatibility of NCs to serving as a versatile matrix for emitters, facilitating afterglow generation and paving the way for new applications.

Opal-Inspired SiO2-Mediated Carbon Dot Doping Enables the Synthesis of Monodisperse Multifunctional Afterglow Nanocomposites for Advanced Information Encryption.

Despite recent advancements in inorganic and organic phosphors, creating monodisperse afterglow nanocomposites (NCs) remains challenging due to the complexities of wet chemistry synthesis. Inspired by nanoinclusions in opal, we introduce a novel SiO2-mediated carbon dot (CD) doping method for fabricating monodisperse, multifunctional afterglow NCs. This method involves growing a SiO2 shell matrix on monodisperse nanoparticles (NPs) and doping CDs into the SiO2 shell under hydrothermal conditions. Our approach preserves the monodispersity of the parent NP@SiO2 NCs while activating a green afterglow in the doped CDs with an impressive lifetime of 1.26 s. Additionally, this method is highly versatile, allowing for various core and dopant combinations to finely tune the afterglow through core-to-CD or CD-to-dye energy transfer. Our findings significantly enhance the potential of SiO2 coatings, transforming them from merely enhancing the biocompatibility of NCs to serving as a versatile matrix for emitters, facilitating afterglow generation and paving the way for new applications.

Metal-Free Wet Chemistry for the Fast Gram-Scale Synthesis of γ-Graphyne and its Derivatives.

γ-Graphyne (GY), an emerging carbon allotrope, is envisioned to offer various alluring properties and broad applicability. While significant progress has been made in the synthesis of GY over recent decades, its widespread application hinges on developing efficient, scalable, and accessible synthetic methods for the production of GY and its derivatives. Here we report a facile metal-free nucleophilic crosslinking method using wet chemistry for fast gram-scale production of GY and its derivatives. This synthesis method involves the aromatic nucleophilic substitution reactions between fluoro-(hetero)arenes and alkynyl silanes in the presence of a catalytic amount of tetrabutylammonium fluoride, where the fluoride plays a crucial role in removing protective groups from alkynyl silanes and generating reactive alkynylides. Our comprehensive analysis of the as-prepared GY reveals a layered structure, characterized by the presence of the C(sp)-C(sp2) bond. The synthetic strategy shows remarkable tolerance to various functional groups and enables the preparation of diverse F-/N-rich GY derivatives, using electron-deficient fluoro-substituted (hetero)arenes as precursors. The feasibility of producing GY and derivatives from fluorinated (hetero)arenes through the metal-free, scalable, and cost-effective approach paves the way for broad applications of GY and may inspire the development of new carbon materials.

Seasonal and Climatic Drivers of Wet Deposition Organic Matter at the Continental Scale

AbstractDissolved organic matter (DOM) concentrations and composition within wet deposition are rarely monitored despite contributing a large input of bioavailable dissolved organic carbon (DOC) and nitrogen (DON) to the Earth's surface. Lacking from the literature are spatially comprehensive assessments of simultaneous measurements of wet deposition DOC and DON chemistry and their dependencies on metrics of climate and environmental factors. Here, we use archived precipitation samples from the US National Atmospheric Deposition Program collected in 2017 to 2018 from 17 sites across six ecoregions to investigate variability in the concentration and composition of depositional DOM. We hypothesize metrics of DOM chemistry vary with ecoregion, season, large‐scale climate drivers, and precipitation geographic source. Findings indicate differences in DOC and DON concentrations and loads among ecoregions. The highest wet deposition concentrations are from sites in the Northern Forests and lowest concentrations from sites in Marine West Coast Forests. Summer and autumn samples contained the highest DOC concentrations and DON concentrations that were consistently above detection limit, corresponding with seasonality of peak air temperatures and the phenology of the growing season in the northern hemisphere. Compositional trends suggest lighter DOM molecules in autumn and winter and heavier molecules in spring and summer. Climate drivers explain 51% of variation in DOM chemistry, revealing differing drivers on the concentrations and loads of DOC versus DON in wet deposition. This study highlights the necessity of incorporating DOC and DON measurements into national deposition monitoring networks to understand spatial and temporal feedbacks between climate change, atmospheric chemistry and landscape biogeochemistry.

Effects of long-term nitrogen and phosphorus fertilization on soil phosphorus forms and dynamics under continuous wheat production in Saskatchewan, Canada

Many agricultural crops require both nitrogen (N) and phosphorus (P) fertilizers to sustain crop yields. However, long-term application of NH4–N fertilizers can cause soil acidification, which alters soil abiotic and biotic processes, including soil P dynamics. Long-term continuous wheat plots in Saskatchewan, Canada, were used to assess effects of N and P fertilization from 1967 and P fertilizer cessation in subplots from 1995. General soil chemical properties and soil P pools and forms were determined and then correlated with soil pH, total N (TN), and total P (TP) concentrations to show the relative importance on soil P dynamics of (a) crop nutrition (TN and TP); (b) soil acidification (pH); or (c) P fertilization/cessation. Fertilization with NH4–N decreased soil pH and altered exchangeable cation concentrations; however, long-term crop growth was poor in no-N plots and was best with both N and P fertilizers, in turn increasing soil carbon and organic matter. Applying P fertilizers without N increased soluble phosphates and the risk of P losses in runoff. Soil organic P (TPo) concentrations were correlated negatively to pH and positively to TN, but the concentrations of P compounds were not correlated to pH. This suggests that TPo accumulation may be from increased long-term crop residue inputs from crops with N and P fertilizers, rather than increased sorption from reduced pH. However, soil pH will continue to decrease with continued NH4–N fertilization, affecting soil chemistry and future P cycling; monitoring with a suite of wet chemistry and spectroscopic techniques is recommended.

Relationship between Xylene Solubles and Crystallization Elution Fractionation of Polypropylene.

The Xylene Soluble (XS) is one of the most important parameters closely related to the performance of polypropylene (PP) materials. In order to obtain precise and accurate XS data, ASTM D 5492-17, based on the wet chemistry separation mechanism, strictly specifies each and every step of the procedure, such as a glassware setup, heating and cooling rates, etc. Meanwhile, crystallization elution fractionation (CEF), a newly developed technique, is capable of quantifying polyolefin structural regularity and comonomer distribution in a fast and automated manner. There have been a few pieces of preliminary work aiming to provide XS value from the CEF test with a limited number of samples. It is important to gain deep insights into the relationship between XS and the purge fraction of CEF by studying a large number of diverse polypropylene materials. In this paper, close to 300 commercial polypropylene and/or homemade polypropylene, both homopolypropylene (hPP) and propylene-ethylene copolymers (P/E) made with various catalysts under different conditions, were employed. XS values were obtained via CRYSTEX QC calibration. It was found that XS and the soluble fraction (SF) from CEF yielded a linear relationship with R 2 = 0.9942. This linearity is applicable regardless of polymer types, which can differ significantly in terms of molecular weight distribution, tacticity, chemical composition, and melt flow rate. One of the prominent advantages of using the CEF test instead of ASTM D 5492-17 is the elimination of the time-consuming procedure for much-improved precision and high productivity. In addition, the catalytic system was found to have an influence on SF and crystalline fractions of copolymers.

Growth of zinc oxide nanowires by a hot water deposition method.

Recently, various methods have been developed for synthesizing zinc oxide (ZnO) nanostructures, including physical and chemical vapor deposition, as well as wet chemistry. These common methods require either high temperature, high vacuum, or toxic chemicals. In this study, we report the growth of zinc oxide ZnO nanowires by a new hot water deposition (HWD) method on various types of substrates, including copper plates, foams, and meshes, as well as on indium tin oxide (ITO)-coated glasses (ITO/glass). HWD is derived from the hot water treatment (HWT) method, which involves immersing piece(s) of metal and substrate(s) in hot deionized water and does not require any additives or catalysts. Metal acts as the source of metal oxide molecules that migrate in water and deposit on the substrate surface to form metal oxide nanostructures (MONSTRs). The morphological and crystallographic analyses of the source-metals and substrates revealed the presence of uniformly crystalline ZnO nanorods after the HWD. In addition, the growth mechanism of ZnO nanowires using HWD is discussed. This process is simple, inexpensive, low temperature, scalable, and eco-friendly. Moreover, HWD can be used to deposit a large variety of MONSTRs on almost any type of substrate material or geometry.

Efficient flotation separation approach of apatite from calcite for phosphate up-grading using phosphorylated starch macromolecules as a selective depressant

Physico-chemical similarities of surface proprieties of calcite and apatite make their separation challenging. Effective flotation separation requires sustainable depressants to mitigate environmental consequences associated with traditional chemical reagents. Here, for the first time we explore the potential of phosphorylated starch (PS) derived from potato waste as a green and effective depressant. Starch was modified using a straightforward phosphorylation process, resulting in PS with a remarkable charge density exceeding 6000 mmol kg−1. The PS was then evaluated for its ability to depress apatite, enhancing the separation efficiency of apatite from calcite in phosphate rock beneficiation via reverse flotation. Micro-flotation experiments revealed PS's distinct depression effect on apatite while minimally impacting calcite. Floatability rates of apatite and calcite were 90.45 % and 92.68 %, respectively. Introducing 10 mg/g PS drastically reduced apatite recovery to <19 %, while calcite recovery remained at 78.80 %. The bench-scale flotation tests demonstrated an upgrading of the phosphate rock to 70,64 % Bone Phosphate of Lime (BPL) with a yield of 89,41 %. Mechanistic studies employing zeta potential (ZP), and wettability analysis elucidated the depression mechanism. Apatite retained hydrophilicity post-PS addition and conditioning with ester, while calcite-acquired hydrophobicity even in the presence of PS. Furthermore, PS exhibited substantial adsorption onto the apatite surface through chemical reactions involving the phosphate groups and the activated calcium sites on the apatite. Overall, PS stands out as a promising, eco-friendly, and remarkably efficient depressant for separating apatite from calcite through flotation.

Assessing the role of seawater in the flotation behavior of chalcopyrite and sphalerite

ABSTRACT In seawater flotation, some chemical properties of seawater affect the flotation separation of chalcopyrite and sphalerite. Using seawater instead of fresh water to separate copper – zinc can save fresh water resources and reduce lime consumption, which has broad prospects in terms of economic and environmental protection. In this paper, the flotation separation behavior of chalcopyrite and sphalerite in seawater was tested and the mechanism was analyzed. As a contrast, the copper grade of concentrate in seawater flotation declined from 23.7% to 22.6%. Meanwhile, the recovery of chalcopyrite declined from 66.2% to 42.8% and the SI value declined from 2.210 to 1.599. With the addition of sodium hexametaphosphate, sodium silicate and EDTA, the SI value increased from 1.599 to 2.176, 2.238 and 2.096, respectively. Nevertheless, when EDTA was excessive, the SI value was only 1.998. This indicated that excessive EDTA is unfavorable to flotation separation of chalcopyrite from sphalerite. Wettability analysis, zeta potential analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, density functional theory calculation and E-DLVO calculation verified the flotation separation behavior and revealed the mechanism.

Response of aquatic ecosystems multi-trophic biological communities under multiple pollutants stress

Industrialization has significantly polluted the Yangtze River Basin, posing phenolic compounds and heavy metals that threaten ecological and human health. This study comprehensively evaluated the impact of these pollutants on the Yangtze River's aquatic ecosystems across multiple trophic levels. Sampling from 84 sites during both dry and wet seasons, water chemistry and biological data were analyzed by advanced molecular and statistical techniques. All organisms are divided into three ecological functional groups with a multitrophic level structure based on their co-occurrence. Our results demonstrate pronounced spatial and seasonal variations in pollutant concentrations, with notable sensitivity in ecological structures to phenolic compounds and heavy metals. The ecological impacts of pollutants are more readily observable (up to 43.1 % maximum) when assessing ecological communities based on functional groups with multi-trophic biological community as opposed to traditional taxonomic classifications. All the data used to develop a predictive model for ecological functional groups, achieving an accuracy rate of 86.1 %. This research provides critical insights into the multi-trophic effects of composite pollution, advocates for the adoption of comprehensive multi-trophic evaluation methods in large-scale ecological monitoring and sustainable watershed management globally.

Determination of the Redox Ratio of Iron in a Diamagnetic Matrix Using Low-Field NMR Relaxometry.

Proton nuclear magnetic resonance (NMR) relaxometry is proposed to determine the iron redox ratio of slag samples. It depends on the paramagnetic effect on bulk water relaxation times. Experiments have been carried out to calibrate the relationship between the concentration of Fe3+ and Fe2+ ions and the measured relaxation times on prepared standard samples. It is shown that Fe2+ ions have very different effects on the relaxation times than Fe3+ ions. For the solid slag samples, digestion in an acid was used to produce solutions with a pH of 1.0. Hydrogen peroxide (H2O2) was then added to the digested samples to oxidize Fe2+ ions to Fe3+ ions. The concentration of Fe2+ and Fe3+ ions in solution can be calculated by measuring the relaxation times before and after oxidation. The Fe3+/∑Fe ratio of slag samples was also investigated by wet chemistry and 57Fe Mössbauer spectroscopy and calculated by FactSage at the equilibrium state. The results obtained from different methods are consistent, indicating that this NMR relaxometry method is reliable.

Trace Amount of Ir Decorated NiFe Phosphide In-Situ Grown on Carbon Cloth as Cost-Effective Electrocatalyst for Oxygen Evolution Reaction.

Cost-effective electrocatalysts is a key constituent to establish the balance of cost and catalytic efficiency for oxygen evolution reaction (OER) via water electrolysis in the area of energy conversion and storage. NiFe phosphide decorated with trace amount of iridium (Ir) species in-situ grown on carbon cloth was prepared by a facile wet chemistry approach followed by a phosphorization post-treatment at a relative low temperature. The optimal electrocatalyst, Ir2-NiFePx/CC, exhibits excellent OER activity, with an low overpotential of 190 mV at 10 mA cm-2 for alkaline OER, and a desirable long-term durability over 90 h. The outstanding OER performance stems from the structural evolution via phosphorization process, Ir decoration with more high-valence stated Ir4+ species, and tight connection between individual components of the electrode, which gives rise to the strong activity to the active sites and faster reaction kinetics in the alkaline OER process. Mover, the Ir loading was as low as approximately ~1.7 wt % (0.29 mg cm-2), showing promissing propective in cost-effective OER.

Characterization of Mechanical Properties and Surface Wettability of Epoxy Resin/Benzoxazine Composites in a Simulated Acid Rain Environment

Despite the robustness of thermosetting coatings in various applications, prolonged exposure to acidic environments can cause gradual deterioration, leading to structural or functional damage. This study investigates composite materials comprised of cycloaliphatic epoxy resin (CER) and benzoxazine (BZ) at three different weight ratios: 50:50, 25:75, and 0:100. These composites were exposed to nitric acid, simulating acid rain, for durations ranging from 1 to 5 h. The specimens were characterized for weight change, mechanical properties (flexural strength and short beam strength), and surface properties (contact angle and contact angle hysteresis). Although minimal changes in the physical and mechanical properties of both homopolymer and copolymer composites were detected after short acid exposure (up to 5 h), surface wettability analysis via static contact angle and contact angle hysteresis revealed more pronounced deterioration. The static contact angle decreased by 24.96% and 28.32% for homopolymer BZ and copolymer BZ-CER composites, respectively. Contact angle hysteresis increased by 19.39% and 27.80% for 5 h acid-exposed homopolymer BZ and copolymer CER, respectively. This study underscores the utility of surface wettability analysis as a valuable tool for monitoring deterioration from acidic aging in polymers, particularly in BZ-CER systems used in structural and high-performance applications.

Design and development of large-diameter Mg-Zn-Ca bulk metallic glass for biomedical applications: A mechanical and corrosion perspective

Being amorphous, bulk metallic glasses (BMGs) exhibit superior properties compared to their crystalline alloy counterparts. Amorphous materials are preferred for their excellent mechanical and degradation behavior. Among the various elemental combinations, MgZnCa has shown the most promising results, as evidenced by the literature. However, the maximum achievable size of the metallic glasses remains a bottleneck. The current work aims to address this challenge and achieve it splendidly with a systematic methodology by developing larger diameter MgZnCa BMGs through vacuum induction casting using a specially designed copper mold. The optimal composition was formalized for glass formation of the Mg65Zn31Ca4 system using the CALPHAD technique. As a result, a 6.5 mm diameter glassy alloy was successfully obtained. The XRD and TEM analysis experiments demonstrated a perfect amorphous structure of the developed sample. The anti-corrosion properties of the as-cast glass increased, followed by enhancement in the yield strength and hardness in contrast to the properties of the human bone. Furthermore, the surface wettability analysis showed an adequate surface obtained to promote fibroblast adhesion. In conclusion, the current work represents a notable progress in the fabrication of larger-diameter MgZnCa BMG for biomedical applications, considering that the biggest diameter ever reported in the MgZnCa system was more than a decade ago.