One-Pot Two-Nanoprobe Assay Uncovers Targeted Glycoprotein Biosignature.

We report a one-pot two-nanoprobe approach coupled to mass spectrometry for simultaneous quantification and post-translational modification (PTM) profiling of targeted protein in biofluid. Using N-glycoprotein as model, the assay employs two nanoprobes, antibody-conjugated SiO2 nanoparticles and lectin-conjugated magnetic Fe3O4 nanoparticles, to achieve target glycoprotein isolation from biofluid and subsequent glycopeptide enrichment in a single tube. As demonstrated on α-fetoprotein (AFP), a serum biomarker for hepatocellular carcinoma (HCC), the assay has high purification specificity (20 glycopeptides) with 2-fold and 10-fold superior total glycopeptide intensity compared to non-one-pot method (9 glycopeptides) or without enrichment (6 glycopeptides), respectively. By multiple reaction monitoring mass spectrometry (MRM-MS) analysis of the nonglycopeptides, the assay can quantify low abundant AFP expression (0.5 ng) with good correlation with conventional ELISA method (Pearson's r = 0.987). Furthermore, we present the first study revealing AFP glycopeptide signatures of individual HCC patients, comprised of 23 heterogeneous glycoforms of bi- and triantennary, core and terminal fucosylation, and mono- to trisialylation. In addition to 12 novel AFP glycoforms, our quantification result uncovers five abundant glycoforms in HCC, including 3 core-fucosylated (CF) forms. These identified CF forms may be evaluated in future studies as potential targets in a glycopeptide biomarker panel to further improve accuracy of conventional AFP-L3 tests. Through this one-pot assay, a comprehensive target protein profile comprised of protein expression and glycosylation pattern was achieved in simple protocol with high sensitivity, reduced analysis time, and minute starting material. This assay can be extended to other PTM biosignatures by conjugation of other affinity ligands on the nanoprobe.

Functionalized HgTe nanoparticles promote laser-induced solid phase ionization/dissociation for comprehensive glycan sequencing.

Glycoconjugates are ubiquitously present and play a critical role in various biological processes. Due to their low stability and incredibly high degree of structural diversity, the structural characterization of glycan generally requires chemical derivatization and sophisticated instrumentation. Herein, we report a method for complicated glycan characterization in a single assay by employing 2,5-dihydroxybenzoic acid functionalized mercury telluride nanoparticles (HgTe@DHB NPs) as a dual ionization-dissociation element in matrix-assisted laser desorption/ionization mass spectrometry. Using a linear glycan, HgTe@DHB NPs promote laser-induced extensive and intense dissociation of the glycan, superior to HgTe microparticles and other inorganic nanoparticles (TiO2, ZnO, and Mn2O3 NPs). Abundant generation of diagnostic glycosidic (Y-, and B-type ions) and cross-ring cleavage (A-type ions) ions permits unambiguous determination of the composition, sequence, branching, and linkage of labile sialylated glycans. The general utility of this approach was demonstrated by the characterization of labile sialylated glycans and two sets of complicated isomeric glycans. This phenomenon was delineated further by investigating the NP's physico-chemical characteristics, revealing that their nanoscale-dependent thermodynamic properties, including UV absorption, photoelectron release dynamics and thermal energy, were the key to levitate temperature synergistically, thus inducing spontaneous glycan decomposition during the nanoparticle-assisted laser desorption-ionization process. Our results show that this "pseudo-MS/MS" obtained by HgTe@DHB can be beneficial for the analysis of biologically relevant and more complicated carbohydrates, without the need for chemical pre-derivatization and conventional tandem mass spectrometry.

Monodispersity of magnetic immuno-nanoprobes enhances the detection sensitivity of low abundance biomarkers in one drop of serum.

To enhance the detection sensitivity of target clinical protein biomarkers, a simple and rapid nanoprobe-based immuno-affinity mass spectrometry assay employing biocompatible monodisperse magnetic nanoparticles (MNPs) is reported herein. The MNPs were synthesized via a streamlined protocol that includes (a) fabrication of core MNPs using the thermal decomposition method to minimize aggregation, (b) surface protection by gold coating (MNP@Au) and surfactant coating using MNP@IGEPAL to improve hydrophilicity, and lastly, (c) oriented functionalization of antibodies to maximize immuno-affinity. The enrichment performances of the monodisperse MNPs for the C-reactive protein (CRP) serum biomarker were then evaluated and compared with aggregated magnetic nanoparticles synthesized from the conventional co-precipitation method (MNP(CP)). The detection sensitivity for CRP at an extremely low amount of serum sample (1 µL) was enhanced ∼19- and ∼15-fold when monodisperse MNP@Au and MNP@IGEPAL, respectively, were used. Furthermore, the detection sensitivity of CRP by this approach (1 ng mL(-1), S/N = 3) provided a 1000-fold sensitivity enhancement to the clinical cut-off (1 µg mL(-1)) of CRP. We supposed that these observed improvements are due to the enhanced nanoparticle dispersibility and size uniformity which eliminated completely other non-specific binding of high-abundance serum proteins. Most interestingly, the enrichment efficiency correlates more closely with the MNP dispersibility than the ligand density. Our investigation revealed the critical role of MNP dispersibility, as well as provided mechanistic insight into its impact on immunoaffinity enrichment and detection of CRP in one drop of serum sample. This strategy offers an essential advantage over the other methods by providing a simple and facile biofunctionalization protocol while maintaining excellent solvent dispersibility of MNPs.

Dopamine-Functionalized Gold Nanoparticles for Colorimetric Detection of Histamine.

Histamine, a primary biogenic amine (BA) generated through the decarboxylation of amino acids, concentration increases in protein-rich foods during deterioration. Thus, its detection plays a crucial role in ensuring food safety and quality. This study introduces an innovative approach involving the direct integration of dopamine onto gold nanoparticles (DCt-AuNP), aiming at rapid histamine colorimetric detection. Transmission electron microscopy revealed the aggregation of uniformly distributed spherical DCt-AuNPs with 12.02 ± 2.53 nm sizes upon the addition of histamine to DCt-AuNP solution. The Fourier-transform infrared (FTIR) spectra demonstrated the disappearance of the dicarboxy acetone peak at 1710 cm-1 along with the formation of well-defined peaks at 1585 cm-1, and 1396 cm-1 associated with the N-H bending modes and the aromatic C=C bond stretching vibration in histamine molecule, respectively, confirming the ligand exchange and interactions of histamine on the surface of DCt-AuNPs. The UV-vis spectra of the DCt-AuNP solution exhibited a red shift and a reduction in surface plasmon resonance (SPR) peak intensity at 518 nm along with the emergence of the 650 nm peak, signifying aggregation DCt-AuNPs with increasing histamine concentration. Notably, color transitions from wine-red to deep blue were observed in the DCt-AuNP solution in response to histamine, providing a reliable colorimetric signal. Dynamic Light Scattering (DLS) characterization showed a significant increase in the hydrodynamic diameter, from ∼15 to ∼1690 nm, confirming the interparticle cross-linking of DCt-AuNPs in the presence of histamine. This newly developed DCt-AuNP sensor provides colorimetric results in less than a minute that exhibits a remarkable naked-eye histamine detection threshold of 1.57 µM and a calculated detection limit of 0.426 µM, making it a promising tool for the rapid and sensitive detection of histamine.

Microplastic ingestion by adult milkfish Chanos chanos (Forsskål, 1775) in aquaculture system: The case of Butuan Bay, Philippines.

The Philippines is an archipelago that relies on marine resources. Butuan Bay in the Philippines supports aquaculture, which can contribute to and can be impacted by plastic pollution. However, the microplastics (MP) in milkfish, an important aquaculture species in the area, are yet to be ascertained. This study determined the prevalence of microplastics in the surrounding seawater and in the gut of adult milkfish from cages in Butuan and Nasipit in Butuan Bay. Water samples in Nasipit and Butuan contain 0.20 items/L and 1.00 items/L, respectively. MPs in milkfish in Butuan (10.27 items/individual) were significantly higher than in Nasipit (5.40 items/individual). A total of 235 MPs in 29 out of 30 fish samples (97 %) from the two sites were detected. The dominant MP shape and color were fiber and blue, respectively. The presence of microplastics in the milkfish may indicate a possible risk to the fish species and human health.

Breathing plastics in Metro Manila, Philippines: presence of suspended atmospheric microplastics in ambient air.

Microplastics (< 5 mm) have lately been identified in the atmosphere of urban, suburban, and even distant places far from plastic particle areas, suggesting the possibility of long-distance atmospheric transport of microplastics. However, the occurrence, fate, transmission, and effects of these suspended atmospheric microplastics (SAMPs) are all currently unknown in the Philippines. This study investigated the presence of suspected microplastic in the atmosphere of sixteen cities and one municipality of Metro Manila, Philippines. Sampling was conducted using a respirable dust sampler mounted with a Whatman GF/C filter paper at an intake flow rate of 1.4 L/min with Whatman GF/C filter paper. Results reveal that all seventeen sampling areas have the presence of SAMPs. A total of 155 SAMPs were found and confirmed in Metro Manila, with the highest concentration in Muntinlupa City and Mandaluyong City (0.023 SAMP/NCM). Fourteen SAMP types were identified across the sampling areas, ⁓ 74% with polyester. This study is the first record of the presence of microplastics suspended in the ambient air in the Philippines. It is estimated that an adult person in Metro Manila has the potential to inhale (5-8 per minute, normal minute ventilation) about 1 SAMP if exposed for about 99.0 to 132 h. Further studies should be done to evaluate the fate and health effects of these SAMPs in Metro Manila's setting.

Improving the efficiency of dye-sensitized solar cells based on rare-earth metal modified bismuth ferrites.

This study reports light energy harvesting characteristics of bismuth ferrite (BiFeO3) and BiFO3 doped with rare-earth metals such as neodymium (Nd), praseodymium (Pr), and gadolinium (Gd) dye solutions that were prepared by using the co-precipitation method. The structural, morphological, and optical properties of synthesized materials were studied, confirming that 5-50 nm sized synthesized particles have a well-developed and non-uniform grain size due to their amorphous nature. Moreover, the peaks of photoelectron emission for bare and doped BiFeO3 were observed in the visible region at around 490 nm, while the emission intensity of bare BiFeO3 was noticed to be lower than that of doped materials. Photoanodes were prepared with the paste of the synthesized sample and then assembled to make a solar cell. The natural and synthetic dye solutions of Mentha, Actinidia deliciosa, and green malachite, respectively, were prepared in which the photoanodes were immersed to analyze the photoconversion efficiency of the assembled dye-synthesized solar cells. The power conversion efficiency of fabricated DSSCs, which was confirmed from the I-V curve, is in the range from 0.84 to 2.15%. This study confirms that mint (Mentha) dye and Nd-doped BiFeO3 materials were found to be the most efficient sensitizer and photoanode materials among all the sensitizers and photoanodes tested.

Coconut power: a sustainable approach for the removal of Cr6+ ions using a new coconut-based polyurethane foam/activated carbon composite in a fixed-bed column.

To attain efficient removal of hexavalent chromium (Cr6+) from aqueous solutions, a novel polyurethane foam-activated carbon (PUAC) adsorbent composite was developed. The composite material was synthesized by the binding of coconut shell-based activated carbon (AC) onto a coconut oil-based polyurethane matrix. To thoroughly characterize the physicochemical properties of the newly developed material, various analytical techniques including FTIR spectroscopy, SEM, XRD, BET, and TGA analyses were conducted. The removal efficiency of the PUAC composite in removing Cr6+ ions from aqueous solutions was evaluated through column experiments with the highest adsorption capacity of 28.41 mg g-1 while taking into account variables such as bed height, flow rate, initial Cr6+ ion concentration, and pH. Experimental data were fitted using Thomas, Yoon-Nelson, and Adams-Bohart models to predict the column profiles and the results demonstrate high breakthrough and exhaustion time dependence on these variables. Among the obtained R2 values of the models, a better fit was observed using the Thomas and Yoon-Nelson models, indicating their ability to effectively predict the adsorption of Cr6+ ions in a fixed bed column. Significantly, the exhausted adsorbent can be conveniently regenerated without any noteworthy loss of adsorption capability. Based on these findings, it can be concluded that this new PUAC composite material holds significant promise as a potent sorbent for wastewater treatment backed by its excellent performance, cost-effectiveness, biodegradability, and outstanding reusability.

Microplastics in surface water of Laguna de Bay: first documented evidence on the largest lake in the Philippines.

The pollution of aquatic systems by microplastics is a well-known environmental problem. However, limited studies have been conducted in freshwater systems, especially in the Philippines. Here, we determined for the first time the amount of microplastics in the Philippines' largest freshwater lake, the Laguna de Bay. Ten (10) sampling stations on the lake's surface water were sampled using a plankton net. Samples were extracted and analyzed using Fourier-transform infrared spectroscopy (FTIR). A total of 100 microplastics were identified from 10 sites with a mean density of 14.29 items/m3. Most microplastics were fibers (57%), while blue-colored microplastics predominated in the sampling areas (53%). There were 11 microplastic polymers identified, predominantly polypropylene (PP), ethylene vinyl acetate copolymer (EVA), and polyethylene terephthalate (PET), which together account for 65% of the total microplastics in the areas. The results show that there is a higher microplastic density in areas with high relative population density, which necessitates implementing proper plastic waste management measures in the communities operating on the lake and in its vicinity to protect the lake's ecosystem services. Furthermore, future research should also focus on the environmental risks posed by these microplastics, especially on the fisheries and aquatic resources.

Synthesis and Characterization of Ferric Vanadate Nanorods for Efficient Electrochemical Detection of Ascorbic Acid.

This study reports the synthesis of ferric vanadate (FeVO4) via a facile hydrothermal method, focusing on demonstrating its exceptional electrochemical (EC) properties on detecting low-density ascorbic acid (AA). The phase purity, crystallinity, structure, morphology, and chemical compositional properties were characterized by employing X-ray diffraction, energy-dispersive X-ray spectroscopy, scanning electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy techniques. EC impedance spectroscopy and cyclic voltammetry techniques were also adopted in order to assess the EC response of a FeVO4-modified glassy carbon electrode for sensing AA at room temperature. The AA concentration range adopted in this experiment is 0.1-0.3 mM at a working electric potential of -0.13 V. The result showed functional excellence of this material for the EC determination of AA with good stability and reproducibility, promising its potentiality in connection with relevant sensing applications.

Biosynthesizing Cassia fistula Extract-Mediated Silver Nanoparticles for MCF-7 Cell Lines Anti-Cancer Assay.

The unique consequence of green synthesis is that the mediator plant is able to release chemicals that are efficacious as reducing as well as stabilizing agents. In this work, the fruit pulp and leaf essences of Cassia fistula have been used to manufacture silver nanoparticles through the green synthesis technique. The sculpturing of nanoparticles was accomplished by utilizing the reduction phenomenon that ensued due to the reaction between plant essences and the precursor solution. These biosynthesized silver nanoparticles were examined, where we used scanning electron microscopy, UV-vis spectroscopy, and X-ray diffraction techniques as means to analyze the structure, optical properties, and crystalline behavior, respectively. The absorption spectra for fruit and leaf extracts obtained from the UV-vis analyses peaked at 401 and 397 nm, and these peaks imply the appearance of optical energy gaps of 2.12 and 2.58 eV, accompanying spherical shapes of particles with diameters in the ranges of 12-20 and 50-80 nm, respectively. These silver nanoparticles together with the adopted green technique have a vast array of applications, specifically in the biomedical realm. In particular, they are being used to treat several diseases and are manifested as strong anti-tumor agents to medicate MCF-7 breast cancer cell lines in order to minimize the cell growth rate depending on their concentrations.

Ab-initio study of pressure influenced elastic, mechanical and optoelectronic properties of Cd0.25Zn0.75Se alloy for space photovoltaics.

The optoelectronic properties of the ternary Cd0.25Zn0.75Se alloy are reported under the influence of a high pressure ranging from 0 to 25 GPa, within a modified Becke-Jhonson potential using density functional theory. This alloy has a cubic symmetry, is mechanically stable, and its bulk modulus rises with pressure. It is observed to be a direct bandgap material with a bandgap energy that increases from 2.37 to 3.11 eV with rise in pressure. Pressure changes the optical and electronic properties, causing the absorption coefficient to rise and absorb visible green-to-violet light. The static dielectric constant, along with the static index of refraction, both increase under the influence of pressure. Optical constants, including dielectric constant, optical conductivity, refractive index, extinction coefficient, and reflection, are also investigated and discussed. This DFT forecast explores important research directions for the usage of the CdZnSe semiconductor alloys in the manufacturing of space photovoltaic and optoelectronic devices operating at different pressures.

UV-activated multilayer nanomatrix provides one-step tunable carbohydrate structural characterization in MALDI-MS.

The structure-specific fragmentation of gas-phase ions in tandem mass spectrometry among other techniques provides an efficient analytical method for confirming unknown analytes or for elucidating chemical structures. Using concentration-dependent UV-absorbing matrix-functionalized magnetic nanoparticles and matrix-assisted laser desorption-ionization mass spectrometry (MALDI MS), we developed a single-step pseudo-MS/MS approach for tunable ionization and fragmentation to facilitate structure determination. Without chemical derivatization, we have demonstrated that this approach successfully distinguished isomeric sets of di-, tri- and tetrasaccharides. Low concentration of nanomatrix provided an enhanced signal for accurate mass determination of the intact molecular ions of analytes present in the sample. In contrast, high concentration of nanomatrix induced extensive and unique fragmentation, including high-energy facile bond breakage (A- and X-type cross-ring cleavages), which facilitated the linkage and sequence characterization of oligosaccharides without conventional tandem mass spectrometric instrumentation. The practicality of this approach for complex sample analysis was evaluated by an oligosaccharide mixture, wherein molecular ions are unambiguously observed and signature product ions are distinguishable enough for molecular identification and isomer differentiation by this simple tunable approach. By probing the roles of the multilayer nanomatrix components: matrix (energy absorption), silane-coating (energy pooling and dissipation) and core Fe3O4 (fragmentation), a plausible energy transfer mechanism was proposed based on a computational study and photoelectron experiments. The differentiation of tri- and tetra-oligosaccharide shown in this study not only demonstrated the first step toward glycan characterization by nanoparticle-assisted MALDI-MS, but also shed some insight on the nanoparticle-mediated energy transfer dynamics behind our approach.