Strategy To Fabricate Naked-Eye Readout Ultrasensitive Plasmonic Nanosensor Based on Enzyme Mimetic Gold Nanoclusters.

It is broadly interesting but remains a big challenge to explore nanomaterials-based methods to enable naked-eye observation and determination of ultratrace biomarkers and drugs. In this study, we developed a straightforward and extendable plasmonic nanosensor to enable visually quantitative determination of ultratrace target molecules through combining the use of enzyme-mimetic gold nanoclusters (AuNCs). Starting from sandwiched antibody-antigen (i.e., an analyte)-antibody structure, we conjugated AuNCs on the outer layer antibody to catalyze the decomposition of hydrogen peroxide used to reduce HAuCl4 into gold nanopartilces (AuNPs) for naked eye readout. This strategy is in theory applicable to all immunoreactions available and the protocol proposed to attach AuNCs onto an antibody is suitable to all proteins. The applicability of this type of nanosensor was validated by the determination of various ultratrace analytes such as protein avidin, breast cancer antigen, thyroid hormone, and even methamphetamine (MA), giving a naked-eye-readout limit of detection (LOD), down to 1.0 × 10(-20) M protein avidin, 7.52 × 10(-14) U/mL breast cancer antigen 15-3, 2.0 × 10(-15) mg/mL 3,5,3'-L-triiodothyronine and 2.3 × 10(-18) mg/mL MA. This strategy is thus considered an ultrasensitive way to fabricate plasmonic nanosensors, having wide and invaluable application potential in clinical, biological, and environmental studies, and in food quality control.

Colorimetric and ultra-sensitive fluorescence resonance energy transfer determination of H2O2 and glucose by multi-functional Au nanoclusters.

Ultra-sensitive colorimetric determination of H2O2 is accomplished based on the intrinsic peroxidase-like activity of Au nanoclusters (AuNCs) stabilized by glutathione (GSH). The color change of 3,3,5,5-tetramethylbenzidine (TMB) catalyzed by AuNCs offers an indirect method to measure glucose. This sensing platform makes use of a dual optical signal change, including the color change in an aqueous solution under visible light illumination and an ultra-sensitive fluorescent assay arising from efficient fluorescence resonance energy transfer (FRET) between the AuNCs and oxidized TMB. The detection limits of H2O2 and glucose are 4.9 × 10(-13) M and 1.0 × 10(-11) M, respectively. In addition, enhanced fluorescence is observed from the AuNCs due to the use of ethanol which produces clear changes in the quantum yield and lifetime of the AuNCs. The quantum yield of AuNCs is enhanced from ∼12.5% as an isolated fluorophore to 38.9% in an AuNCs-ethanol complex. The enhanced fluorescence lowers the detection limits of H2O2 and glucose by 2 orders of magnitude compared to those attained from the original AuNCs.

Magnolol against enterovirus 71 by targeting Nrf2-SLC7A11-GSH pathway.

Enterovirus 71 (EV71), a prominent pathogen associated with hand, foot, and mouth disease (HFMD), has been reported worldwide. To date, the advancement of effective drugs targeting EV71 remains in the preliminary experimental stage. In this study, magnolol demonstrated a significant dose-dependent inhibition of EV71 replication in vitro. It upregulated the overall expression level of nuclear factor erythroid 2 - related factor 2 (Nrf2) and facilitated its nucleus translocation, resulting in the increased expression of various ferroptosis inhibitory genes. This process led to a reduction in reactive oxygen species (ROS) accumulation induced by viral infection. Additionally, magnolol exhibited a broad-spectrum antiviral effect against enteroviruses. Notably, treatment with magnolol substantially enhanced the survival rate of EV71-infected mice, attenuated viral load in heart, liver, brain, and limb tissues, and mitigated tissue inflammation. Taken together, magnolol emerges as a promising candidate for the development of anti-EV71 drugs.

Multiplex plasmonic sensor for detection of different metal ions based on a single type of gold nanorod.

In this paper, a label-free multiplex plasmonic sensor has been developed to selectively determine different metal ions including Fe(3+), Hg(2+), Cu(2+), and Ag(+) ions based on a single type of gold nanorod (GNR). Under proper conditions, these metal ions can react with GNRs, resulting in changes of nanostructure and composition. The determination of Fe(3+), Hg(2+), Cu(2+), and Ag(+) ions is therefore readily implemented due to changes of longitudinal plasmon wavelength (LPW) of nanorods. Moreover, the GNR-based assay can not only determine all four kinds of metal ions successively but also can detect which of any one or several kinds of metal ions. This assay is sensitive to detect Fe(3+), Hg(2+), Cu(2+), and Ag(+) as low as 10(-6), 10(-8), 10(-10), and 10(-8) M, respectively. Importantly, the special nanostructure and composition of the nanorods are induced by these metal ions, which allow this sensor to maintain high selectivity to determine these metal ions. This nanosensor abrogates the need for complicated chemosensors or sophisticated equipment, providing a simple and highly selective detection platform.

Ultrasensitive determination of copper in complex biological media based on modulation of plasmonic properties of gold nanorods.

Accurate determination of copper in complex biological media such as cells is quite difficult, and an analytical strategy based on copper-modulated formation of core-shell gold nanorods is described. Selective and label-free sensing can be achieved by measuring the change in the localized surface plasmon resonance absorption. The technique can determine trace amounts of copper in human serum, urine, and red blood cells without or with minimal sample pretreatment. The Cu detection limits are 20.67 µM in human serum, 0.193 µM in human urine, and 3.09 × 10(-16) g in a single cell. The advantages of the technique are the high selectivity, simple or no sample pretreatment, and label free. Boasting a practical detection limit down to 2 fM, only 10(3) red blood cells are needed to conduct the analysis and the technique may be extended to the detection of trace amounts of copper in a single cell.

Da vinci robotic-assisted treatment of pediatric choledochal cyst.

Objective: To evaluate the advantages and disadvantages of da Vinci robot and laparoscopy in treating pediatric choledochal cysts. Methods: We retrospectively analyzed clinical data from forty-two children diagnosed with choledochal cysts in our hospital from January 2018 to January 2021. Twenty children underwent da Vinci robotic surgery, and the others underwent traditional laparoscopy. We compared differences in general information and preoperative, intraoperative, and postoperative differences between the two surgical groups. Results: There was no statistically significant difference in age, gender, weight, type, maximum cyst diameter, preoperative C-reactive protein (CRP) value, postoperative complication rate, and postoperative pain score between the two surgical groups (P > 0.05). The average age of the robot-assisted group was 3.62 ± 0.71 years old (range = 1-12 years). There were nineteen cases of Todani type I, one patients of other types, and the maximum cyst diameter was 35.45 ± 9.32 mm (range = 12-56 mm). In the laparoscopic group, the average age was 3.08 ± 0.82 years old (range = 3-10 years). Twenty-one patients had Todani type I, and one had other types. The maximum cyst diameter was 31.94 ± 8.64 mm (range = 10-82 mm). The robot-assisted group had better abdominal drainage, postoperative CRP value, fasting time, and discharge time than the laparoscopic group (P < 0.05). Conclusion: Compared with laparoscopy, the da Vinci system has the advantages of less tissue damage, faster recovery, and better healing in the treatment of children with congenital choledochal cysts. With technological advancements and an increased number of experienced surgeons, robotic surgery may become a new trend in surgery.

Fabricating and regulating peroxidase-like activity of eggshell membrane-templated gold nanoclusters for colorimetric detection of staphylococcal enterotoxin B.

Fluorescent eggshell membrane-templated gold nanoclusters (Au-ESM) can be obtained in a facile and low-cost manner in this study. The fluorescence of the Au-ESM may be significantly quenched by mercapto-compounds and peroxidase-like activity of Au-ESM could be regulated by the reaction process with glutathione. Moreover, the catalytic activity of the mimetic enzyme membrane could be modulated by immunoreactions. An immunoassay for colorimetric determination of staphylococcal enterotoxins B (SE-B) using colored gold nanoparticles was established based on the catalytic activity adjusted by the target molecules. This colorimetric assay can detect SE-B at the concentration range of 0.4-20 ng/mL and the limit of detection (LOD) is 0.12 ng/mL. As a practical application, the proposed colorimetric assay was further utilized to detect SE-B in food samples such as flour, corn and rice, requiring very low volume of sample and exhibiting great sensitivity and high accuracy, which provides promising platform for development of point-of-care diagnostic devices with biomedical and food safety applications.

Preparation and optical properties of worm-like gold nanorods.

A type of worm-like nanorods was successfully synthesized through conventional gold nanorods reacting with Na2S2O3 or Na2S. The generated worm-like gold nanorods comprise shrunk nanorod cores and enwrapped shells. Therefore, a gold-gold sulfide core-shell structure is formed in the process, distinguishing from their original counterparts. The formation of the gold chalcogenide layers was confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy. Experimental results showed that the thickness of the gold chalcogenide layers is controllable. Since the increase of shell thickness and decrease of gold nanorod core take place simultaneously, it allows one to tune the plasmon resonance of nanorods. Proper adjustment of reaction time, temperature, additives and other experimental conditions will produce worm-like gold nanorods demonstrating desired longitudinal plasmon wavelength (LPW) with narrow size distributions, only limited by properties of starting original gold nanorods. The approach presented herein is capable of selectively changing LPW of the gold nanorods. Additionally, the formed worm-like nanorods possess higher sensitive property in localized surface plasmon resonance than the original nanorods. Their special properties were characterized by spectroscopic methods such as Vis-NIR, fluorescence and resonance light scattering. These features imply that the gold nanorods have potential applications in biomolecular recognition study and biosensor fabrications.

A novel density-tunable nanocomposites of CdTe quantum dots linked to dendrimer-tethered multi-wall carbon nanotubes.

A novel nanocomposite of CdTe-PAMAM-MWNT was synthesized by covalently linking CdTe quantum dots (QDs) onto highly water-soluble multi-wall carbon nanotubes (MWNTs) functionalized with dendritic poly(amidoamine) (PAMAM). The IR, UV-vis and TEM methods has been used for the characterization of the composites. A facile method for controlling the density of QDs in the composite by simply changing the ratio of CdTe QDs/PAMAM-MWNT, as was verified by the TEM images. The experiments revealed that PAMAM and PAMAM-MWNT, once covalently linked with CdTe QDs, had remarkable effect on their fluorescence property. The fluorescence intensity of the CdTe-PAMAM hybrid was substantially enhanced as a compared to that of QDs, and the fluorescence was quenched greatly when QDs reacted with PAMAM-MWNT. The experimentally observed phenomena indicate that electron and energy transfer took place efficiently between CdTe QDs, PAMAM and MWNTs in the novel composite. These nanocomposits might hold great potential in photoelectron device and biotechnology applications.

Simultaneous electrochemical determination of uric acid and ascorbic acid on a glassy carbon electrode modified with cobalt(II) tetrakisphenylporphyrin.

A cobalt(II) tetrakisphenylporphyrin (Co(II)TPP) film modified glassy carbon electrode (Co(II)TPP-GCE) was prepared by just coating Co(II)TPP solution on the surface of the electrode. It can be used for the simultaneous determination of ascorbic acid and uric acid. The anodic peaks of AA and UA can be separated well. Owing to the strongly hydrophobic property of porphyrin, the modified electrode has good stability and long life. The linear range for UA and AA were 2.0 x 10(-6)-1.0 x 10(-4) M and 9.0 x 10(-6)-2.0 x 10(-3) M with detection limits of 5.0 x 10(-7) and 5.0 x 10(-6) M, respectively. Furthermore, metalloporphyrins of other kinds were also used to construct modified electrodes. Their performances were inferior compared with that of the Co(II)TPP modified electrode.

Absorbable polymeric surgical clips for appendicular stump closure: A randomized control trial of laparoscopic appendectomy with lapro-clips.

A randomized control trial was performed to evaluate the effectiveness and safety of absorbable polymeric clips for appendicular stump closure in laparoscopic appendectomy (LA). Patients were randomly enrolled into an experimental group (ligation of the appendicular base with Lapro-Clips, L-C group) or control group (ligation of the appendicular base with Hem-o-lok Clips, H-C group). We identified 1,100 patients who underwent LA between April 1, 2012 and February 3, 2015. Overall, 99 patients (9.0%, 99/1,100) developed a complication following LA (47 [8.5%] in the L-C group and 52 [9.5%] in the H-C group (P = 0.598). No statistically significant differences were observed in intra-abdominal abscesses, stump leakage, superficial wound infections, post-operative abdominal pain, overall adverse events, or the duration of the operations and hospital stays between the groups (all p > 0.05). Adverse risk factors associated with the use of absorbable clips in LA included body mass index ≥ 27.5 kg/m2, diabetes, American Society of Anesthesiologists degree ≥ III, gangrenous appendicitis, severe inflammation of the appendix base, appendix perforation, and the absence of peritoneal drainage. The results indicate that the Lapro-Clip is a safe and effective device for closing the appendicular stump in LA in select patients with appendicitis.

Multiplex sensor for detection of different metal ions based on on-off of fluorescent gold nanoclusters.

In this study, a multiplex fluorescence sensor for successive detection of Fe(3+), Cu(2+) and Hg(2+) ions based on "on-off" of fluorescence of a single type of gold nanoclusters (Au NCs) is described. Any of the Fe(3+), Cu(2+) and Hg(2+) ions can cause quenching fluorescence of Au NCs, which established a sensitive sensor for detection of these ions respectively. With the introduction of ethylene diamine tetraacetic acid (EDTA) to the system of Au NCs and metal ions, a restoration of fluorescence may be found with the exception of Hg(2+). A highly selective detection of Hg(2+) ion is, thus, achieved by masking Fe(3+) and Cu(2+). On the other hand, the masking of Fe(3+) and Cu(2+) leads to the enhancement of fluorescence of Au NCs, which in turn provides an approach for successive determination of Fe(3+) and Cu(2+) based on "on-off" of fluorescence of Au NCs. Moreover, this assay was applied to the successful detection of Fe(3+), Cu(2+) and Hg(2+) in fish, a good linear relationship was found between these metal ions and the degree of quenched fluorescent intensity. The dynamic ranges of Hg(2+), Fe(3+) and Cu(2+) were 1.96×10(-10)-1.01×10(-9), 1.28×10(-7)-1.27×10(-6) and 1.2×10(-7)-1.2×10(-6) M with high sensitivity (the limit of detection of Fe(3+) 2.0×10(-8) M, Cu(2+) 1.9×10(-8) M and Hg(2+) 2×10(-10) M). These results indicate that the assay is suitable for sensitive detection of these metal ions even under the coexistence, which can not only determine all three kinds of metal ions successively but also of detecting any or several kinds of metal ions.

A novel method for aqueous synthesis of CdTe duantum dots.

We have developed a simple and an economical one-pot method to synthesize water-soluble CdTe quantum dots (QDs) using hydroxylamine hydrochloride (HAH) as reduction and l-cysteine (CYS) as the ligand. The size of the CdTe QDs could easily be controlled by the duration of reflux and monitored by absorption and photoluminescence spectra. The factors influencing the photoluminescence quantum yields (PL QYs) on the QYs of CdTe NCs were investigated and the optimum conditions were determined. Under the optimum conditions (pH=11.0, the concentration of Cd(2+) was 1.0mmolL(-1) and the molar ratio of Cd(2+):Te(2)(-):CYS:HAH was 1:0.05:2.4:5), photoluminescence quantum yields of the CdTe QDs have been improved significantly and the maximum QYs of the QDs can achieve to 47%. The QDs were characterized by Fourier transform infrared spectrometry (FTIR), transmission-electron microscopy (TEM) and X-ray powder diffraction (XRD). The XRD patterns indicated that CdS was formed in the preparation process of CdTe QDs. This CdS shell could effectively passivate the surface trap states, and enhance the PL QY and stability of the CdTe QDs.

An ultrasensitive method for the determination of melamine using cadmium telluride quantum dots as fluorescence probes.

An ultrasensitive and simple method for the determination of melamine was developed based on the fluorescence quenching of thioglycolic acid (TGA) capped CdTe quantum dots (QDs) at pH 11.0. In strong alkaline aqueous solution, the selectivity of the method has been greatly improved due to most heavy metal ions show no interference as they are in the precipitation form or in their anion form. Furthermore, CdTe quantum dots have higher quantum yields at higher pH. The method has a wider concentration range and lower detection limit. The influence factors on the determination of melamine were investigated and the optimum conditions were determined. Under optimum conditions, the fluorescence intensity change of TGA coated CdTe quantum dots was linearly proportional to melamine over a concentration range from 1.0×10(-11) to 1.0×10(-5) mol L(-1) with a correlation coefficient of 0.9943 and a detection limit of 5×10(-12) mol L(-1). The mechanism of fluorescence quenching of the QDs has been proposed based on the infrared spectroscopy information and electrophoresis experiments in presence of melamine under alkaline condition. The proposed method was employed to detect trace melamine in milk powder and pet feeds with satisfactory results.

Enhanced fluorescence of chitosan based on size change of micelles and application to directly selective detecting Fe³âº in human serum.

In this paper, we have developed an approach to significantly enhance fluorescence of chitosan by simply heated the inherently low fluorescent chitosan aqueous solution. Enhanced blue fluorescence of chitosan solution was observed as originated from the formation of small size of chitosan micelle after long time heated. The fluorescence of chitosan micelles was quenched and recovered when Fe³âº ions were combined and released from chitosan micelles. Therefore, chitosan without modification of functional groups can recognize Fe³âº with very high selectivity. As a result, a new fluorescence sensor for sensitively detecting Fe³âº ion based on the change of chitosan micelles sizes was subsequently fabricated. This enhanced fluorescence enables the chitosan sensor to be sensitive to low concentrations of Fe³âº, and it is linear responsive in the range of 1.96×10⁻8 to 2.00×10⁻5 M. Importantly, this novel sensor may be applied in human serum for direct detection of Fe³âº ion without sample pretreatment. Analysis of 5 samples of human serum shows that the average concentration of Fe³âº is 26.95 µM, which is consistent with the results determined by other methods. Moreover, the advantage of chitosan-based assay is that Fe³âº rather than Fe²âº in human serum can be directly measured, avoiding costly, time-consuming and complex process.

Sensitive and simultaneous detection of different disease markers using multiplexed gold nanorods.

A multiplexed bioanalytical assay is produced by incorporating two types of gold nanorods (GNRs). Besides retaining the desirable features of common GNRs LSPR sensors, this sensor is easy to fabricate and requires only a visible-NIR spectrometer for detection. This assay can simultaneously detect different acceptor-ligand pairs by choosing the proper GNRs possessing various LPWs in a wide detection wavelength range and can be developed into a high-throughput detection method. This bioanalytical assay allows easy detection of human serum specimens infected by S. japonicum and tuberculosis (TB) from human serum specimens (human serum/Tris-HCl buffer ratio=1:10(4)) without the need for sample pretreatment. The technique is very sensitive compared to other standard methods such as indirect hemagglutination assays (IHA) that require a serum concentration ratio of larger than 1:20 and enzyme-linked immunosorbent assays (ELISA) requiring a ratio larger than 1:100. This methodology can be readily extended to other immunoassays to realize wider diagnostic applications.

High-sensitivity biosensors fabricated by tailoring the localized surface plasmon resonance property of core-shell gold nanorods.

An enhanced sensitive biosensor has been developed to detect biological targets by tailoring the localized surface plasmon resonance property of core-shell gold nanorods. In this new concept, a shell layer is produced on gold nanorods by generating a layer of chalcogenide on the gold nanorod surface after attachment of the recognition reagent, namely, goat IgG and antigen of schistosomiasis japonica. The bioactivity of these attached biomolecules is retained and the sensitivity of this biosensor is thus enhanced significantly. The plasmonic properties of the gold nanorods attached with the biomolecules can be adjusted and the plasmon resonance wavelength can be red-shifted up to several hundred nanometers in the visible or near infrared (NIR) region, which is extremely important to biosensing applications. This leads to a lager red-shift in the localized surface plasmon resonance absorption compared to the original gold nanorod-based sensor and hence offers greatly enhanced sensitivity in the detection of schistosomiasis japonica. The human serum infected with schistosomiasis japonica diluted to 1:50,000 (volume ratio, serum/buffer solution) can be detected readily. The technique offers enhanced sensitivity and can be easily extended to other sensing applications based on not only immuno-recognition but also other types of specific reactions.

A novel method for iodate determination using cadmium sulfide quantum dots as fluorescence probes.

We have developed a novel method for the determination of iodate based on the carboxymethyl cellulose-capped CdS quantum dots (QDs). Factors affecting the iodate detection were investigated, and the optimum conditions were determined. Under the optimum conditions, the relative fluorescence intensity of CdS quantum dots was linearly proportional to IO(3)(-) over a concentration range from 1.0 × 10(-8) to 1.0 × 10(-5) mol L(-1) with a correlation coefficient of 0.9987 and a detection limit of 6.0 nmol L(-1). Iodide, being oxidized by bromine to form iodate, was detected indirectly. The method was successfully applied to the determination of iodate and total amount of iodine in table salt samples. The related mechanism was also discussed.

Label-free optical biosensor based on localized surface plasmon resonance of immobilized gold nanorods.

We describe the fabrication and characterization of a localized surface plasmon resonance (LSPR) biosensor that utilizes gold nanorods immobilized as the optical transducer which requires the intensity change at a single wavelength to be monitored as a function of receptor-analyte binding at the nanorod surface. In contrary to free gold nanorods suspended in an aqueous solution with high sensitivity to the longitudinal plasmon wavelength to the surrounding environment, the intensity of the longitudinal plasmon band based on immobilized gold nanorods is more sensitive to changes in the surrounding dielectric properties than the change in the longitudinal plasmon wavelength. Quantitative calculation gives a linear equation between the concentration (X) of the test sample and intensity of LPB (Y) as Y=0.0881+12.9502X and 0.1 pM anti-goat can be detected using this IgG probe in this study. This sensor chip made of immobilized gold nanorods is very stable. The immobilized gold nanorods preserved under 4 degrees C for 1 year yield almost the same extinction spectrum as the original nanorods. This study reveals a reliable and sensitive method to measure the intensity of longitudinal plasmon bands based on the highly stable LSPR substrate. Moreover, the performance is comparable to dynamic SPR measurements in immunoassays and can monitor the receptor-analyte reactions in real time.

Optical and biological sensing capabilities of Au2S/AuAgS coated gold nanorods.

Gold nanorods coated with a multiplex component, namely Au(2)S/AuAgS coated gold nanorods, are produced without precipitation and aggregation among the nanorods. Both the thickness of the shell and size of the core can be readily controlled by this technique allowing one to tune the plasmon resonance of the nanocomposites over a range of several hundred nanometers. These Au(2)S/AuAgS coated gold nanorods exhibit interesting optical properties and are suitable for many biological sensing applications. Functionalization of the Au(2)S/AuAgS coated gold nanorods is achieved by manipulating the affinity between the Au(2)S/AuAgS and thiol compounds. Biomolecules can be covalently attached via the NH(2) bond of the antibodies to the NHS-terminated nanorods. The longitudinal peaks of the Au(2)S/AuAgS coated gold nanorods are extremely sensitive to the refractive index changes induced by target binding, suggesting that they are excellent sensors for target-specific binding events and have the potential to achieve single-molecule sensitivity in microspectroscopy.