Antibacterial, antibiofilm, anti-inflammatory, and wound healing effects of nanoscale multifunctional cationic alternating copolymers.

Infectious diseases caused by new or unknown bacteria and viruses, such as anthrax, cholera, tuberculosis and even COVID-19, are a major threat to humanity. Thus, the development of new synthetic compounds with efficient antimicrobial activity is a necessity. Herein, rationally designed novel multifunctional cationic alternating copolymers were directly synthesized through a step-growth polymerization reaction using a bivalent electrophilic cross-linker containing disulfide bonds and a diamine heterocyclic ring. To optimize the activity of these alternating copolymers, several different diamines and cross-linkers were explored to find the highest antibacterial effects. The synthesized nanopolymers not only displayed good to excellent antibacterial activity as judged by minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) against Staphylococcus aureus, Enterococcus faecalis, Pseudomonas aeruginosa, and Escherichia coli, but also reduced the number of biofilm cells even at low concentrations, without killing mammalian cells. Furthermore, in vivo experiments using infected burn wounds in mice demonstrated good antibacterial activity and stimulated wound healing, without causing systemic inflammation. These findings suggest that the multifunctional cationic nanopolymers have potential as a novel antibacterial agent for eradication of multidrug resistant bacterial infections.

Synthesis of Magnetic Ions-Doped QDs Synthesized Via a Facial Aqueous Solution Method for Optical/MR Dual-Modality Imaging Applications.

This research reports the preparation and examination of Cadmium Telluride (CdTe) Quantum Dots and doping CdTe QDs with Europium (Eu), Gadolinium (Gd), and Manganese (Mn) prepared in aqueous solution using TGA as a capping agent. Magnetic QDs (MQDs) are important agents for fluorescence (FL) /magnetic resonance (MR) dual-modal imaging due to their excellent optical and magnetic properties. Herein, the chemical bonds, structural, fluorescence, and magnetized properties of CdTe QDs and effect of Mn, Eu, and Gd ions doping on their properties were examined by X-ray powder diffraction (XRD), high-resolution transmission electron microscopy (HRTM), Energy-dispersive X-ray spectroscopy (EDX), Fourier-transform infrared spectroscopy (FTIR), photoluminescence spectroscopy (PL), Ultraviolet-visible spectroscopy (UV-Vis), and vibrating sample magnetometer measurements (VSM). Almost similar X-Ray patterns with the absence/presence of ions for all samples with cubic crystal structures were obtained which indicated that the introduction of ions into CdTe QDs could not alter the cubic primary structure of CdTe. Monodisperse size distributed with seemingly-spherical shapes, and also, the estimated mean diameters about 3 and less than 3 nm of QDs were obtained. The effect of X ions injection on the fluorescence and UV-Vis properties of the QDs were also investigated. Optical studies showed the decreases in bandgap as the heating time increases during synthesis while undergoing red-shift. The CdTe nanocrystals with high PL quantum yields were achieved in more than 6 h of heating. Also, investigations have shown the quenching of fluorescence by the existence of ions in the CdTe QDs. Then, all the ions doped QDs exhibited ferromagnetic behavior at room temperature by a vibrating sample magnetometer which confirmed the success of the presentation of ions into CdTe cubic crystal structure. They can have been employed as a suitable contrast agent successfully for biological applications such as FL/MR dual-modal imaging.

Development of an anti-CD45RA-quantum dots conjugated scFv to detect leukemic cancer stem cells.

Leukemic cancer stem cells (LSCs), aberrantly overexpressing CD45RA are among the major causes of relapse following chemotherapy in patients with acute myeloid leukemia and serve as a highly sensitive marker for predicting relapse occurrence following chemotherapy. The main purpose of current study was to develop a sensitive approach for detecting LSCs based on a conjugate of an anti-CD45 scFv and quantum dot. The variable light and heavy chain sequences of a recently developed anti-CD45RA monoclonal antibody were derived from hybridoma cells and PCR amplified to construct scFv. Following insertion of scFv gene into a pET32a-lic vector and expression in Escherichia coli and purification, the purified scFv, was conjugated with carbon dots (C dots) and used for the detection of CD45RA +cells while CD45RA-cells served as negative control. Subsequently, Functional activity of the conjugate was analyzed by flow cytometry and ICC to detect the cell surface antigen binding and detection ability. Based on results, purified CD45RA scFv conjugated C dots could specifically recognize CD45RA positive cells, but not any CD45RA negative ones. In conclusion, here we developed a low-cost but very efficient approach for detection of CD45RA positive cells including LSCs.

Smart micro/nanoparticles in stimulus-responsive drug/gene delivery systems.

New achievements in the realm of nanoscience and innovative techniques of nanomedicine have moved micro/nanoparticles (MNPs) to the point of becoming actually useful for practical applications in the near future. Various differences between the extracellular and intracellular environments of cancerous and normal cells and the particular characteristics of tumors such as physicochemical properties, neovasculature, elasticity, surface electrical charge, and pH have motivated the design and fabrication of inventive "smart" MNPs for stimulus-responsive controlled drug release. These novel MNPs can be tailored to be responsive to pH variations, redox potential, enzymatic activation, thermal gradients, magnetic fields, light, and ultrasound (US), or can even be responsive to dual or multi-combinations of different stimuli. This unparalleled capability has increased their importance as site-specific controlled drug delivery systems (DDSs) and has encouraged their rapid development in recent years. An in-depth understanding of the underlying mechanisms of these DDS approaches is expected to further contribute to this groundbreaking field of nanomedicine. Smart nanocarriers in the form of MNPs that can be triggered by internal or external stimulus are summarized and discussed in the present review, including pH-sensitive peptides and polymers, redox-responsive micelles and nanogels, thermo- or magnetic-responsive nanoparticles (NPs), mechanical- or electrical-responsive MNPs, light or ultrasound-sensitive particles, and multi-responsive MNPs including dual stimuli-sensitive nanosheets of graphene. This review highlights the recent advances of smart MNPs categorized according to their activation stimulus (physical, chemical, or biological) and looks forward to future pharmaceutical applications.

Atomic Layer Deposition-A Versatile Toolbox for Designing/Engineering Electrodes for Advanced Supercapacitors.

Atomic layer deposition (ALD) has become the most widely used thin-film deposition technique in various fields due to its unique advantages, such as self-terminating growth, precise thickness control, and excellent deposition quality. In the energy storage domain, ALD has shown great potential for supercapacitors (SCs) by enabling the construction and surface engineering of novel electrode materials. This review aims to present a comprehensive outlook on the development, achievements, and design of advanced electrodes involving the application of ALD for realizing high-performance SCs to date, as organized in several sections of this paper. Specifically, this review focuses on understanding the influence of ALD parameters on the electrochemical performance and discusses the ALD of nanostructured electrochemically active electrode materials on various templates for SCs. It examines the influence of ALD parameters on electrochemical performance and highlights ALD's role in passivating electrodes and creating 3D nanoarchitectures. The relationship between synthesis procedures and SC properties is analyzed to guide future research in preparing materials for various applications. Finally, it is concluded by suggesting the directions and scope of future research and development to further leverage the unique advantages of ALD for fabricating new materials and harness the unexplored opportunities in the fabrication of advanced-generation SCs.

Hole-Transport Material Engineering in Highly Durable Carbon-Based Perovskite Photovoltaic Devices.

Despite the fast-developing momentum of perovskite solar cells (PSCs) toward flexible roll-to-roll solar energy harvesting panels, their long-term stability remains to be the challenging obstacle in terms of moisture, light sensitivity, and thermal stress. Compositional engineering including less usage of volatile methylammonium bromide (MABr) and incorporating more formamidinium iodide (FAI) promises more phase stability. In this work, an embedded carbon cloth in carbon paste is utilized as the back contact in PSCs (having optimized perovskite composition), resulting in a high power conversion efficiency (PCE) of 15.4%, and the as-fabricated devices retain 60% of the initial PCE after more than 180 h (at the experiment temperature of 85 °C and under 40% relative humidity). These results are from devices without any encapsulation or light soaking pre-treatments, whereas Au-based PSCs retain 45% of the initial PCE at the same conditions with rapid degradation. In addition, the long-term device stability results reveal that poly[bis(4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA) is a more stable polymeric hole-transport material (HTM) at the 85 °C thermal stress than the copper thiocyanate (CuSCN) inorganic HTM for carbon-based devices. These results pave the way toward modifying additive-free and polymeric HTM for scalable carbon-based PSCs.

Ultrafast and stable planar photodetector based on SnS2 nanosheets/perovskite structure.

Two-dimensional (2D) transition metal dichalcogenides are promising candidates of photodetectors where they are commonly grown parallel to the substrate due to their 2D characteristics in micrometer scales from exfoliation of bulk crystals or through high temperature chemical vapor deposition (CVD) methods. In this study, semi-hexagonal vertical nanosheets of SnS2 layered have been fabricated on FTO substrate without using Sn source through CVD method at relatively low temperature (500 °C). Due to exceptional band alignment of triple cation lead perovskite (TCLP) with semi-hexagonal SnS2 nanosheets, an improved photodetector has been fabricated. This type of photodetectors fabricated through lithography-free and electrodes metallization free approach with remarkable fast response (20.7 µs/31.4 µs as rising /falling times), showed high photoresponsivity, external quantum efficiency and detectivity of 1.84 AW-1, 513% and 1.69 × 1011, respectively under illumination of incident light with wavelength of 445 nm. The stability of the photodetectors has been studied utilizing a protective PMMA layer on the perovskite layer in 100% humidity. The introduced growth and fabrication process of the planar photodetector, including one/two dimensional interface through the edges/basal planes of layered materials with perovskite film, paves a way for the large scale, cost-effective and high-performance optoelectronic devices.

Bottom-up synthesis of nitrogen and oxygen co-decorated carbon quantum dots with enhanced DNA plasmid expression.

In this paper, a bottom-up hydrothermal route is reported for the synthesis of oxygen and nitrogen co-decorated carbon quantum dots (CQDs) using ammonium hydrogen citrate (AHC) as a single precursor. DLS data approved the formation of 4.0 nm (average size) CQDs. XRD pattern shows the interlayer spacing (002) of 3.5 Šfor CQDs, which is exactly the same as that of crystalline graphite. XPS and FTIR spectra verified the formation of oxygen and nitrogen functional groups on the CQDs surface. Co-decorated carboxyl, hydroxyl and amine groups on the CQDs surfaces make them as promising polyelectrolyte for gene delivery. Toxicity assay showed a survival rate of 70% under different incubation times and up to 500 µg/mL. The highly water-soluble, stable fluorescence and low toxic CQDs increased the gene expression of DNA plasmid in E. coli bacteria 4-fold more than the control group.

Effect of graphene oxide nanosheets on visible light-assisted antibacterial activity of vertically-aligned copper oxide nanowire arrays.

In the present work, the effect of graphene oxide (GO) nanosheets on the antibacterial activity of CuO nanowire arrays under visible light irradiation is shown. A combined thermal oxidation/electrophoretic deposition technique was employed to prepare three-dimensional networks of graphene oxide nanosheets hybridized with vertically aligned CuO nanowires. With the help of standard antibacterial assays and X-ray photoelectron spectroscopy, it is shown that the light-activated antibacterial response of the hybrid material against gram-negative Escherichia coli is significantly improved as the oxide functional groups of the GO nanosheets are reduced. In order to explore the physicochemical mechanism behind this behavior, ab-initio simulations based on density functional theory were performed and the effect of surface functional groups and hybridization were elucidated. Supported by the experiments, a three-step photo-antibacterial based mechanism is suggested: (i) injection of an electron from CuO into rGO, (ii) localization of the excess electron on rGO functional groups, and (iii) release of reactive oxygen species lethal to bacteria. Activation of new photoactive and physical mechanisms in the hybrid system makes rGO-modified CuO nanowire coatings as promising nanostructure devices for antimicrobial applications in particular for dry environments.

Graphene-silica hybrid in efficient preconcentration of heavy metal ions via novel single-step method of moderate centrifugation-assisted dispersive micro solid phase extraction.

Novel nanoadsorbent of graphene-silica hybrid was synthesized via chemical vapor deposition (CVD) method. Graphene sheets were catalytically grown on a silica-based substrate and after being characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), their high efficacy in adsorption of metal ions (lead, cadmium, and chromium) was examined. It was found that the presence of silica within the G-SiO2 structure imparts an amphiphilic property to the hybrid that enables it to interact with both free and bounded metal ions present in the biological samples. Utilization of the innovative method of moderate centrifugation-assisted dispersive micro solid phase extraction (MCDµSPE) coupled with electrothermal atomic absorption spectrometry (ETAAS), not only facilitated absolute separation of the fabricated nanoadsorbent from the solvent, but also helped complete recovering of the scant volume of desorbed supernatant. Thus, microliter amount of desorption solvent can be regained completely by MCDµSPE method without sorbent loss. Various parameters affecting the extraction efficiency were investigated and admirable linearity from 0.012 to 12.5 µg L(-1) and favorable detection limits (LOD) could be recorded. Intra day precision (RSD, n=10) ranged from 3.1 to 3.8%, whereas inter day precision (RSD, n=5) ranged from 6.3 to 7.2%.

Innovative separation and preconcentration technique of coagulating homogenous dispersive micro solid phase extraction exploiting graphene oxide nanosheets.

A uniquely novel, fast, and facile technique is introduced for the first time in which a scant amount of graphene oxide (GO), without modification, has been utilized in dispersive mode of solid phase extraction (SPE) for an efficient yet simple separation. The proposed method of coagulating homogenous dispersive micro solid phase extraction (CHD-µSPE) is based on coagulation of homogeneous GO solution with the aid of polyetheneimine (PEI). CHD-µSPE use full adsorption capacity of GO because in this method was used GO solution obtained from synthesis process without drying step and stacking nanosheets. In optimized condition, 30 µL GO solution (7 mg mL(-1)), obtained in synthesis process, was injected into 1.5 mL the sample solution followed by immediate injection of 53 µL PEI solution (1 mg mL(-1)). After inserting PEI, GO sheets aggregate and can be readily separated by centrifugation. PEI not only cause aggregation of GO, but also form three-dimensional network of GO with easy handling in following separation steps. Lead, cadmium, and chromium were selected as model analytes and the effecting parameters including the amount of GO, concentration of PEI, sample pH, extraction time, and type of desorption solvent were investigated and optimized. The results indicate that the proposed CHD-µSPE method can be successfully applied GO in dispersive mode of SPE without effecting on good capability adsorption of GO. The novel method was applied in determination of lead, cadmium, and chromium in water, human saliva, and urine samples by electrothermal atomic absorption spectrometry. The detection limits are as low as 0.035, 0.005, and 0.012 µg L(-1) for Pb, Cd, and Cr respectively. The intra-day precisions (RSDs) were lower than 3.8%. CHD-µSPE method showed a good linear ranges of 0.24-15.6, 0.015-0.95 and 0.039-2.33 µg L(-1) for Pb, Cd and Cr respectively. Method performance was investigated by determination of mentioned metal ions in river water, human urine and saliva sample with good recoveries in range of 94.2-103.0%. The accuracy of the method was underpinned by correct analysis of a standard reference material (SRM: 2668 level I, Urine).

Ultra-sensitive detection of leukemia by graphene.

Graphene oxide nanoplatelets (GONPs) with extremely sharp edges (lateral dimensions ∼ 20-200 nm and thicknesses <2 nm) were applied in extraction of the overexpressed guanine synthesized in the cytoplasm of leukemia cells. The blood serums containing the extracted guanine were used in differential pulse voltammetry (DPV) with reduced graphene oxide nanowall (rGONW) electrodes to develop fast and ultra-sensitive electrochemical detection of leukemia cells at leukemia fractions (LFs) of ∼ 10(-11) (as the lower detection limit). The stability of the DPV signals obtained by oxidation of the extracted guanine on the rGONWs was studied after 20 cycles. Without the guanine extraction, the DPV peaks relating to guanine oxidation of normal and abnormal cells overlapped at LFs <10(-9), and consequently, the performance of rGONWs alone was limited at this level. As a benchmark, the DPV using glassy carbon electrodes was able to detect only LFs ∼ 10(-2). The ultra-sensitivity obtained by this combination method (guanine extraction by GONPs and then guanine oxidation by rGONWs) is five orders of magnitude better than the sensitivity of the best current technologies (e.g., specific mutations by polymerase chain reaction) which not only are expensive, but also require a few days for diagnosis.

In vivo SPECT imaging of tumors by 198,199Au-labeled graphene oxide nanostructures.

Graphene oxide (GO) sheets functionalized by aminopropylsilyl groups (8.0 wt.%) were labeled by (198,199)Au nanoparticle radioisotopes (obtained through reduction of HAuCl4 in sodium citrate solution followed by thermal neutron irradiation) for fast in vivo targeting and SPECT imaging (high purity germanium-spectrometry) of tumors. Using instant thin layer chromatography method, the physicochemical properties of the amino-functionalized GO sheets labeled by (198,199)Au NPs ((198,199)Au@AF-GO) were found to be highly stable enough in organic phases, e.g. a human serum, to be reliably used in bioapplications. In vivo biodistribution of the (198,199)Au@AF-GO composite was investigated in rats bearing fibrosarcoma tumor after various post-injection periods of time. The (198,199)Au@AF-GO nanostructure exhibited a rapid as well as high tumor uptake (with uptake ratio of tumor to muscle of 167 after 4h intravenous injection) that resulted in an efficient tumor targeting/imaging. Meantime, the low lipophilicity of the (198,199)Au@AF-GO caused to its fast excretion (~24 h) throughout the body by the kidneys (as also confirmed by the urinary tract). Because of the short half-life of (198,199)Au radioisotopes, the (198,199)Au@AF-GO with an excellent tumor targeting/imaging and fast washing out from the body can be suggested as one of the most effective and promising nanomaterials in nanotechnology-based cancer diagnosis and therapy.

Toward single-DNA electrochemical biosensing by graphene nanowalls.

Graphene oxide nanowalls with extremely sharp edges and preferred vertical orientation were deposited on a graphite electrode by using electrophoretic deposition in an Mg(2+)-GO electrolyte. Using differential pulse voltammetry (DPV), reduced graphene nanowalls (RGNWs) were applied for the first time, in developing an ultra-high-resolution electrochemical biosensor for detection of the four bases of DNA (G, A, T, and C) by monitoring the oxidation signals of the individual nucleotide bases. The extremely enhanced electrochemical reactivity of the four free bases of DNA, single-stranded DNA, and double-stranded DNA (dsDNA) at the surface of the RGNW electrode was compared to electrochemical performances of reduced graphene nanosheet (RGNS), graphite, and glassy carbon electrodes. By increasing the number of DPVs up to 100 scans, the RGNW electrode exhibited an excellent stability with only 15% variation in the oxidation signals, while for the RGNS electrode no detectable signals relating to T and C of 0.1 µM dsDNA were observed. The linear dynamic detection range of the RGNW electrode for dsDNA was checked in the wide range of 0.1 fM to 10 mM, while for the RGNS electrode, it was from 2.0 pM to <10 mM. The lower limits of dsDNA detection of the RGNW and RGNS electrodes were estimated as 9.4 zM (∼5 dsDNA/mL) and 5.4 fM, respectively. The RGNWs were efficient in label-free detection of single nucleotide polymorphisms of 20 zM oligonucleotides (∼10 DNA/mL) having a specific sequence. Therefore, the RGNWs can effectively contribute to the development of ultra-high-sensitive electrochemical biosensors with single-DNA resolutions.