Doxorubicin encapsulated blend of sitagliptin-lignin polymeric drug delivery system for effective combination therapy against cancer.

In this research, a sitagliptin-lignin biopolymer (SL) containing zinc selenide quantum dots (ZnSe QDs) and doxorubicin (doxo) was synthesized. The fabricated polymeric drug delivery system was characterized via FTIR, XRD, SEM, TGA, IR, and DSC. SLQD-Doxo exhibited an irregular surface with a 32 nm diameter and well-defined surface chemistry. Drug loading efficiency was assessed at different concentrations, pH levels, time intervals, and temperatures, and drug kinetics were calculated. Maximum drug release was observed at 6 µmol concentration after 24 h, pH of 6.5 and 45 °C. The maximum drug encapsulation efficiency was 81.75 %. SLQD-Doxo demonstrated 24.4 ± 1.04 % anti-inflammatory activity, and the maximum lipoxygenase inhibition in a concentration-dependent manner was 71.45 ± 2.02 %, compared to indomethacin, a standard anticancer drug. The designed system was applied to breast cancer MCF-7 cells to evaluate anticancer activity. Cytotoxicity of SLQD-Doxo resulted in 24.48 ± 1.64 dead cells and 74.39 ± 4.12 viable cells. Lignin's polyphenolic nature resulted in good antioxidant activity of LLQD-Doxo. The combination of SLQD-Doxo was appropriate for drug delivery at high temperatures and acidic pH of tumor cells compared to healthy cells.

Novel thymohydroquinone gallate (THQG) derivative loaded ligand Modified quantum dots as pH-Sensitive Multi-Modal theragnostic agent for cancer treatment.

BACKGROUND: Nanomedicine, as the combination of radiopharmaceutical and nanocarrier (QDs), is developed for treating cancer. Gallic acid is antimutagenic, anti-inflammatory, and anti-carcinogenic. Typical retention time of gallic acid is approximately 4 to 8 h. To increase the retention time gallic acid is converted to prodrug by adding lipophilic moieties, encapsulating in lipophilic nanoparticles, or liposome formation. Similarly, thymoquinone is powerful antioxidant, anti-apoptotic, and anti-inflammatory effect, with reduced DNA damage. METHODS: In this study, a hydrophilic drug (gallic acid) is chemically linked to the hydrophobic drug (thymohydroquinone) to overcome the limitations of co-delivery of drugs. Thymohydroquinone (THQG) as the combination of gallic acid (GA) and thymoquinone (THQ) is loaded onto the PEI functionalized antimonene quantum dots (AM-QDs) and characterized by FTIR, UV-visible spectroscopy, X-ray powder diffraction, Zeta sizer, SEM and AFM, in-vitro and in-vivo assay, and hemolysis. RESULTS: The calculated drug loading efficiency is 90 %. Drug release study suggests the drug combination is pH sensitive and it can encounters acidic pH, releasing the drug from the nanocarrier. The drug and drug-loaded nanocarrier possesses low cytotoxicity and cell viability on MCF-7 and Cal-27 cell lines. The proposed drug delivery system is radiolabeled with Iodine-131 (131I) and Technetium (99mTc) and its deposition in various organs of rats' bodies is examined by SPECT-CT and gamma camera. Hemolytic activity of 2, 4, 6, and 8 µg/ml is 1.78, 4.16, 9.77, and 15.79 %, respectively, reflecting low levels of hemolysis. The system also sustains oxidative stress in cells and environment, decreasing ROS production to shield cells and keep them healthy. CONCLUSIONS: The results of this study suggest that the proposed drug carrier system can be used as a multi-modal theragnostic agent in cancer.

2D MXenes and their composites; design, synthesis, and environmental sensing applications.

Novel 2D layered MXene materials were first reported in 2011 at Drexel University. MXenes are widely used in multidisciplinary applications due to their anomalous electrical conductivity, high surface area, and chemical, mechanical, and physical properties. This review summarises MXene synthesis and applications in environmental sensing. The first section describes different methods for MXene synthesis, including fluorinated and non-fluorinated methods. MXene's layered structure, surface terminal groups, and the space between layers significantly impact its properties. Different methods to separate different MXene layers are also discussed using various intercalation reagents and commercially synthesized MXene without compromising the environment. This review also explains the effect of MXene's surface functionalization on its characteristics. The second section of the review describes gas and pesticide sensing applications of Mxenes and its composites. Its good conductivity, surface functionalization with negatively charged groups, intrinsic chemical nature, and good mechanical stability make it a prominent material for room temperature sensing of environmental samples, such as polar and nonpolar gases, volatile organic compounds, and pesticides. This review will enhance the young scientists' knowledge of MXene-based materials and stimulate their diversity and hybrid conformation in environmental sensing applications.

Synthesis of novel nonsteroidal anti-inflammatory galloyl ß-sitosterol-loaded lignin-capped Ag-based drug.

Biocompatible anti-inflammatory lignin-capped Ag (LCAg) nanoparticles (NPs) were synthesized for the delivery of galloyl ß-sitosterol (Galloyl-BS). ß-Sitosterol (BS) is effective against inflammatory responses, like cancer-induced inflammations. BS was modified via gallic acid esterification to enhance its anti-inflammatory potential. LCAg NPs were synthesized by a green method and loaded with galloyl-BS. For comparison, pure BS was also loaded onto LCAg NPs in a separate assembly. The antioxidant potential of Galloyl-BS was greater (IC50 177 µM) than pure BS. Materials were characterized by FT-IR, SEM, XRD, and Zeta potential. Using UV-Vis spectroscopy, drug release experiments were performed by varying pH, time, concentration, and temperature. Maximum drug release was observed after 18 h at pH 6 and 40 °C. Galloyl-BS showed improved drug loading efficiency, release %age, and antioxidant activity compared to pure BS when loaded onto LCAg NPs. DLCAg exhibited excellent anti-inflammatory activity in rat models. These findings indicate that galloyl-BS (drug)-loaded LCAg (DLCAg) NPs have the potential as an anti-inflammatory agent without any prior release and scavenging in normal cells.

Smartphone-Assisted EY@MOF-5-Based Dual-Emission Fluorescent Sensor for Rapid On-Site Detection of Daclatasvir and Nitenpyram.

Fluorescent metal-organic frameworks (MOFs) are promising sensing materials with tunable and robust structural properties and remarkable luminescent capabilities. In this study, a novel dual-emission fluorescent metal-organic framework (EY@MOF-5) composite is synthesized by a one-pot bottle-around-ship approach. Eosin Y (EY) is encapsulated in MOF-5 to enhance its fluorescence properties and selectivity, effectively addressing typical MOF-5 limitations. EY@MOF-5 serves as a versatile dual-functional fluorescent sensor for two different analytes, daclatasvir (DCT) and nitenpyram (NTP), showing an impressive linear range of 10-200 nM and 0.1-300 µM, with detection limits of 233 pM and 65 nM, respectively. The established method is ultrafast, highly sensitive, and extremely selective for DCT and NTP detection in complex biological and food samples. Fluorescence results are compared and validated with the recommended UPLC method. Then, a smartphone-integrated sensing system is introduced for on-site, real-time, and quantitative analysis of DCT and NTP. The smartphone-assisted intelligent sensing method manifests promising results for DCT and NTP monitoring in biological and food samples, demonstrating its promising potential for the on-site detection of biologically and environmentally significant analytes.

Recent advancements in the fabrication and photocatalytic applications of graphitic carbon nitride-tungsten oxide nanocomposites.

The present review focuses on the widely used graphitic carbon nitride (g-C3N4)-tungsten oxide (WO3) nanocomposite in photocatalytic applications. These catalysts are widely employed due to their easy preparation, high physicochemical stability, nontoxicity, electron-rich properties, electronic band structure, chemical stability, low cost, earth-abundance, high surface area, and strong absorption capacity in the visible range. These sustainable properties make them predominantly attractive and unique from other photocatalysts. In addition, graphitic carbon nitride (g-C3N4) is synthesized from nitrogen-rich precursors; therefore, it is stable in strong acid solutions and has good thermal stability up to 600 °C. This review covers the historical background, crystalline phases, density-functional theory (DFT) study, synthesis method, 0-D, 1-D, 2-D, and 3-D materials, oxides/transition/nontransition metal-doped, characterization, and photocatalytic applications of WO3/g-C3N4. Enhancing the catalytic performance strategies such as composite formation, element-doping, heterojunction construction, and nanostructure design are also summarized. Finally, the future perspectives and challenges for WO3/g-C3N4 composite materials are discussed to motivate young researchers and scientists interested in developing environment-friendly and efficient catalysts.

Mapping the low abundant plasma glycoproteome using Ranachrome-5 immobilized magnetic terpolymer as improved HILIC sorbent.

HILIC (hydrophilic interaction liquid chromatography) materials enrich glycopeptides. The non-specific interactions because of support material and inadequate hydrophilicity render loss of less abundant glycopeptides in SPE-based enrichments. In this work, magnetic terpolymer (Fe3O4@MAA/DVB/1,2-Epoxy-5-hexene) is functionalized with Ranachrome-5 to generate enhanced hydrophilicity. Amine, carboxylic, and amide groups of ranachrome-5 provide zwitterionic chemistry. Material's magnetic core contributes to ease of operation while higher surface area 97.0711 m2 g-1 immobilizes better quantities of Ranachrome-5. Homogeneous morphology, nano-size, and super hydrophilicity enhance enrichment. Ranachrome-5 functionalized polymeric core-shell beads enrich 25, 18 and 16 N-linked glycopeptides via SPE strategy from tryptic digests of model glycoproteins i.e., immunoglobulin G (IgG), horseradish peroxidase (HRP) and chicken avidin, respectively. Zwitterionic chemistry of ranachrome-5 helps in achieving higher selectivity (1:250, HRP / Bovine Serum Albumin), and lower detection limit (100 attomole, HRP digest) with complete glycosylation profile of each standard digest. High binding capacity (137.1 mg/g) and reuse of affinity material up to seven cycles reduce the cost and amount of affinity material for complex sample analysis. A recovery of 91.76% and relative standard deviation (RSD) values less than 1 define the application of HILIC beads for complex samples like plasma. 508 N-linked intact low abundant glycopeptides corresponding to 50 glycoproteins are identified from depleted human plasma samples via nano-Liquid Chromatography-Tandem Mass Spectrometry (nLC-MS/MS). Using Single Nucleotide Variances (BioMuta) for low abundant plasma glycoproteins, the potential association of proteins to four cancers, i.e., breast, lung, uterine, and melanoma is evaluated. Via the bottom-up approach, HILIC beads can analyze clinically important low-abundant glycoproteins.

Stearic Acid and CeO2 Nanoparticles Co-functionalized Cotton Fabric with Enhanced UV-Block, Self-Cleaning, Water-Repellent, and Antibacterial Properties.

Superhydrophobic cotton fabrics with multifunctional features are highly desired in domestic and outdoor applications. However, the short coating longevity and hazardous reagents significantly reduce their commercial-scale applications. Herein, we introduce CeO2 nanoparticles and stearic acid (SA) to develop a fluorine-free, durable superhydrophobic cotton fabric that mimics the lotus effect. The pristine cotton fabric is treated with APTES-functionalized CeO2 nanoparticles by immersion followed by a dip and drying treatment with a 2% myristic acid solution. This sequential process creates a stable superhydrophobic cotton fabric (SA/CeO2-cotton fabric) with a water contact angle of 158° and a water sliding angle of 5°. The results are attributed to the combined effect of CeO2 nanoparticles and stearic acid that enhances surface roughness and reduces surface sorption energy. APTES facilitates the durable attachment of CeO2 nanoparticles and stearic acid to the cotton fabric. The modified cotton fabric is characterized by advanced analytical tools, demonstrating enhanced superhydrophobicity, self-cleaning, and antiwater absorption properties. Additionally, it exhibits remarkable UV-blocking (UPF 542) and antibacterial properties. The designed superhydrophobic cotton fabric unveils good mechanical, thermal, and chemical durability. The proposed strategy is simple, green, and economical and can be used commercially for functional fabric preparation.

Quantification of tramadol and serotonin by cobalt nickel tungstate in real biological samples to evaluate the effect of analgesic drugs on neurotransmitters.

In this work, CoNiWO4 nanocomposite was used as an electrochemical sensor for the simultaneous electrochemical detection of tramadol and serotonin. The nanocomposite was synthesized using a hydrothermal method and characterized via XRD, SEM, TGA, Zeta, UV, and FTIR. The sensor was developed by depositing CoNiWO4-NPs onto the glassy carbon electrode surface. Tramadol and serotonin were detected by employing cyclic voltammetry (CV), differential pulse voltammetry (DPV), electrochemical impedance spectroscopy (EIS), and chronoamperometry. Analytes were detected at different pH, concentrations, and scan rates. The prepared sensor showed a 0-60 µM linear range, with a LOD of 0.71 µM and 4.29 µM and LOQ of 14.3 µM and 2.3 µM for serotonin and tramadol, respectively. Finally, the modified electrode (CoNiWO4-GCE) was applied to determine tramadol and serotonin in biological samples.

Profiling of phosphorylated metabolites from lung cancer by zeolite loaded Mg-Al-Ce ternary hydroxide (Zeolite@MAC) composite.

Phosphorylated metabolites are linked to metabolism, and the dysregulation of metabolic reactions brings cancer. Dysregulated levels lead to hyperactivation of glycolytic and mitochondrial oxidative phosphorylation pathways. Abnormal concentrations are the indicators of energy-related disorders. In this work, Zeolite-loaded Mg-Al-Ce hydroxides (Zeolite@MAC) are prepared by co-precipitation and characterized through FTIR, XRD, SEM, BET, AFM, TEM, and DLS. Magnesium-Aluminum-Cerium-Zeolite particles enrich phosphate-containing small molecules. These ternary hydroxides carried out the main adsorption mechanism, which swapped the surface hydroxyl group ligands for phosphate and the inner-sphere complex of CePO4. XH2O. Cerium plays a significant role in the complexation of phosphate, and adding Mg and Al further helps disperse Ce and increase the surface charge on the adsorbent. ΑTP and AMP are the standard molecules for parameter optimization. Zeolite@MAC enriches phosphorylated metabolites followed by their desorption via UV-vis spectrophotometry. MS profiles for healthy and lung cancer serum samples are obtained for phosphorylated metabolites. Characteristic phosphorylated metabolites have been detected in lung cancer samples with high expression. The role of phosphorylated metabolites is explored for abnormal metabolic pathways in lung cancer. The fabricated material is sensitive, selective, and highly enriched for identifying phosphate-specific biomarkers.

Facile synthesis of Ag@Fe3O4/ZnO nanomaterial for label-free electrochemical detection of methemoglobin in anemic patients.

Methemoglobinemia (MetHb, Fe3+) is a chronic disease arising from the unequal distribution of oxyhemoglobin (HbFe2+, OHb) in the blood circulatory system. The oxidation of standard oxyhemoglobin forms methemoglobin, causing cyanosis (skin bluish staining). Methemoglobin cannot bind the pulmonary gaseous ligands such as oxygen (O2) and carbon monoxide (CO). As an oxidizing agent, the biochemical approach (MetHb, Fe3+) is modified in vitro by sodium nitrite (NaNO2). The silver-doped iron zinc oxide (Ag@Fe3O4/ZnO) is hydrothermally synthesized and characterized by analytical and spectroscopic techniques for the electrochemical sensing of methemoglobin via cyclic voltammetry (CV). Detection parameters such as concentration, pH, scan rate, electrochemical active surface area (ECSA), and electrochemical impedance spectroscopy (EIS) are optimized. The linear limit of detection for Ag@Fe3O4/ZnO is 0.17 µM. The stability is determined by 100 cycles of CV and chronoamperometry for 40 h. The serum samples of anemia patients with different hemoglobin levels (Hb) are analyzed using Ag@Fe3O4/ZnO modified biosensor. The sensor's stability, selectivity, and response suggest its use in methemoglobinemia monitoring.

Facile synthesis of the SnTe/SnSe binary nanocomposite via a hydrothermal route for flexible solid-state supercapacitors.

Environmental degradation and energy shortage are the two biggest problems facing the world right now. Because of the limited supply of non-renewable sources, the production of environment-friendly energy and its storage has gained significant importance. Pseudocapacitors have lately caught the interest of energy specialists due to their greater energy/power density and prolonged cycle life. In this work, binding-free SnTe/SnSe (STSS) electrodes deposited onto Ni foam (NF) as the conductive substrate have been developed by a facile hydrothermal route for supercapacitor applications. Several analytical tools were utilized to study the morphological, structural and textural characteristics. The electrochemical results obtained from a three-electrode system suggest that the STSS electrode material exhibits great specific capacitance (C s) of 1276 F g-1, specific energy (E d) of 46.45 W h kg-1 and specific power (P d) of 256 W kg-1 @ 1 A g-1. The results of C dl indicate that the STSS (31.28 mF) has a larger C dl value than those of SnTe (23.22 mF) and SnSe (26.35 mF). The analysis of electrochemical stability indicates that the STSS displays structural stability over 5000 cycles with a maximum capacitance retention of 96%. The Nyquist plot profile displayed a smaller R ct value for STSS (0.89 Ω) than SnSe (1.13 Ω) and SnTe (1.97 Ω). The symmetric behavior of STSS was determined in 2.0 M potassium hydroxide. The results reveal that this material has a specific capacitance of 537.72 F g-1 and specific energy of 78.32 W h kg-1. These findings suggest that the STSS electrode might serve as a potential candidate for supercapacitors and other energy-saving equipment.

Fabrication and employment of cobalt-doped yttrium iron garnets for the electrochemical analysis of anti-diabetic, metformin in serum of type 2 diabetes mellitus patients.

Metformin (MET) is an anti-diabetic drug employed as the first-line therapy for patients of type II diabetes mellitus (T2DM). Overdosage of drugs leads to severe outcomes, and its monitoring in biofluids is vital. The present study develops cobalt-doped yttrium iron garnets and employs them as an electroactive material immobilized on a glassy carbon electrode (GCE) for the sensitive and selective detection of metformin via electroanalytical techniques. The fabrication procedure via the sol-gel method is facile and gives a good yield of nanoparticles. They are characterized by FTIR, UV, SEM, EDX, and XRD. Pristine yttrium iron garnet particles are also synthesized for comparison, where the electrochemical behaviors of varying electrodes are analyzed via cyclic voltammetry (CV). The activity of metformin at varying concentrations and pH is investigated via differential pulse voltammetry (DPV), and the sensor generates excellent results for metformin detection. Under optimum conditions and at a working potential of 0.85 V (vs. Ag/AgCl/3.0 M KCl), the linear range and limit of detection (LOD) obtained through the calibration curve are estimated as 0-60 µM and 0.04 µM, respectively. The fabricated sensor is selective for metformin and depicts a blind response toward interfering species. The optimized system is applied to directly measure MET in buffers and serum samples of T2DM patients.

Human serum N-glycome profiling via the newly developed asparagine immobilized cellulose/polymer nanohybrid.

Human serum N-linked glycans expression levels change during the disease progression. The low abundance, structural diversity, and coexisting matrices hinder their detection in mass spectrometry analysis. Considering the hydrophilic nature of N-glycans, cellulose/polymer (1,2-Epoxy-5-hexene) nanohybrid is fabricated with oxirane groups functionalized of asparagine to develop solid phase extraction based hydrophilic interaction liquid chromatography sorbent (cellulose/1,2-Epoxy-5-hexene/asparagine). The morphology, elemental analysis, and surface properties are studied through scanning electron microscopy, energy dispersive X-ray spectroscopy, and Fourier-transform infrared spectroscopy. The large surface area of cellulose/polymer nanohybrid (2.09 × 102  m2 /g) facilitates the high density of asparagine immobilization resulting in better hydrophilic interaction liquid chromatography enrichment under optimized conditions. The enrichment capability of nanohybrid/asparagine is assessed by the N-Linked glycans released from ovalbumin and immunoglobulin G where 23 and 13 N-glycans are detected respectively. The nanohybrid/asparagine shows selectivity of 1:1200 with spiked bovine serum albumin and sensitivity down to 100 attomole. Human serum profiling for N-glycans identifies 52 glycan structures. This new enrichment strategy enriches serum N-linked glycans in the presence of salts, proteins, endogenous serum peptides, and so forth.

Terpolymeric platform with enhanced hydrophilicity via cysteic acid for serum intact glycopeptide analysis.

A new polymeric (methyl methacrylate/ethylene glycol dimethacrylate/1,2-epoxy-5-hexene) base/matrix has been fabricated and decorated with zwitterionic hydrophilic cysteic acid (Cya) for the enrichment of intact N-glycopeptides from standards and biological samples. Terpolymer-Cya provides good enrichment efficiency, improved hydrophilicity, and selectivity by virtue of better surface area (2.09 × 102 m2/g) provided by terpolymer and the zwitterionic property offered by cysteic acid. Cysteic acid-functionalized polymeric hydrophilic interaction liquid chromatography (HILIC) sorbent enriches 35 and 24 N-linked glycopeptides via SPE (solid phase extraction) mode from tryptic digests of model glycoproteins, i.e., immunoglobulin G (IgG) and horseradish peroxidase (HRP), respectively. Zwitterionic chemistry of cysteine helps in achieving higher selectivity with BSA digest (1:200), and lower detection limit down to 100 attomoles with a complete glycosylation profile of each standard digest. The recovery of 81% and good reproducibility define the application of terpolymer-Cya for complex samples like a serum. Analysis of human serum provides a profile of 807 intact N-linked glycopeptides via nano-liquid chromatography-tandem mass spectrometry (nLC-MS/MS). To the best of our knowledge, this is the highest number of glycopeptides enriched by any HILIC sorbent. Selected glycoproteins are evaluated in link to various cancers including the breast, lung, uterine, and melanoma using single-nucleotide variances (BioMuta). This study represents the complete idea of using an in-house developed strategy as a successful tool to help analyze, relate, and answer glycoprotein-based clinical issues regarding cancers.

Facile hydrothermal synthesis of NiTe nanorods for non-enzymatic electrochemical sensing of whole blood hemoglobin in pregnant anemic women.

Electrochemical sensing methods monitor biomolecules because of their specificity, rapid response, lower cost, and automation. Hemoglobin is an abundant protein in the human body and is correlated with various physiological processes. Levels of hemoglobin in blood are associated with anemia in pregnant women. In this research, a non-enzymatic sensor based on NiTe nanorods is developed for the detection and quantification of hemoglobin (Hb) from anemic pregnant patients. NiTe nanorods are synthesized by the single-step method. After characterizing the material, sensing parameters such as the effect of scan rate, pH, concentration, and interferences are optimized using standard hemoglobin samples. Linearity, the limit of detection (LOD), and the limit of quantification (LOQ) for NiTe nanorods are 0.99698, 0.012 nM, and 0.04 nM, respectively. Stability is measured by cyclic chronoamperometry (12 h) and voltammetry (100 cycles). Recovery of hemoglobin from blood samples is in the range of 63-90%. NiTe nanorods quantitatively determine hemoglobin from the blood samples of anemic pregnant women.

Iminodiacetic acid (IDA)-generated mesoporous nanopolymer: a template to relate surface area, hydrophilicity, and glycopeptides enrichment.

A three-step strategy is introduced to develop inherent iminodiacetic (IDA)-functionalized nanopolymer. SEM micrographs show homogenous spherical beads with a particle size of 500 nm. Further modification to COOH-functionalized 1,2-epoxy-5-hexene/DVB mesoporous nanopolymer enriches glycopeptides via hydrophilic interactions followed by their MS determination. Significantly high BET surface area 433.4336 m2 g-1 contributes to the improved surface hydrophilicity which is also shown by high concentration of ionizable carboxylic acids, 14.59 ± 0.25 mmol g-1. Measured surface area is the highest among DVB-based polymers and in general much higher in comparison to the previously reported BET surface areas of co-polymers, terpolymers, MOFs, and graphene-based composites. Thirty-one, 19, and 16 N-glycopeptides are enriched/identified by nanopolymer beads from tryptic digests of immunoglobulin G, horseradish peroxidase, and chicken avidin, respectively, without additional desalting steps. Material exhibits high selectivity (1:400 IgG:BSA), sensitivity (down to 0.1 fmol), regeneration ability up to three cycles, and batch-to-batch reproducibility (RSD > 1%). Furthermore, from 1 µL of digested human serum, 343 N-glycopeptide characteristics of 134 glycoproteins including 30 FDA-approved serum biomarkers are identified via nano-LC-MS/MS. The developed strategy to self-generate IDA on polymeric surface with improved surface area, porosity, and ordered morphology is insignia of its potential as chromatographic tool contributing to future developments in large-scale biomedical glycoproteomics studies.

Apo-H (beta-2-glycoprotein) intact N-glycan analysis by MALDI-TOF-MS using sialic acid derivatization.

Apo-H is a plasma glycoprotein. Nearly 19% of the molecular weight of this protein is composed of glycans. Up- and down-regulation and structural changes in protein glycans provide diagnostic value for disease detection. Here, an efficient, sensitive, and optimized method is developed for Apo-H N-glycans analysis by MALDI-TOF-MS in positive mode. This bioanalytical method includes sample preparation, sample purification, and detection. An Apo-H enrichment method is developed using standard proteins by anti-Apo-H beads followed by enrichment from plasma samples. SDS-PAGE confirms the Apo-H protein enrichment, which is further verified by LC-MS/MS analysis. The lower ionization efficiency of sialylated glycan hampers their analysis by MALDI-MS. For this, stabilization of sialic acids is done by selective derivatization of carboxyl groups to differentiate between α(2,3)- and α(2,6)-linked sialic acids. Glycans are further purified by HILIC-SPE and analyzed by MALDI-MS. Several branched bi- and tri-antennary glycans with fucosylation and sialylation are identified. The reproducibility of the developed method is tested by analyzing multiple replicates of human plasma, where the same glycans are consistently identified. This method could be applied for the Apo-H glycan profiling of large clinical cohorts for diagnostic purposes.

Tin derived antimony/nitrogen-doped porous carbon (Sb/NPC) composite for electrochemical sensing of albumin from hepatocellular carcinoma patients.

An electrochemical sensor based on an antimony/nitrogen-doped porous carbon (Sb/NPC) composite has been developed for the quantitative detection of albumin from hepatocellular carcinoma (HCC) patients. Sb/NPC is hydrothermally synthesized from Sn/NPC precursors. The synthesized precursor (Sn/NPC) and the product (Sb/NPC) are characterized by XRD, FTIR, TGA, UV/Vis, SEM, and AFM. Cyclic voltammetry, chronoamperometry, and electrochemical impedance studies are used to investigate the electrochemical performance of Sb/NPC-GCE. Sb/NPC-GCE detects albumin at physiological pH of 7.4 in the potential range 0.92 V and 0.09 V for oxidation and reduction, respectively. LOD and recovery of Sb/NPC-GCE for the determination of albumin are 0.13 ng.mL-1 and 66.6 ± 0.97-100 ± 2.73%, respectively. Chronoamperometry of the modified working electrode demonstrates its stability for 14 h, indicating its reusability and reproducibility. Sb/NPC-GCE is a selective sensor for albumin detection in the presence of interfering species. The electrode has been applied for albumin detection in human serum samples of HCC patients. A negative correlation of albumin with alpha-fetoprotein levels in HCC patients is observed by statistical analysis.

Graphene oxide-metal oxide nanocomposites for on-target enrichment and analysis of phosphorylated biomolecules.

The surface of matrix-assisted laser desorption/ionization mass spectrometry target is modified for improved signal strength and detection of analytes. The developed method includes on-target enrichment and detection of phosphopeptides/phospholipids using graphene oxide-lanthanide metal oxides (samarium, gadolinium, dysprosium, and erbium) nanocomposites. Enriched phosphopeptides are detected using material enhanced laser desorption/ionization mass spectrometry and phospholipids by laser desorption/ionization-mass spectrometry. Nanocomposites are prepared using graphene oxide with respective metal salts at high pH. They are characterized for nano-morphology, chemistry, porosity, composition, crystallinity, and thermal stability. Phosphopeptides enrichment protocol is developed and optimized for tryptic ß-casein digest and that of phospholipids by phosphatidylcholine standard. Statistical analyses of phosphopeptides and phospholipids from milk show overlapping results for gadolinium, dysprosium, and erbium oxide nanocomposites. GO-Gd2 O3 has better enrichment efficiency and application as LDI material. Selectivity for GO-Dy2 O3 is 1:2500, for GO-Sm2 O3 is 1:3500, and 1:4000 for GO-Gd2 O3 . GO-Er2 O3 has a sensitivity of 25 fmol, whereas the highest sensitivity is down to 0.5 fmol for GO-Gd2 O3 . On-target enrichment is batch to batch reproducible with a standard deviation of <1, reduced time of enrichment to 10 min, and ease of operation compared to solid-phase batch extraction. The developed method enriches serum phosphopeptides characteristic of cancer-related phosphoproteins.