Hydrogeochemical facies and pollution status of groundwater resources of Owerri and environs, Southeastern Nigeria.

The aim of the study was to assess the status of groundwater quality of Owerri and environs, for drinking and irrigation purposes. Twenty-two (22) groundwater samples were collected and analyzed for both chemical and physical compositions. The result of the study showed that groundwater in the area is of good quality for drinking purposes, except for pH and Fe, which had higher concentrations in some areas. A weak correlation matrix within the sampled parameters of the groundwater was observed. Hydrogeochemical studies revealed that 91% of the samples are within the geochemical zone of 4 (strong acids (SO4 + Cl) exceed weak acids (CO3 + HCO3)), while 9% are of the geochemical zone of 3 (weak acids (CO3 + HCO3) exceed strong acids (SO4 + Cl)). The study shows an ionic trend of Cl- > Ca2+ > HCO3- > Na+ + K+ > Mg2+ > SO42- and hydrogeochemical facies of Na-Cl, Ca-Cl, Ca-CO3, Mg-Cl, and Mg-HCO3 of 45.5%, 36.4%, 4.5%, 4.5%, and 9.1% respectively. Chloro-alkaline values were negative except for B4 which was positive. The water quality index (WQI) revealed water quality status of excellent (4.5%), good (27.3%), poor (40.9%), and very poor (27.3%). Contamination factor (CF) reveals that the groundwater is slightly polluted while the pollution load index (PLI) revealed no noticeable pollution. Gibbs diagram revealed that the entire samples are within the rock dominance zone. Irrigation suitability studies showed that SAR of the groundwater was of excellent quality; %Na had good quality (27.3%), permissible quality (45.4%), and doubtful quality (27.3%); MH had 86.4% of the groundwater suitable, while 13.6% are not suitable; KR had suitable groundwater (59.1%) and unsuitable (40.9%); while the Wilcox diagram had 72.7% excellent water for irrigation and 27.3% permissible for irrigation. A routine check of groundwater in the study area is recommended.

Research progress and mechanism of nanomaterials-mediated in-situ remediation of cadmium-contaminated soil: A critical review.

Cadmium contamination of soil is a global issue and in-situ remediation technology as a promising mitigation strategy has attracted more and more attention. Many nanomaterials have been applied for the in-situ remediation of cadmium-contaminated soil due to their excellent properties of the nano-scale size effect. In this work, recent research progress of various nanomaterials, including carbon nanomaterials, metal-based nanomaterials and nano mineral materials, in the removal of cadmium and in-situ remediation of cadmium-contaminated soil were systematically discussed. Additional emphases were particularly laid on both laboratory and field restoration effects. Moreover, the factors which can affect the stability of cadmium, main interaction mechanisms between nanomaterials and cadmium in the soil, and potential future research direction were also provided. Therefore, it is believed that this work will ultimately contribute to the myriad of environmental cleanup advances, and further improve human health and sustainable development.

Ten-Gram-Scale Facile Synthesis of Organogadolinium Complex Nanoparticles for Tumor Diagnosis.

The market of available contrast agents for clinical magnetic resonance imaging (MRI) has been dominated by gadolinium (Gd) chelates based T1 contrast agents for decades. However, there are growing concerns about their safety because they are retained in the body and are nephrotoxic, which necessitated a warning by the U.S. Food and Drug Administration against the use of such contrast agents. To ameliorate these problems, it is necessary to improve the MRI efficiency of such contrast agents to allow the administration of much reduced dosages. In this study, a ten-gram-scale facile method is developed to synthesize organogadolinium complex nanoparticles (i.e., reductive bovine serum albumin stabilized Gd-salicylate nanoparticles, GdSalNPs-rBSA) with high r1 value of 19.51 mm-1 s-1 and very low r2 /r1 ratio of 1.21 (B0 = 1.5 T) for high-contrast T1 -weighted MRI of tumors. The GdSalNPs-rBSA nanoparticles possess more advantages including low synthesis cost (≈0.54 USD per g), long in vivo circulation time (t1/2 = 6.13 h), almost no Gd3+ release, and excellent biosafety. Moreover, the GdSalNPs-rBSA nanoparticles demonstrate excellent in vivo MRI contrast enhancement (signal-to-noise ratio (ΔSNR) ≈ 220%) for tumor diagnosis.

A Hybrid Organo-Nanotheranostic Platform of Superlative Biocompatibility for Near-Infrared-Triggered Fluorescence Imaging and Synergistically Enhanced Ablation of Tumors.

The quest for an all-organic nanosystem with negligible cytotoxicity and remarkable in vivo tumor theranostic capability is inescapably unending. Hitherto, the landscape of available photothermal agents is dominated by metal-based nanoparticles (NPs) with attendant in vivo negatives. Here, an all-organic-composed theranostic nanosystem with outstanding biocompatibility for fluorescence image-guided tumor photothermal therapy, and as a potential alternative to metal-based photothermal agents is developed. This is rationally achieved by compartmentalizing indocyanine green (ICG) in glycol chitosan (GC)-polypyrrole (PP) nanocarrier to form hybrid ICG@GC-PP NPs (≈65 nm). The compartmentalization strategy, alongside the high photothermal conversion ability of PP jointly enhances the low photostability of free ICG. Advantageously, ICG@GC-PP is endowed with an impeccable in vivo performance by the well-known biocompatibility track records of its individual tri organo-components (GC, PP, and ICG). As a proof of concept, ICG@GC-PP NPs enables a sufficiently prolonged tumor diagnosis by fluorescence imaging up to 20 h post-injection. Furthermore, owing to the complementary heating performances of PP and ICG, ICG@GC-PP NPs-treated mice by one-time near-infrared irradiation exhibit total tumor regression within 14 days post-treatment. Therefore, leveraging the underlying benefits of this study will help to guide the development of new all-organic biocompatible systems in synergism, for safer tumor theranostics.

Nanoparticle-Based Wound Dressing: Recent Progress in the Detection and Therapy of Bacterial Infections.

Bacterial infections in wounds often delay the healing process, and may seriously threaten human life. It is urgent to develop wound dressings to effectively detect and treat bacterial infections. Nanoparticles have been extensively used in wound dressings because of their specific properties. This review highlights the recent progress on nanoparticle-based wound dressings for bacterial detection and therapy. Specifically, nanoparticles have been applied as intrinsic antibacterial agents or drug delivery vehicles to treat bacteria in wounds. Moreover, nanoparticles with photothermal or photodynamic property have also been explored to endow wound dressings with significant optical properties to further enhance their bactericidal effect. More interestingly, nanoparticle-based smart dressings have been recently explored for bacteria detection and treatment, which enables an accurate assessment of bacterial infection and a more precise control of on-demand therapy.

Deep Penetration of Targeted Nanobubbles Enhanced Cavitation Effect on Thrombolytic Capacity.

Sonothrombolysis with microbubbles can enhance the dissolution of thrombus through the cavitation effect of microbubbles under ultrasound irradiation. However, the detailed mechanism of thrombolysis with microscaled or nanoscaled bubbles is still not so clear. This study compared the thrombolytic capacity of cRGD-targeted or nontargeted bubbles with different particle sizes combined with urokinase (UK). The size of the microscaled bubbles (Mbs or Mbs-cRGD) was mostly approximately 3 µm, while the nanoscaled bubbles (Nbs or Nbs-cRGD) were mainly around 220 nm. In vitro testing was performed on an extracorporeal circulation device that mimics human vascular thromboembolism. The rabbit clots in Mbs with UK groups showed peripheral worm-like dissolution, while the clots in Nbs with UK groups showed internal fissure-like collapse. In addition, the thrombolysis rate of Nbs-cRGD with the UK group was the highest. Furthermore, the scanning electron microscopic images showed that the fibrin network was the most severely damaged by the Nbs-cRGD, and most of the fibrin strands were dissolved. Especially, the Nbs-cRGD can penetrate much deeper than Mbs-cRGD into the thrombus and loosen the fibrin network. Taken together, benefiting from the specific identification and deep penetration to thrombus, our developed novel targeted Nbs may have broad application prospects in the clinic.

The design and biomedical applications of self-assembled two-dimensional organic biomaterials.

The design and applications of some inorganic two-dimensional (2D) nanomaterials such as graphene, graphyne, and borophene have been widely studied in recent years. Meanwhile, it has been noticed that self-assembling two-dimensional organic biomaterials (2DOBMs) including films, membranes, nanosheets, nanoribbons, grids, arrays, and lattices based on various biomolecules also exhibited promising structures, functions, and applications. The in-depth studies on the self-assembly formation, structural and functional tailoring of 2DOBMs open new avenues for the next generation of novel nanomaterials with adjustable structure and functions, which would further promote the applications of 2DOBMs in materials science, nanodevices, energy and environmental science, biomedicine, tissue engineering, and analytical science. In this review, we summarize important information on the basic principles to fabricate self-assembling 2DOBMs based on peptides, proteins, DNA, RNA, viruses, and other biopolymers. The potential strategies and techniques for tailoring and controlling the structures and functions of 2DOBMs are presented and discussed further. The function-specific biomedical applications of 2DOBMs in biosensors, biomimetic mineralization, cell growth, drug/gene delivery, and bioimaging are also highlighted.

Nanozymes-Engineered Metal-Organic Frameworks for Catalytic Cascades-Enhanced Synergistic Cancer Therapy.

The efficiency of chemical intercommunication between enzymes in natural networks can be significantly enhanced by the organized catalytic cascades. Nevertheless, the exploration of two-or-more-enzymes-engineered nanoreactors for catalytic cascades remains a great challenge in cancer therapy because of the inherent drawbacks of natural enzymes. Here, encouraged by the catalytic activity of the individual nanozyme for benefiting the treatment of solid tumors, we propose an organized in situ catalytic cascades-enhanced synergistic therapeutic strategy driven by dual-nanozymes-engineered porphyrin metal-organic frameworks (PCN). Precisely, catalase-mimicking platinum nanoparticles (Pt NPs) were sandwiched by PCN, followed by embedding glucose oxidase-mimicking ultrasmall gold nanoparticles (Au NPs) within the outer shell, and further coordination with folic acid (P@Pt@P-Au-FA). The Pt NPs effectively enabled tumor hypoxia relief by catalyzing the intratumoral H2O2 to O2 for (1) enhancing the O2-dependent photodynamic therapy and (2) subsequently accelerating the depletion of ß-d-glucose by Au NPs for synergistic starving-like therapy with the self-produced H2O2 as the substrate for Pt NPs. Consequently, a remarkably strengthened antitumor efficiency with prevention of tumor recurrence and metastasis was achieved. This work highlights a rationally designed tumor microenvironment-specific nanoreactor for opening improved research in nanozymes and provides a means to design a catalytic cascade model for practical applications.

The Transition from Metal-Based to Metal-Free Contrast Agents for T1 Magnetic Resonance Imaging Enhancement.

Magnetic resonance imaging (MRI) has received significant attention as the noninvasive diagnostic technique for complex diseases. Image-guided therapeutic strategy for diseases such as cancer has also been at the front line of biomedical research, thanks to the innovative MRI, enhanced by the prior delivery of contrast agents (CAs) into patients' bodies through injection. These CAs have contributed a great deal to the clinical utility of MRI but have been based on metal-containing compounds such as gadolinium, manganese, and iron oxide. Some of these CAs have led to cytotoxicities such as the incurable Nephrogenic Systemic Fibrosis (NSF), resulting in their removal from the market. On the other hand, CAs based on organic nitroxide radicals, by virtue of their structural composition, are metal free and without the aforementioned drawbacks. They also have improved biocompatibility, ease of functionalization, and long blood circulation times, and have been proven to offer tissue contrast enhancement with longitudinal relaxivities comparable with those for the metal-containing CAs. Thus, this Review highlights the recent progress in metal-based CAs and their shortcomings. In addition, the remarkable goals achieved by the organic nitroxide radical CAs in the enhancement of MR images have also been discussed extensively. The focal point of this Review is to emphasize or demonstrate the crucial need for transition into the use of organic nitroxide radicals-metal-free CAs-as against the metal-containing CAs, with the aim of achieving safer application of MRI for early disease diagnosis and image-guided therapy.

Porous Gold Nanoshells on Functional NH2 -MOFs: Facile Synthesis and Designable Platforms for Cancer Multiple Therapy.

AuroShell nanoparticles (sealed gold nanoshell on silica) are the only inorganic materials that are approved for clinical trial for photothermal ablation of solid tumors. Based on that, porous gold nanoshell structures are thus critical for cancer multiple theranostics in the future owing to their inherent cargo-loading ability. Nevertheless, adjusting the diverse experimental parameters of the reported procedures to obtain porous gold nanoshell structures is challenging. Herein, a series of amino-functionalized porous metal-organic frameworks (NH2 -MOFs) nanoparticles are uncovered as superior templates for porous gold nanoshell deposition (NH2 -MOFs@Aushell ) by means of a more facile and general one-step method, which combines the enriched functionalities of NH2 -MOFs with those of porous gold nanoshells. Moreover, in order to illustrate the promising applications of this method in biomedicine, platinum nanozymes-encapsulated NH2 -MOFs are further designed with porous gold nanoshell coating and photosensitizer chlorin e6 (Ce6)-loaded nanoparticles with continuous O2 -evolving ability (Pt@UiO-66-NH2 @Aushell -Ce6). The combination of photodynamic and photothermal therapy is then carried out both in vitro and in vivo, achieving excellent synergistic therapeutic outcomes. Therefore, this work not only presents a facile strategy to fabricate functionalized porous gold nanoshell structures, but also illustrates an excellent synergistic tumor therapy strategy.

Unraveling Water-Based Lubrication with Carbon Dots of Asphaltene Origin.

Despite the lower toxicity of water-based lubricants over nonrenewable petroleum-based analogues, they face challenges in achieving widespread adoption due to low stability and inadequate friction-reduction performance. To address this, a cost-effective nanoadditive is synthesized by expansive oxidation of asphaltenes to create biocompatible asphaltene-derived carbon dots [(ACDs); 5 nm]. These ACDs exhibit excellent water redispersibility, promoting long-term friction reduction and marking the first use of an asphaltene-based system for friction reduction in water or oil. Even at low loadings (0.2-4.0 wt %), ACDs significantly reduce friction on steel surfaces (>54%) with tribofilm stability surpassing pristine carbon dots, typical carbon-based graphene quantum dots, and inorganic nanomaterials (commercial 5 and 20 nm silica). The ACDs' attributes include high negative zeta potential, considerable water uptake, varied functional groups, biocompatibility, and a nanodisc shape conducive to stable tribofilm formation through effective particle stacking. The scalable synthesis, high yield, and impressive water redispersibility of ACDs position them favorably for commercial water-based lubrication.

Recent progress on near-infrared fluorescence heptamethine cyanine dye-based molecules and nanoparticles for tumor imaging and treatment.

Recenly, near-infrared fluorescence heptamethine cyanine dyes have shown satisfactory values in bioengineering, biology, and pharmacy especially in cancer diagnosis and treatment, owing to their excellent fluorescence property and biocompatibility. In order to achieve broad application prospects, diverse structures, and chemical properties of heptamethine cyanine dyes have been designed to develop novel functional molecules and nanoparticles over the past decade. For fluorescence and photoacoustic tumor imaging properties, heptamethine cyanine dyes are equipped with good photothermal performance and reactive oxygen species production properties under near-infrared light irradiation, thus holding great promise in photodynamic and/or photothermal cancer therapies. This review offers a comprehensive scope of the structures, comparisons, and applications of heptamethine cyanine dyes-based molecules as well as nanoparticles in tumor treatment and imaging in current years. Therefore, this review may drive the development and innovation of heptamethine cyanine dyes, significantly offering opportunities for improving tumor imaging and treatment in a precise noninvasive manner. This article is categorized under: Diagnostic Tools > In Vivo Nanodiagnostics and Imaging Therapeutic Approaches and Drug Discovery > Nanomedicine for Oncologic Disease.

Transformable Neuropeptide Prodrug with Tumor Microenvironment Responsiveness for Tumor Growth and Metastasis Inhibition of Triple-Negative Breast Cancer.

Triple-negative breast cancer (TNBC) has the worst prognosis among all breast cancer subtypes due to lack of specific target sites and effective treatments. Herein, a transformable prodrug (DOX-P18) based on neuropeptide Y analogue with tumor microenvironment responsiveness is developed for TNBC treatment. The prodrug DOX-P18 can achieve reversible morphological transformation between monomers and nanoparticles through the manipulation of protonation degree in different environments. It can self-assemble into nanoparticles to enhance the circulation stability and drug delivery efficiency in the physiological environment while transforming from nanoparticles to monomers and being endocytosed into the breast cancer cells in the acidic tumor microenvironment. Further, the DOX-P18 can precisely be enriched in the mitochondria, and efficiently activated by matrix metalloproteinases. Then, the cytotoxic fragment (DOX-P3) can subsequently be diffused into the nucleus, generating a sustained cell toxicity effect. In the meanwhile, the hydrolysate residue P15 can assemble into nanofibers to construct nest-like barriers for the metastasis inhibition of cancer cells. After intravenous injection, the transformable prodrug DOX-P18 demonstrated superior tumor growth and metastasis suppression with much better biocompatibility and improved biodistribution compared to free DOX. As a novel tumor microenvironment-responsive transformable prodrug with diversified biological functions, DOX-P18 shows great potential in smart chemotherapeutics discovery for TBNC.

Platelet-Membrane-Coated Polydopamine Nanoparticles for Neuroprotection by Reducing Oxidative Stress and Repairing Damaged Vessels in Intracerebral Hemorrhage.

Intracerebral hemorrhage (ICH) has a high morbidity and mortality rate. Excessive reactive oxygen species (ROS) caused by primary and second brain injury can induce neuron death and inhibit neurological functional recovery after ICH. Therefore, exploring an effective way to noninvasively target hemorrhage sites to scavenge ROS is urgently needed. Inspired by the biological function of platelets to target injury vessel and repair injury blood vessels, platelet-membrane-modified polydopamine (Menp@PLT) nanoparticles are developed with targeting to hemorrhage sites of ICH. Results demonstrate that Menp@PLT nanoparticles can effectively achieve targeting to the location of intracranial hematoma. Furthermore, Menp@PLT with excellent anti-ROS properties can scavenge ROS and improve neuroinflammation microenvironment of ICH. In addition, Menp@PLT may play a role in decreasing hemorrhage volume by repairing injury blood vessels. Combining platelet membrane and anti-ROS nanoparticles for targeting brain hemorrhage sites provide a promising strategy for efficiently treating ICH.

Ablation of Gap Junction Protein Improves the Efficiency of Nanozyme-Mediated Catalytic/Starvation/Mild-Temperature Photothermal Therapy.

Reactive oxygen species (ROS)-mediated tumor catalytic therapy is typically hindered by gap junction proteins that form cell-to-cell channels to remove cytotoxic ROS, thereby protecting tumor cells from oxidative damage. In this work, a multifunctional nanozyme, FePGOGA, is designed and prepared by Fe(III)-mediated oxidative polymerization (FeP), followed by glucose oxidase (GOx) and GAP19 peptides co-loading through electrostatic and π-π interactions. The FePGOGA nanozyme exhibits excellent cascade peroxidase- and glutathione-oxidase-like activities that efficiently catalyze hydrogen peroxide conversion to hydroxyl radicals and convert reduced glutathione to oxidized glutathione disulfide. The loaded GOx starves the tumors and aggravates tumor oxidative stress through glucose decomposition, while GAP19 peptides block the hemichannels by inducing degradation of Cx43, thus increasing the accumulation of intracellular ROS, and decreasing the transport of intracellular glucose. Furthermore, the ROS reacts with primary amines of heat shock proteins to destroy their structure and function, enabling tumor photothermal therapy at the widely sought-after mild temperature (mildPTT, ≤45 °C). In vivo experiments demonstrate the significant antitumor effectof FePGOGA on cal27 xenograft tumors under near-infrared light irradiation. This study demonstrates the successful ablation of gap junction proteins to overcome resistance to ROS-mediated therapy, providing a regulator to suppress tumor self-preservation during tumor starvation, catalytic therapy, and mildPTT.

Transition metal ion-doped ferrites nanoparticles for bioimaging and cancer therapy.

Magnetic nanoparticles (MNPs) have been extensively researched and implemented in biomedicine for more than half a century due to their non-invasive nature, ease of temporal and spatial manipulation, and considerable biocompatibility. However, the complex magnetic behaviour of MNPs is influenced by several parameters (e.g., particle size, shape, composition, core-shell structure, etc.), among which the amount of transition metal doping plays an important factor. For this reason, the doping of ferrite with transition metals has been used as an effective strategy to precisely tailor MNPs to achieve satisfactory performance in biomedical applications. In this review, we first introduced the main properties of coordinated MNPs (including magnetic moment and saturated magnetisation) and provide a comprehensive overview of the mechanistic studies related to the doping of transition metal ions into ferrite to precisely modulate its magnetic properties. We also highlighted the potential mechanisms and recent advances in transition metal ion-doped MNPs (TMNPs) for bioimaging (magnetic resonance imaging and magnetic particle imaging) and tumour therapy (e.g., magneto-mechanical killing, magnetothermal therapy, and drug delivery). Finally, we summarised the current challenges and future trends of TMNPs in the biomedical field based on the latest advances by researchers.

Chemotherapeutic nanomaterials in tumor boundary delineation: Prospects for effective tumor treatment.

Accurately delineating tumor boundaries is key to predicting survival rates of cancer patients and assessing response of tumor microenvironment to various therapeutic techniques such as chemotherapy and radiotherapy. This review discusses various strategies that have been deployed to accurately delineate tumor boundaries with particular emphasis on the potential of chemotherapeutic nanomaterials in tumor boundary delineation. It also compiles the types of tumors that have been successfully delineated by currently available strategies. Finally, the challenges that still abound in accurate tumor boundary delineation are presented alongside possible perspective strategies to either ameliorate or solve the problems. It is expected that the information communicated herein will form the first compendious baseline information on tumor boundary delineation with chemotherapeutic nanomaterials and provide useful insights into future possible paths to advancing current available tumor boundary delineation approaches to achieve efficacious tumor therapy.

Nature-Inspired Polyethylenimine-Modified Calcium Alginate Blended Waterborne Polyurethane Graded Functional Materials for Multiple Water Purification.

In recent years, natural disasters such as hurricanes and floods have become more frequent, which usually leads to the pollution of drinking water. Drinking contaminated water may cause public health emergencies. The demand for healthy drinking water in disaster-affected areas is huge and urgent. Therefore, it is necessary to develop a simple water treatment technology suitable for emergencies. Inspired by nature, a fractional spray method was used to prepare graded purification material under mild conditions. The material consists of a calcium alginate isolation layer and a functional layer composed of calcium alginate, polyethylenimine, and water-based polyurethane, which can purify complex pollutants in water such as heavy metals, oils, pathogens, and micro/nano plastics through percolation. It does not require additional energy and can purify polluted water only under gravity. A disposable paper cup model was also designed, which can be used to obtain purified water by immersing in polluted water directly without other filtering devices. The test report shows that the water obtained from the paper cup was deeply purified. This design makes the material user-friendly and has the potential as a strategic material. This discovery can effectively improve the safety of drinking water after disasters and improve people's quality of life.

The strategy of precise targeting and in situ oxygenating for enhanced triple-negative breast cancer chemophototherapy.

The absence of effective therapeutic targets and tumor hypoxia are the main causes of failure in the treatment of triple-negative breast cancer (TNBC). Biomimetic nanotechnology and tumor microenvironment (TME) responsiveness bring hope and opportunity to address this problem. Here, we develop a core membrane nanoplatform (HM/D-I-BL) using hollow mesoporous manganese dioxide (HM) coated with a biomimetic cancer cell membrane for enhanced chemotherapy/phototherapy via the strategy of precise drug delivery and hypoxia amelioration. Cancer cell membrane modification endows HM/D-I-BL with excellent homologous targeting and immune escape performance. Cellular uptake and fluorescence imaging studies confirmed that HM/D-I-BL can be accurately delivered to tumor sites. HM/D-I-BL also features efficient in situ O2 generation in tumors upon laser irradiation, and subsequently enhanced chemotherapy/phototherapy, pointing to its usefulness as a TME-responsive nanozyme to alleviate tumor hypoxia in the presence of H2O2. In addition, HM/D-I-BL showed good fluorescence and magnetic resonance imaging performances, which offers a reliable multimodal image-guided combination tumor therapy for precision theranostics in the future. In general, this intelligent biomimetic nanoplatform with its homotypic tumor targeting, in situ alleviation of tumor hypoxia and synergetic chemophototherapy would open up a new dimension for the precision treatment of TNBC.