Carbon-coated copper nanocrystals with enhanced peroxidase-like activity for sensitive colorimetric determination of 2,4-dinitrophenylhydrazine.

Carbon-coated copper nanocrystals (CuNCs) with peroxidase-like activity were hydrothermally prepared by using copper acetate, citric acid (CA) and histidine (His) as the precursors. Various shaped CuNCs, including urchin-like, slab-like and spherical appearance were facilely prepared by addition of different amount of NaNO2 in the precursor solutions. When 3,3',5,5'-tetramethylbenzidine (TMB) was used as the substrate, the CuNCs with urchin-like appearance have greatest peroxidase-like activity and their Michaelis-Menten constant (Km) and the maximum rate constant (νmax) are respectively 8.8 and 1.2 times higher than that obtained from horseradish peroxidase (HRP). The production of reactive oxygen species (ROS) was confirmed by radical quenching and electron spin resonance (ESR) tests. Subsequent studies have found that the CuNCs catalyzed color reaction of TMB can be selectively quenched by the environmental pollutant 2,4-dinitrophenylhydrazine (2,4-DNPH). Thus a new colorimetric method for the determination of 2,4-DNPH with a linear range of 0.60-20 µM was developed and a limit of detection (LOD) as low as 0.166 µM was achieved. The results obtained not only reveal the tunability of the peroxidase-like activity of Cu-based nanomaterials, but also provide a new method for the sensitive determination of environmental contaminate.

Fabrication of nitrogen-doped graphene nanosheets anchored with carbon nanotubes for the degradation of tetracycline in saline water.

The treatment of wastewater with high salinity is still a challenge because of the quenching effect of various anions on radical processes. The nonradical process may be a more promising pathway. Herein, a 3D structured nitrogen-doped graphene nanosheet anchored with carbon nanotubes (N-GS-CNTs) was prepared by direct pyrolysis of K3Fe(CN)6. The as-prepared catalyst can effectively activate peroxymonosulfate (PMS) for mineralization of tetracycline (TC) over a wide pH range (from 3 to 11) and even in high saline water (500 mM Cl-, HCO3-, etc.). The degradation mechanism was elucidated by both experimental characterizations and DFT calculations. The high catalytic efficiency was attributed to accelerated electron transfer from donor (TC) to acceptor (PMS) in the presence of the catalyst, which acts as electron shuttle mediators to promote a nonradical process. At the same time, the catalyst also enhances the production of singlet oxygen (1O2), hence further increasing the degradation rate. This study not only provides a simple method for synthesizing N-GS-CNT catalysts but also provides new insights into the electron transfer pathway for the removal of organic pollutants under high salinity conditions.

Luminescent Chemosensor Based on Ru(II) Bipyridine Complex for Detection of Sudan I through Inner Filter Effect.

Presence of Sudan I in food stuff can be problematic and need to be checked in order to protect our health from possible carcinogen. Therefore, it is essential to detect Sudan I by efficient, rapid and reliable method. In this work, we have designed a Ru(II) polypyridyl complex, [Ru(bpy)2(CIP)]2+ probe for the selective and sensitive detection of Sudan I. Upon addition of Sudan I to the solution of [Ru(bpy)2(CIP)]2+ in ethanol, the luminescence quenched rapidly, and linear concentration range with analyte has been obtained from 0.8 to 100 µM with the limit of detection as low as 0.26 µM (S/N = 3). The effective luminescence quenching was resulted due to the inner filter effect (IFE) between luminophore, [Ru(bpy)2(CIP)]2+ and quencher, Sudan I. Our spectroscopic study was essentially provided sufficient analytical evidences in order to prove occurrence of IFE mechanism. As there were no interferences observed in luminescence measurement from the other substances the present probe has been successfully applied for the detection of Sudan I in commercial chili powder sample, making the probe suitable for practical usage.

Potassium Ferrate(VI) as a Highly Efficient and Environmentally Friendly Chemiluminescence Reagent in Acidic Solution.

Herein we report that the reactions of potassium ferrate (VI) with a number of reductants can produce strong chemiluminescence (CL) in acidic aqueous solution. The CL Spectra were registered and compared with the classical KMnO4 and NaClO-H2O2 CL systems. The characteristic emission peaks at 1268 and 1050 nm were observed, which are consistent to the spectrum obtained from the NaClO-H2O2 system. Additional emission bands at 680 nm further confirmed the formation of singlet oxygen dimers. The high CL intensity and the chemically green nature of K2FeO4, prompt us to further develop it as a novel CL reagent. Sensitive response and wide calibration ranges were obtained for dopamine, ascorbic acid, and ethanol. The linear range for the determination of three analytes were 50 nM to 50 µM for dopamine (LOD: 20 nM), 5.0 µM to 1.0 mM for ascorbic acid (LOD: 2.21 µM), and 0.5 µM to 1.0 mM for ethanol (LOD: 0.30 µM). Thus, K2FeO4 has a great potential for the postcolumn detection of those UV featureless compounds.

Rational Design of Magnetic Micronanoelectrodes for Recognition and Ultrasensitive Quantification of Cysteine Enantiomers.

Driven by the urgent need for recognition and quantification of trace amino acids enantiomers in various biologic samples, we demonstrate for the first time an ultrasensitive electrochemical chiral biosensor for cysteine (Cys) based on magnetic nanoparticles (Fe3O4@PDA/Cu xO) as electrode units. d-Cys-Cu2+-d-Cys formed in the presence of cysteine exhibits strong stability and a shielding effect on the redox current of indicator Cu2+, which can be used to quantify and recognize d-Cys by square wave voltammetry. Simultaneous detection of d-Cys and homocysteine (Hcy) is achieved in the presence of other amino acids, demonstrating an excellent selectivity of the sensor. Moreover, aided by the enrichment treatment effect of magnetic micronanoelectrodes, an ultrahigh sensitivity up to 102 µA µM-1 cm-2 was achieved, the detection limit is reduced to picomolar level (83 pM) for d-Cys and can be used for the recognition of cysteine enantiomers. The proposed method has been verified by real sample analysis with satisfactory results. The results highlight the feasibility of our proposed strategy for magnetic micronanoelectrode sensor, electrochemical recognition, and quantification of d-Cys, which can be more broadly applicable than that with traditional electrode structures and further advance the field of electrochemical sensors.

Fluorescent iridium nanoclusters for selective determination of chromium(VI).

Fluorescent iridium nanoclusters (IrNCs) consisting of up to 7 Ir atoms were prepared by heating IrCl3 in N,N-dimethylformamide. No other reagents are required. High resolution transmission electron microscopy (HRTEM) shows the IrNCs to be monodispersed with an average size of 0.9 ± 0.2 nm. They are well soluble in polar solvents and stable in these solvents for at least 6 months. Under photoexcitation with 365 nm light, they emit strong bluish green fluorescence with peaks that depend on the excitation wavelength and range from 530 to 650 nm. The fluorescence lifetime typically is 2.2 ns and the quantum yield is 8.3%. Fluorescence is quenched by Cr(VI) ion (chromate), and the emission peak is gradually red-shifted. According to the absorbance spectra of IrNCs in the presence and absence of Cr(VI) and Stern-Volmer quenching behavior study, static quenching is involved. Based on these findings, a selective assay was developed for the determination of Cr(VI). It has a linear response in the 0.1 to 100 µM chromate concentration range and a 25 nM detection limit. Graphic abstract Fluorescent iridium nanoclusters (IrNCs), consisting of up to 7 Ir atoms, were prepared in N,N-dimethylformamide (DMF) solution without using any other reagents. Their fluorescence is statically quenched by Cr(VI).

Development of a 10-litre pilot scale micro-nano bubble (MNB)-enhanced photocatalytic system for wastewater treatment.

A 10-litre pilot scale micro-nano bubble (MNB)-enhanced photocatalytic degradation system was developed using ZnO as the photocatalyst and salicylic acid (SA) as the model pollutant. The effectiveness of the MNB/ZnO/UV system was systematically compared with those of MNB, UV, MNB/UV, MNB/ZnO and ZnO/UV degradation systems. The effects of process parameters, including catalyst dosage, pollutant concentration, air-intake rate, pH and salt content on the degradation of SA, were comprehensively investigated. Optimum performance was obtained at neutral conditions with a catalyst dosage of 0.3 g/L and an air-intake rate of 0.1 L/min. For the degradation of SA, a kinetic constant of 0.04126/min was achieved in the MNB/ZnO/UV system, which is 4.5 times greater than that obtained in the conventional ZnO/UV system. The substantial increase in the degradation rate can be attributed to that the air MNB not only enhanced the gas-liquid mass transfer efficiency but also elevated the concentration of dissolved oxygen. A 10-litre pilot scale MNB/ZnO/UV system was successfully applied to the purification of lake water and river water, demonstrating great application potential for wastewater treatment.

Dimethyl Sulfoxide: An Ideal Electrochemical Probe for Hydroxyl Radical Detection.

In situ and real-time determination of hydroxyl radicals (•OH) in physiological and pathological processes is a great challenge due to their ultrashort lifetime. Herein, an electrochemical method was developed by using dimethyl sulfoxide (DMSO) as a trapping probe for rapid determination of •OH in aqueous solution. When DMSO reacted with •OH, an intermediate product methane sulfinic acid (MSIA) was formed, which can be electrochemically oxidized to methanesulfonic acid (MSA) on the glassy carbon electrode (GCE), resulting in a distinct voltammetric signal that is directly proportional to the concentration of •OH. Other commonly encountered reactive oxygen species (ROS), including hypochlorite anions (ClO-), superoxide anions (O2•-), sulfate radicals (SO4•-), and singlet oxygen (1O2), have showed no interference for •OH determination. Thus, an electrochemical method was developed for the determination of •OH, which exhibits a wide linear range (0.4-5120 µM) and a low limit detection of 0.13 µM (S/N = 3) and was successfully applied for the quantification of •OH in aqueous extracts of cigarette tar (ACT). Alternatively, the same reaction mechanism is also applicable for the determination of DMSO, in which a linear range of 40-320 µM and a detection limit 13.3 µM (S/N = 3) was achieved. The method was used for the evaluation of DMSO content in cell cryopreservation medium. This work demonstrated that DMSO can serve as an electrochemical probe and has valuable application potential in radical study, biological research, and environmental monitoring.

Clinical characteristics of a case of multiple mitochondrial dysfunction syndrome 3.

OBJECTIVE: To further comprehend the phenotype of multiple mitochondrial dysfunction syndrome type 3 (MMDS3:OMIM#615330) caused by IBA57 mutation. We present a case involving a patient who experienced acute neurological regression, and the literature was reviewed. METHODS: Clinical data and laboratory test results were collected; early language and development progress were tested; and genetic testing was performed. Bioinformatics analysis was performed using Mutation Taster and PolyPhen-2, and the literature in databases such as PubMed and CNKI was searched using MMDS3 and IBA57 as keywords. RESULTS: The child, aged 1 year and 2 months, had motor decline, unable to sit alone, limited right arm movement, hypotonia, hyperreflexia of both knees, and Babinski sign positivity on the right side, accompanied by nystagmus. Blood lactate levels were elevated at 2.50 mmol/L. Brain MR indicated slight swelling in the bilateral frontoparietal and occipital white matter areas and the corpus callosum, with extensive abnormal signals on T1 and T2 images, along with the semioval center and occipital lobes bilaterally. The multiple abnormal signals in the brain suggested metabolic leukoencephalopathy. Whole-exome sequencing analysis revealed that the child had two heterozygous mutations in the IBA57 gene, c.286T>C (p.Y96H) (likely pathogenic, LP) and c.992T>A (p.L331Q) (variant of uncertain significance, VUS). As of March 2023, a literature search showed that 56 cases of MMDS3 caused by IBA57 mutation had been reported worldwide, with 35 cases reported in China. Among the 35 IBA57 mutations listed in the HGMD database, there were 28 missense or nonsense mutations, 2 splicing mutations, 2 small deletions, and 3 small insertions. CONCLUSION: MMDS3 predominantly manifests in infancy, with primary symptoms including feeding difficulties, neurological functional regression, muscle weakness, with severe cases potentially leading to mortality. Diagnosis is supported by elevated lactate levels, multisystem impairment (including auditory and visual systems), and distinctive MRI findings. Whole-exome sequencing is crucial for diagnosis. Currently, cocktail therapy offers symptomatic relief.

(4-Chloro-acetanilido-κ(2)N,O)bis-[2-(pyridin-2-yl)phenyl-κ(2)C(1),N]iridium(III).

In the neutral mononuclear iridium(III) title compound, [Ir(C(8)H(7)ClNO)(C(11)H(8)N)(2)], the Ir(III) atom adopts an octa-hedral geometry, and is coordinated by two 2-phenyl-pyridyl ligands and one anionic 4-chloro-acetanilide ligand. The 2-phenyl-pyridyl ligands are arranged in a cis-C,C' and cis-N,N' fashion. Each 2-phenyl-pyridyl ligand forms a five-membered ring with the Ir(III) atom. The 2-phenyl-pyridyl planes are perpendicular to each other [dihedral angle = 89.9 (1)°]. The Ir-C and Ir-N bond lengths are comparable to those reported for related iridium(III) 2-phenyl-pyridyl complexes. The remaining two coordination sites are occupied by the amidate N and O atoms, which form a four-membered ring with the iridium atom (Ir-N-C-O). The amidate plane is nearly perpendicular to both 2-phenyl-pyridyl ligands [dihedral angles = 87.8 (2) and 88.3 (2)°].

Biorecognition element-free electrochemical detection of recombinant glycoproteins using metal-organic frameworks as signal tags.

Accurate and sensitive determination of recombinant glycoproteins is in great demand for the treatment of anemia-induced chronic kidney disease and the illegal use of doping agents in sports. In this study, an antibody and enzyme-free electrochemical method for the detection of recombinant glycoproteins was proposed via the sequential chemical recognition of hexahistidine (His6) tag and glycan residue on the target protein under the cooperation interaction of nitrilotriacetic acid (NTA)-Ni2+complex and boronic acid, respectively. Specifically, NTA-Ni2+ complex-modified magnetic beads (MBs-NTA-Ni2+) are employed to selectively capture the recombinant glycoprotein through the coordination interaction between His6 tag and NTA-Ni2+ complex. Then, boronic acid-modified Cu-based metal-organic frameworks (Cu-MOFs) were recruited by glycans on the glycoprotein via the formation of reversible boronate ester bonds. MOFs with abundant Cu2+ ions acted as efficient electroactive labels to directly produce amplified electrochemical signals. By using recombinant human erythropoietin as a model analyte, this method showed a wide linear detection range from 0.01 to 50 ng/mL and a low detection limit of 5.3 pg/mL. With the benefits from the simple operation and low cost, the stepwise chemical recognition-based method shows great promise in the determination of recombinant glycoproteins in the fields of biopharmaceutical research, anti-doping analysis and clinical diagnosis.

A colorimetric and fluorometric dual-mode carbon dots probe derived from phenanthroline precursor for the selective detection of Fe2+ and Fe3.

Iron's metabolism is heavily involved in the regulation of redox balance for cell functions, however, the simultaneous monitoring of Fe2+/3+ concentration is still a great challenge due to their transitional nature in biological systems. A novel type of carbon dots (CDs) was synthesized by solvothermal treatment with 5-amino-1,10-phenanthroline (Aphen) and salicylic acid as precursors, and the resulting targeted CDs (T-CDs) were used to simultaneously detect Fe2+ and Fe3+. Comprehensive experimental characterizations revealed that the strong binding affinity of Aphen moiety to Fe2+ leads to the formation of rigid T-CDs aggregates, which causes a substantial enhancement of fluorescence intensity, whereas Fe3+ could cause the fluorescence quenching of T-CDs due to the oxidation-reduction induced electron transfer. These different fluorescence responses allow T-CDs to sensitively differentiate Fe2+ from Fe3+, and give the limit of detection (LOD) of 1.78 and 2.78 µM for Fe2+ and Fe3+, respectively. Furthermore, the Aphen dominated structure endows the T-CDs with a colorimetric response to Fe2+ with a LOD of 0.13 µM, which is very different from Fe3+. Thus, the dynamic changes of Fe2+ and Fe3+ in solution can be accurately monitored by T-CDs within the total iron concentration of 50 µM, which is probably the most sensitive dual-mode probe reported so far. In addition, this probe is successfully applied to detect the Fe2+/3+ concentration in cells, demonstrating a huge application potential in the sensing of the dynamic equilibrium of these important transition metals during the cell metabolism or stimulated process. The dynamic changes of Fe2+ and Fe3+ in solution can be accurately monitored by carbon dots based on the colorimetric and fluorometric dual-mode.

Tartaric acid stabilized iridium nanoparticles with excellent laccase-like activity.

Iridium nanoparticles with an average size of 1.7 nm (Tar-IrNPs) were synthesized by the reduction of IrCl3 with NaBH4 in the presence of tartaric acid. As prepared Tar-IrNPs showed not only oxidase, peroxidase and catalase activities but also exhibited unprecedented laccase-like activity, which can catalyze the oxidation of the substrates o-phenylenediamine (OPD) and p-phenylenediamine (PPD) accompanied by significant color changes. The superb catalytic performance is evidenced by the fact that Tar-IrNPs can achieve better laccase-like activity with only 2.5% of the dosage of natural laccase. Furthermore, they also exhibited superior thermal stability and broader pH adaptability (2.0-11) over that of natural laccase. Tar-IrNPs can retain more than 60% of their initial activity at 90 °C, while the natural laccase has totally lost its activity at 70 °C. At a prolonged reaction time, the oxidation products of OPD and PPD can form precipitates due to oxidation induced polymerization. Thus Tar-IrNPs have been successfully used for the determination and degradation of PPD and OPD.

Electrochemical detection of glycoproteins using boronic acid-modified metal-organic frameworks as dual-functional signal reporters.

The sensitive analysis of glycoproteins is of great importance for early diagnosis and prognosis of diseases. In this work, a sandwich-type electrochemical aptasensor was developed for the detection of glycoproteins using 4-formylphenylboric acid (FPBA)-modified Cu-based metal-organic frameworks (FPBA-Cu-MOFs) as dual-functional signal probes. The target captured by the aptamer-modified electrode allowed the attachment of FPBA-Cu-MOFs based on the interaction between boronic acid and glycan on glycoproteins. Large numbers of Cu2+ ions in FPBA-Cu-MOFs produced an amplified signal for the direct voltammetric detection of glycoproteins. The electrochemical aptasensor showed a detection limit as low as 6.5 pg mL-1 for prostate specific antigen detection. The method obviates the use of antibody and enzymes for molecular recognition and signal output. The dual-functional MOFs can be extended to the design of other biosensors for the determination of diol-containing biomolecules in clinical diagnosis.

Recombinant human erythropoietin protects against immature brain damage induced by hypoxic/ischemia insult.

To investigate the neuroprotection of recombinant human erythropoietin (rhEPO) against hypoxic/ischemic (HI) insult in three-day-old rats. Postnatal day 3 (PD3) rats were randomly divided into three groups: Sham group, HI group and HI+rhEPO group. Ligation of the right common carotid artery and hypoxia to induce HI brain injury. After HI insult, the rats received intraperitoneal injection of rhEPO (5000 IU/Kg, qod) in HI+rhEPO group or equal saline in other groups. On PD10, damage of brain tissue was examined by hematoxylin-eosin (HE) staining, observation of neuronal apoptosis in the hippocampus and cortex using immunofluorescence assay (marker: TUNEL). Immunohistochemical staining or western blotting was performed to detect the expression of cyclooxygenase-2 (COX-2), Caspase-3 and phosphorylated Akt (p-Akt) protein. On PD28, cognitive ability of rats was assessed by Morris water maze test. HI injury causes brain pathological morphology and cognitive function damage in PD3 rats, which can be alleviated by rhEPO intervention. Compared with the HI group, the HI+rhEPO group showed an increase in platform discovery rate and cross platform frequency, while the search platform time was shortened (P < 0.05). The proportion of TUNEL positive neurons and the expression of COX-2 and Caspase-3 proteins in brain tissue in the hippocampus and cortex was decreased, while the expression of p-Akt protein was upregulated (P < 0.05). RhEPO could protect against the pathological and cognitive impairment of immature brain induced by HI insult. This neuroprotective activity may involve in inhibiting inflammatory and apoptosis by activation of PI3K/Akt signaling pathway.

Intramolecular hydrogen bond-tuned thermal-responsive carbon dots and their application to abnormal body temperature imaging.

A steric hindrance strategy was used to prepare intramolecular hydrogen bond-controlled thermosensitive fluorescent carbon dots (CDs) via the solvothermal treatment of o-phenylenediamine respectively with three dihydroxybenzene isomers. The CDs obtained from different isomers have very similar morphology, surfaces, and photophysical properties but exhibited different thermal sensitivities. Meanwhile, the orange-emitting CDs (p-CDs) obtained from o-phenylenediamine and p-hydroquinone exhibited an optimal thermal sensitivity of 1.1%/°C. Comprehensive experimental characterizations and theoretical calculations revealed that even a small difference in substituent locations in the phenyl ring of the precursors can considerably affect the formation of intramolecular hydrogen bonds and that the CDs with strong intramolecular hydrogen bonds exhibited poor thermosensitivity. The p-CDs were incorporated with reference CDs (B-CDs) that exhibited heating-quenching blue emission through electrostatic self-assembly to construct a dual-emission probe (p-CDs/B-CDs), which exhibited a thermal sensitivity of 2.0%/°C. Test strips based on the p-CDs/B-CDs were prepared to measure temperature fluctuations based on sensitive and instant fluorescence color evolution. Further, this fluorescent colorimetry was successfully applied to a test strip-integrated wearable wristband to measure the body temperature. This study establishes an inherent relationship between precursors and the resulting intramolecular hydrogen bonds for precisely tuning the thermal sensitivity of CDs. It also offers a visual quantitative strategy for the early warning of abnormal body temperatures.

ORMDL3­mediated bronchial epithelial pyroptosis leads to lung inflammation in obese mice with asthma.

Asthma associated with obesity is a chronic disease that poses a threat to health in children and results in severe wheezing, earlier airway remodeling and increased insensitivity to hormone therapy compared with those who only have asthma. Despite its clinical importance, knowledge on the underlying mechanisms of this disease is limited. The present study aimed to elucidate the pathogenesis of asthma associated with obesity using a murine model. A total of 30 female BALB/c mice were divided into three groups: Normal, mice with asthma and obese mice with asthma. Obese mice with asthma were fed a high­fat diet to induce obesity. Mice with asthma were sensitized and challenged with ovalbumin (OVA). Obese mice were subjected to OVA sensitization and challenge to develop asthma associated with obesity. Airway remodeling was observed in obese mice with asthma through HE and Masson staining. Proteomic and bioinformatics analyses were conducted on lung tissue from obese mice with asthma and normal mice. A total of 200 proteins were differentially expressed in obese mice with asthma compared with normal mice; of these, 53 and 47% were up­ and downregulated, respectively. Pathway analysis revealed that asthma associated with obesity primarily affected the 'lysosome', 'phagosome', and 'sphingolipid metabolism' pathways. Gene Set Enrichment Analysis demonstrated the presence of pyroptosis in obese asthmatic mice, along with significant increases in pyroptosis­-associated factors such as GSDMD and Caspase. High protein expression of orosomucoid­like 3 (ORMDL3), NOD­like receptor thermal protein domain associated protein 3 (NLRP3) and Gasdermin­D (GSDMD) was observed in obese mice with asthma. In vitro experiments using HBE cells infected with ORMDL3­overexpressing lentivirus demonstrated that the overexpression of ORMDL3 led to increased expression of NLRP3, GSDMD and cathepsin D (CTSD). These findings suggested that ORMDL3 may regulate pyroptosis and subsequent airway remodeling in asthma associated with obesity via the CTSD/NLRP3/GSDMD pathway.

Cadmium induced aggregation of orange-red emissive carbon dots with enhanced fluorescence for intracellular imaging.

Cadmium is a notorious toxic heavy metal, that poses serious threat to human health. Sensitive and selective detection of cadmium in cells is of great significance in poison screening and disease diagnosis. Orange-red emissive carbon dots (OR-CDs), prepared from the calcination of selected carbon sources 5-amino-1, 10-phenanthroline (Aphen) and salicylic acid (SA), were found to act as a "turn on" type fluorescence probe for Cd2+ detection. The structure and optical properties of OR-CDs were comprehensively investigated by both experimental characterizations and density functional theory (DFT) calculations. The OR-CDs consist of a basic unit of nine aromatic rings, and the N/O binding sites on the OR-CDs can specifically bind with Cd2+, leading to aggregation induced enhanced emission (AIEE). A detection limit of 0.30 µM was achieved for Cd2+ with a linear range of 0.80-100 µM. OR-CDs can not only be used for intracellular Cd2+ imaging but also have the potential to alleviate cadmium poison in living organisms.

The finite-difference time-domain (FDTD) guided preparation of Ag nanostructures on Ti substrate for sensitive SERS detection of small molecules.

Surface-enhanced Raman Scattering (SERS) has become a powerful analytical technique for highly sensitive detection of target molecules. Its performance, however, is heavily dependent on the substrates. Relatively low sensitivity for small molecules and poor reproducibility in quantitative analysis are often encountered in most of nanoparticle modified SERS substrate. The present work starts by theoretical investigation of the electromagnetic field enhancement by nanomaterials of coinage metals with different sizes. The finite-difference time-domain (FDTD) simulation results revealed that the Ag NPs with the size around 100 nm exhibit the strongest SERS effect and the 'Ag-Ag' gaps have shown higher electromagnetic field enhancement than that of the 'Ag-Ti' gap. Subsequently, a multilayered Ag nanoparticles SERS substrate (or other coinage metals) was prepared by a two-step electroless deposition of Ag on Ti substrate. This was achieved by in situ reduction of Ag precursor to subsequently form a Ag nanoflake (Ag NF) layer and a Ag nanoparticle (Ag NPs) layer on the Ti base (Ti/AgNFs/AgNPs). The as-prepared SERS substrate showed a substantially enhanced SERS effect for small molecule detection and detection limit as low as 1.0 × 10-17 M for picric acid (PA), 1.0 × 10-14 M for p-nitrotoluene (PNT) and 1.0 × 10-6 M for uric acid (UA) were obtained respectively. The facile method developed in this work should be widely applicable for in-situ preparation of other SERs substrates.

Template-Free Synthesis of Porous Fluorescent Carbon Nanomaterials with Gluten for Intracellular Imaging and Drug Delivery.

A series of carbon nanomaterials, including carbon dots, carbon nanorings (CNRs), and porous carbon nanoballs, were facilely prepared by a template-free hydrothermal treatment of gluten as the sole carbon source. Driven by the hydrophobicity interaction, a concentration-dependent self-assembly of gluten was observed in an aqueous solution, leading to the subsequent formation of different morphologies of carbon nanomaterials in a hydrothermal treatment. Among these carbon nanomaterials, the CNRs exhibit bright photoluminescence with a quantum yield of 47.0%. Furthermore, CNRs also have a large surface area and low toxicity, making them an excellent drug carrier for chemotherapeutics. A model drug molecule doxorubicin (DOX) was successfully loaded on the CNRs, and the CNRs-DOX complexes exhibit a pH-dependent DOX release behavior. Compared with free DOX, the CNRs-DOX complexes can induce a higher level of apoptosis and lower level of necrosis, showing promise as anticancer agents.