Triquinane Sesquiterpene Glycosides from the Basidiomycete Antrodiella zonata.

In our ongoing study of fungal bioactive natural products, 12 previously undescribed triquinane sesquiterpene glycosides, namely, antrodizonatins A-L (1-12), and four known compounds (13-16) have been obtained from the fermentation of the basidiomycete Antrodiella zonata. The structures were established unambiguously via extensive spectroscopic analysis and theoretical calculations of electronic circular dichroism spectra. This is the first report of triquinane sesquiterpene glycosides. Compounds 1, 5, and 12 displayed antibacterial activity against Staphylococcus aureus with MIC50 values of 35, 34, and 69 µM, respectively.

Distance-Dependence Study of Plasmon Resonance Energy Transfer with DNA Spacers.

Plasmon resonance energy transfer (PRET) in hybrid plasmonic-molecular systems has a broad range of applications from catalysis to analytical/biochemical/biophysical imaging and sensing. Herein, we experimentally and theoretically probed the influence of the distance (d) between the plasmonic nanoparticle and the conjugated molecules on the PRET efficiency (ηPRET) using two PRET systems, which involved tetramethylrhodamine (TAMRA) or Cy3 molecules as acceptors and single spherical gold nanoparticles (AuNPs) as donors. The double-stranded DNA (dsDNA) sequences precisely adjusted within 12.0 nm were utilized as a donor-acceptor spacer. Then, the ηPRET of the two systems under varied d-values was available from the reduction of the scattering intensity of AuNPs. Both experimental and quasi-static approximation data show that ηPRET displays a d-value-dependent decay function. This study would provide new insights into optimal PRET-based chemical/biochemical sensors.

Plasmonic Cu2- xS ySe1- y Nanoparticles Catalyzed Click Chemistry Reaction for SERS Immunoassay of Cancer Biomarker.

Nature enzyme-based immunoassays have been widely used in fundamental scientific research and clinical diagnosis. However, the limitations of natural enzyme, such as the low physical/chemical stability or susceptibility to protein denaturation, greatly restrained its applications. In this article, we reported a new enzyme-free SERS immunoassay by utilizing plasmonic Cu2- xS ySe1- y nanoparticles (NPs) as nanocatalyst to catalyze the click chemistry between the azido and alkynyl substrate which is used as the SERS signal reporter. The unique vibration of C≡C of alkynyl in the Raman-silent region (1800-2800 cm-1) is not overlapped with the signals of the other conventional Raman reporters or endogenous biological species, and thus it can make sure the enzyme-free SERS immunoassay has high selectivity and sensitivity. As a proof of concept, prostate-specific antigen (PSA), a biomarker of prostate cancer in blood, has been detected. The SERS immunoassay shows good analytical performance for PSA in the range of 3-120 ng mL-1, and it has been successfully applied to detect PSA in the serum samples of prostate cancer patients, proving that the proposed enzyme-free SERS immunoassay has great potential in the clinical diagnosis of cancer.

General Sensitive Detecting Strategy of Ions through Plasmonic Resonance Energy Transfer from Gold Nanoparticles to Rhodamine Spirolactam.

Plasmonic resonance energy transfer (PRET), which occurs between the plasmonic nanoparticles and organic dyes, has significant potential in target sensing chemistry owing to its sensitivity at the single nanoparticle level. In this contribution, by using AuNPs, which has localized surface plasmonic resonance light scattering (LSPR-LS) around 550 nm, as the donor of PRET, a general sensitive detecting strategy of ions were developed. Targets can specifically react with a ring-close structured rhodamine spirolactam, which was prepared from rhodamines in the presence of different primary amine wherein the option of the primary amine is up to the targets, forming ring-open structured rhodamine spirolactam with the strong absorption around 550 nm. This process triggered the PRET from gold nanoparticles (AuNPs) to the ring-open structured rhodamine spirolactam. As a proof of concept, Cu2+ and Hg2+ were detected by using rhodamine B hydrazide and N-(rhodamine B)lactam-ethylenediamine, respectively. With the aid of a dark field microscope, the LSPR-LS of AuNPs gets decreased within 10 min with the addition of Cu2+ or Hg2+. The scattering light spectra get red-shifted during the targets addition due to the quenching dip phenomenon. Further theoretical simulation indicated the PRET process could be aroused by the electric field diminishment of AuNPs via the interaction of rhodamine. This single nanoparticle based detecting strategy could be further applied for other anions, cations, or small organic molecules detection by simply changing the rhodamine spirolactam.

"Click" on Alkynylated Carbon Quantum Dots: An Efficient Surface Functionalization for Specific Biosensing and Bioimaging.

Surface functionalization is an essential pre requisite for wide and specific applications of nanoparticles such as photoluminescent (PL) carbon quantum dots (CQDs), but it remains a major challenge. In this report, alkynylated CQDs, prepared from carboxyl-rich CQDs through amidation with propargylamine in the presence of 1,1'-carbonyldiimidazole, were modified efficiently with azido molecular beacon DNA through a copper(I)-catalyzed alkyne-azide cycloaddition reaction (CuAAC). As a proof-of-concept, the DNA-modified CQDs are then bonded with gold nanoparticles (AuNPs, 5 nm) through a gold-sulfur bond. Owing to the emission enhancement, this complex can then be applied to the recognition of a single-base- mismatched target. The same functionalizing strategy applied to click the alkynylated CQDs with a nuclear localization sequence (NLS) peptide showed that the NLS-modified CQDs could target the nuclei specifically. These results indicate that surface functionalization of CQDs through a nonstoichiometric copper chalcogenide nanocrystal- (nsCuCNC-) catalyzed click reaction is efficient, and has significant potential in the fields of biosensing and bioimaging.

Nonstoichiometric copper chalcogenides for photo-activated alkyne/azide cycloaddition.

Nonstoichiometric copper chalcogenides with heavy copper vacancies can be used as an effective photo-activated catalyst for the Huisgen [3+2] cycloaddition reaction as Cu(i) can be released corresponding to holes (Cu-defects) under light irradiation. These strategies expand new possibilities for carrying out prototypical click chemistry in the presence of functional groups.

Polydopamine-embedded Cu(2-x)Se nanoparticles as a sensitive biosensing platform through the coupling of nanometal surface energy transfer and photo-induced electron transfer.

Full understanding and easy construction of specific biosensing principles is necessary for disease diagnostics and therapeutics in the hope of creating new types of biosensors. Herein, we developed a new conceptual nanobiosensing platform by coupling nanometal surface energy transfer (NSET) and photo-induced electron transfer (PET) with polydopamine-embedded Cu(2-x)Se nanoparticles (Cu(2-x)SeNPs@pDA) and DNA-conjugated fluorescent organic dyes. The new prepared Cu(2-x)SeNPs@pDA has intense and broad localized surface plasmon resonance (LSPR) absorption over UV to near infrared (NIR) wavelengths, with different affinities toward ssDNA versus dsDNA. It also exhibits a high multiplexed fluorescence quenching ability, and thus can act as an acceptor in the energy transfer and electron transfer interactions between Cu(2-x)SeNPs@pDA and fluorescent organic dyes. As a proof of concept, a new biosensing platform has been successfully developed to target biomacromolecules such as DNA and proteins, in which the NSET and PET interactions between Cu(2-x)SeNPs@pDA and three different DNA-conjugated fluorescent dyes have been identified using steady-state and time-resolved fluorescence. A simple mathematical model was further applied to simulate the respective contributions of the coexisting NSET and PET to the total quenching observed for each DNA-conjugated dye in this sensing system. This study highlights the importance of understanding the mechanistic details of NSET and PET coupling processes, and the disclosed coupling mechanism of NSET and PET (NSET©PET) in the systems of Cu(2-x)SeNPs@pDA with wide wavelength range dyes provides new opportunities for sensitive biosensing applications.

Polyketides from the fungus Pochonia chlamydosporia and their bioactivities.

Three previously undescribed griseofulvin derivatives, namely pochonichlamydins A-C, one small polyketide, namely pochonichlamydin D, together with nine known compounds, have been isolated from cultures of the fungus Pochonia chlamydosporia. Their structures with absolute configurations were elucidated on the basis of extensive spectrometric methods and single-crystal X-ray diffraction. Dechlorogriseofulvin and griseofulvin exhibited inhibitory activities against Candida albicans at the concentration of 100 µM, with inhibition rates of 69.1% and 56.3%, respectively. Meanwhile, pochonichlamydin C showed mild cytotoxicity against the human cancer MCF-7 cell line with an IC50 value of 33.1 µM.

Surgical treatment of osteoporotic thoracolumbar compressive fractures with open vertebral cement augmentation of expandable pedicle screw fixation: a biomechanical study and a 2-year follow-up of 20 patients.

BACKGROUND: The incidence of screw loosening increases significantly in elderly patients with severe osteoporosis. Open vertebral cement augmentation of expandable pedicle screw fixation may improve fixation strength in the osteoporotic vertebrae. MATERIALS AND METHODS: Twenty cadaveric vertebrae (L1-L5) were harvested from six osteoporotic lumbar spines. Axial pullout tests were performed to compare the maximum pullout strength (Fmax) of four methods: 1. Conventional pedicle screws (CPS), 2. Expandable pedicle screws (EPS), 3. Cement augmentation of CPS (cemented-CPS), 4. Cement augmentation of EPS (cemented-EPS). Thirty-six consecutive patients with single-vertebral osteoporotic compressive fractures received posterior decompression and spinal fusion with cemented-CPS (16 cases) or cemented-EPS (20 cases). Plain film and/or CT scan were conducted to evaluate the spinal fusion and fixation effectiveness. RESULTS: The Fmax and energy absorption of cemented-EPS were significantly greater than three control groups. The mean BMD in the severe osteoporosis group was significantly lower than that in the osteoporosis group (t = 2.04, P = 0.036). In the osteoporosis group, cemented-EPS improved the Fmax by 43% and 21% over CPS and cemented-CPS group. In the severe osteoporosis group, cemented-EPS increased the Fmax by 59%, 22%, and 26% over CPS, EPS, and cemented-CPS, respectively. The clinical results showed that all patients suffered from severe osteoporosis. Six months after operation, the JOA and VAS scores in cemented-EPS group improved from 11.4 ± 2.6 and 7.0 ± 1.4 mm to 24.9 ± 1.6 and 2.1 ± 1.3 mm, respectively. No screw loosening occurred in the cemented-EPS group and spinal fusion was achieved. In the cemented-CPS group, four screws loosened (4.2%) according to the radiolucency. Six months after operation, the JOA and VAS scores improved from 13.1 ± 1.9 and 7.6 ± 1.5 mm to 22.8 ± 2.2 and 2.5 ± 1.6 mm, respectively. No cement leaked into the spinal canal in both groups. CONCLUSIONS: Cemented-EPS could increase fixation strength biomechanically. It could reduce the risks of screw loosening in patients with severe osteoporosis, requiring instrumented arthrodesis.

A study of low elastic modulus expandable pedicle screws in osteoporotic sheep.

STUDY DESIGN: Low elastic modulus expandable pedicle screw (L-EPS) was inserted into osteoporotic sheep. Biomechanical tests, micro-CT analysis and histologic observation were performed. OBJECTIVE: To find out whether the L-EPS can further improve fixation strength compared to the expandable pedicle screws (EPS) in osteoporotic sheep spine. The screw-bone interface is also detected by micro-computed tomography (CT) and histologic techniques. SUMMARY OF BACKGROUND DATA: There are some studies on EPS in vivo; however, no earlier study has focused on the elastic modulus of EPS, especially in osteoporosis. METHODS: Twelve months after ovariectomy, bilateral pedicles of lumbar vertebrae (L1 to L5) of 4 female sheep were fixed with EPSs. The L-EPS and EPS were randomly placed into each pedicle and then were expanded. Six months later, the sheep were sacrificed and biomechanical tests, micro-CT analysis, and histologic observation were conducted on the isolated specimen vertebrae. RESULTS: Twelve months after ovariectomy, animal model of osteoporosis was established successfully. The axial pull-out strength in L-EPS group was significantly enhanced compared with that in the EPS group (P < 0.05). Micro-CT reconstruction and analysis showed that there was more bone around the L-EPS group compared with those in EPS group (P < 0.05), meanwhile the more homogeneous bone formation distribution around the screws was found in the L-EPS group. Histologic observation showed that newly formed bone extended along the expandable fissures and grew into the center of EPS; meanwhile, the more direct contact and the less fibrous tissue on the screw-bone interface were observed in the L-EPS group. CONCLUSIONS: The L-EPS can further improve the biomechanical fixation strength of EPS in the osteoporotic sheep. The screw elastic matching with surrounding bone is helpful to distribute stress uniformly, relieve the stress shielding effect, and strengthen the screw-bone interface. Although the experience with the L-EPS is very limited and preliminary, results to date indicate that it is of value in treating patients with osteoporosis and warrants further study.

[Two different techniques combined with MIS-TLIF in the treatment of degenerative lumbar spondylolisthesis:a case-control study].

OBJECTIVE: To analyze the difference in clinical efficacy of minimally invasive transforaminal lumbar interbody fusion (MIS-TLIF) under Quadrant channel system combined with microscope and percutaneous pedicle screw in the treatment of degenerative lumbar spondylolisthesis. METHODS: A total of 114 patients with single-segment degenerative lumbar spondylolisthesis from June 2015 to February 2019, were divided into three groups according to the surgical methods, such as the MIS-TLIF under the microscope surgery group ( microscope group), MIS-TLIF combined with percutaneous pedicle screw technique surgery group(percutaneous group) and posterior lumbar interbody fusion surgery group (open group). In the microscope group, there were 12 males and 26 females, aged from 42 to 83 years with an average of (63.29±9.09) years. In the percutaneous group, there were 16 males and 22 females, aged from 45 to 82 years with an average of (63.37±7.50) years. In the open group, there were 12 males and 26 females, aged from 51 to 82 years with an average of (63.76±8.21) years. The general conditions of operation, such as operation time, intraoperative blood loss, postoperative drainage, length of surgical incision, frequency of intraoperative fluoroscopy and postoperative time of lying in bed were recorded to analyze the differences in surgical related indicators. Visual analogue scale (VAS) of waist and leg pain in preoperative and postoperative period (3 days, 3 months, 6 months and 12 months) were recorded to evaluate pain remission;Oswestry Disability Index(ODI), Japanese Orthopaedic Association (JOA) score were recorded to evaluate the recovery of waist and leg function on preoperative and postoperative 12 months. The lumbar spondylolisthesis rate and intervertebral height at 12 months after operation were recorded to evaluate the reduction of spondylolisthesis. The Siepe intervertebral fusion standard was used to analyze the intervertebral fusion rate at 12 months after operation. RESULTS: ①All 114 patients were followed up more than 1 year, and no complications related to incision infection occurred. In the microscope group, there was 1 case of subcutaneous effusion 8 days after operation. After percutaneous puncture and drainage, waist compression, and then the healing was delayed. In the percutaneous group, 2 cases of paravertebral muscle necrosis occurred on the side of decompression, and the healing was delayed after debridement. In open group, there was 1 case of intraoperative dural tear, which was packed with free adipose tissue during the operation. There was no postoperative cerebrospinal fluid leakage and other related complications.① Compared with microscope group, percutaneous group increased in operation time, intraoperative blood loss, postoperative wound drainage, surgical incision length, intraoperative fluoroscopy times, and postoperative bed rest time. In open group, intraoperative blood loss, postoperative wound drainage, surgical incision length, and postoperative bed rest time increased, but the intraoperative fluoroscopy time decreased. Compared with percutaneous group, the intraoperative blood loss, wound drainage, surgical incision length, and postoperative bed rest time in open group increased, but operative time and the intraoperative fluoroscopy time decreased(P<0.05). ②ODI and JOA scores of the three groups at 12 months after operation were improved compared with those before operation (P<0.05), but there was no significant difference between the three group(P>0.05). ③Compared with microscope group, the VAS of low back pain in percutaneous group increased at 3 days after operation, and VAS of low back pain in open group increased at 3 days, and 12 month after operation. Compared with percutaneous group, the VAS low back pain score of the open group increased at 3 months after operation (P<0.05). ④ The lumbar spondylolisthesis rate of the three groups of patients at 12 months afrer operation was decreased compared with that before operation(P<0.05), and the intervertebral heigh was increased compared with that before operation(P<0.05), however, there was no significant difference among three groups at 12 months afrer operation(P>0.05). ⑤ There was no significant difference between three groups in the lumbar fusion rate at 12 months afrer operation(P>0.05). CONCLUSION: The MIS-TLIF assisted by microscope and the MIS-TLIF combined with percutaneous pedicle screw are safe and effective to treat the degenerative lumbar spondylolisthesis with single-segment, and the MIS-TLIF assisted by microscope may be more invasive, cause less blood loss and achieve better clinical efficacy.

Augmentation of pedicle screw stability with calcium sulfate cement in osteoporotic sheep: biomechanical and screw-bone interfacial evaluation.

STUDY DESIGN: Augmentation of pedicle screws with calcium sulfate cement (CSC) was performed in osteoporotic sheep. Biomechanical tests, micro-computed tomography (CT) analysis, and histological observation were performed. OBJECTIVE: To investigate the long-term biomechanical performance of pedicle screws augmented with CSC in vivo and evaluated the screw-bone interfacial bonding with micro-CT and histological techniques. SUMMARY OF BACKGROUND DATA: There is little information on the long-term biomechanical performance and screw-bone interfacial bonding of pedicle screws augmented with CSC in osteoporosis in vivo. METHODS: Twelve months after ovariectomy, bilateral pedicles of lumbar vertebrae (L1 to L5) of 6 female sheep were fixed with pedicle screws. One pedicle of each vertebral body was treated with a screw augmented with CSC (CSC group) and the contralateral pedicle was treated with a screw without any augmentation (control group). Three months later, the sheep were killed and biomechanical tests, micro-CT analysis, and histological observation were conducted on the isolated specimen vertebrae. RESULTS: Twelve months after ovariectomy, animal model of osteoporosis was established successfully. Both the axial and vertical stabilities of the pedicle screws in CSC group were significantly enhanced compared with those in the control group (P<0.05). Micro-CT reconstruction and analysis showed that there were more bone trabeculae around the screws in CSC group compared with those in control group (P<0.05), and the bone trabeculae were significantly denser than those in control group (P<0.05). Histological observation showed that CSC was completely degradated and bone trabeculae around the screws in CSC group were more and denser than that in the control group. Bone trabeculae held the screws tightly without any interspaces between screw and bone, which formed strong bonding between bone and screw. CONCLUSIONS: CSC can significantly improve screw-bone interfacial bonding and strengthen the long-term stability of pedicle screws in osteoporotic sheep. Augmentation with CSC may be a potentially useful method to increase the stability of pedicle screws in patients with osteoporosis.

Expandable pedicle screw trajectory in cadaveric lumbar vertebra: an evaluation using microcomputed tomography.

STUDY DESIGN: An in-vitro cadaver-based measurement using microcomputed tomography. OBJECTIVES: To evaluate the safety of removal of expandable pedicle screws (EPSs) in human vertebral bodies after a long (6 mo) insertion time. SUMMARY OF BACKGROUND DATA: Transpedicular fixation is commonly used for posterior fixation of the spine. Osteoporotic patients are in high risk of internal fixation failure. EPS is an available device for increasing transpedical fixation in the osteoporotic spine. However, it is unclear that how much the diameter of the expanding screw tip increases in the human vertebral body, and no reports have assessed the potential for fracture of the pedicle when the EPS is removed. Therefore, the safety of removal of EPS needs to be evaluated. METHODS: In this study, 6.50 mm EPSs were inserted into cadaveric lumbar vertebrae. The maximum diameters of expansion, the maximum diameters of the EPS trajectories, and the diameters of the EPS trajectories in the pedicles were measured using microcomputed tomography imaging and 3-dimensional reconstruction. Regions of interest of the same size adjacent to the EPS in the pedicle and in the vertebral body were reconstructed and analyzed using the same thresholds (1000). Bone volume divided by total volume (BV/TV) in these regions of interest was determined. RESULTS: The maximum diameter of expansion of the EPSs in the vertebral body was 7.63 mm, a 17.38% increase from the original diameter. The maximum diameter of the EPS trajectory and the diameter of the EPS trajectory in the pedicle were 7.56 mm and 7.09 mm, respectively, increases of 16.31% and 9.08%. The differences were statistically significant (P < 0.05). In the pedicle, there was a negative correlation between the diameter of the EPS trajectory and the BV/TV along the EPS trajectory (r = -0.88; P = 0.002). In the vertebral body, a negative correlation occurred between the maximum expansion diameter of the EPS and vertebral BV/TV (r = -0.85; P = 0.004). CONCLUSIONS: The EPS could be reliably removed after expansion without fracturing the pedicle. Furthermore, the BV/TV had an important influence on the degree of expansion of EPS and whether or not pedicle fracture occurs.

A new method of partial screw augmentation in sheep vertebrae in vitro: biomechanical and interfacial evaluation.

STUDY DESIGN: Partial screw augmentation was carried out by the injection of polymethylmethacrylate (PMMA) through the novel tap into the bone tissue in sheep vertebrae in vitro. Biomechanical tests and microcomputerized tomography analysis were done. OBJECTIVE: To evaluate the stability of the screw and the interface between the bone and the screw in partial screw augmentation. SUMMARY OF BACKGROUND DATA: Augmentation of the pedicle screw with PMMA improves screw stability significantly. However, it results in the full envelopment of the screw by PMMA and the formation of a full "screw-PMMA-bone" interface, which may increase the difficulties in screw removal. Therefore, it is urgent to develop a novel method to augment screw fixation, which avoids full wrapping of PMMA around the screw and facilitates screw removal. We designed a novel tap with an inner hollow and the multiple lateral apertures. METHODS: A total of 78 fresh adult sheep lumbar vertebrae were randomly divided into 3 groups. No screw augmentation was performed in the control group. The pilot hole was filled with PMMA in the full screw augmentation group, whereas PMMA was injected through the tap into the bone tissue in the partial screw augmentation group. Pedicle screws were ultimately inserted into all the holes. Axial pullout tests, cyclic bending tests, and microcomputerized tomography analysis were carried out 24 hours after screw fixation. RESULTS: Both partial screw augmentation and full screw augmentation caused significant increase in pedicle screw stability compared with the control group in both the axial pullout tests and the cyclic bending resistance tests. Partial screw augmentation resulted in the formation of a partial "screw-bone" interface and a partial screw-PMMA-bone interface, which seems like 3 anchors or roots extending and fixing in the bone tissue in a cross section of the interface. It was obviously different from the complete screw-PMMA-bone interface with a complete PMMA mantle around the screw in the full screw augmentation group. CONCLUSIONS: Our proof-of-concept study showed that partial screw augmentation could enhance pedicle screw fixation strength, avoided the full surrounding of the PMMA around the screw, and generated a partial screw-PMMA-bone and a partial screw-bone interface. Partial screw augmentation may be a potential method to augment pedicle screw stability.

Biomechanical comparison of different techniques in primary spinal surgery in osteoporotic cadaveric lumbar vertebrae: expansive pedicle screw versus polymethylmethacrylate-augmented pedicle screw.

INTRODUCTION: Transpedicular fixation can be challenging in the osteoporotic spine. Expansive pedicle screw (EPS) and polymethylmethacrylate-augmented pedicle screw (PMMA-PS) were both used to increase screw stability. However, there are a little or no biomechanical comparisons of EPS and PMMA-PS, especially in primary spinal surgery in osteoporotic vertebrae. The purpose of this study was to compare the stability of EPS and PMMA-PS in primary spinal surgery. MATERIALS AND METHODS: Fifteen osteoporotic vertebrae were randomly divided into three groups. The conventional pedicle screw (CPS) was inserted in CPS group, the pilot hole was filled with PMMA followed by CPS insertion in PMMA-PS group, and EPS was inserted in EPS group. Twenty-four hours later, X-ray and CT examination and biomechanical tests were performed to all vertebrae. RESULTS: In PMMA-PS group, PMMA existed in bone tissue around the CPS in both vertebral body and pedicle of vertebral arch, and PMMA surrounding the screw formed a spindle-shaped structure in vertebral body. In EPS group, anterior part of EPS presented an obvious expansion in vertebral body and formed a clawlike structure. Screw stabilities in PMMA-PS and EPS groups were significantly enhanced compared with those in CPS group (P < 0.05). However, there was no significant difference between PMMA-PS and EPS groups (P > 0.05). CONCLUSION: Expansive pedicle screw can markedly enhance screw stability with a similar effect to the traditional method of screw augmentation with PMMA in primary surgery in osteoporotic vertebrae. In addition, EPS can overcome pedicle fracture, leakage and compression caused by lager screw and augmentation with PMMA. We propose that EPS is an effective, safe and easy method and has a great application potential in augmentation of screw stability in osteoporosis in clinic.

An enzyme-induced Au@Ag core-shell nanoStructure used for an ultrasensitive surface-enhanced Raman scattering immunoassay of cancer biomarkers.

Early detection of cancer is helpful for the control and prevention of diseases. Due to the low content of cancer biomarkers in the early disease phases, however, an ultrasensitive and selective method is critical. In this contribution, an ultrasensitive surface-enhanced Raman scattering (SERS) immunoassay is newly developed with the principle of introducing a common enzyme-induced deposition (EID) reaction to coat a silver layer on the surface of gold nanoparticles and to form a core-shell nanostructure of Au@Ag. By using alkaline phosphatase (ALP) to dephosphorylate its substrate, 2-phospho-l-ascorbic acid trisodium salt (AAP), to form vitamin C, silver ions could be reduced into silver atoms and coated on the surface of the AuNPs; a greatly enhanced SERS signal was then obtained. As a proof of concept, α-fetoprotein (AFP) was detected as a target, which is a biomarker of liver cancer. Excellent analytical performance of the SERS immunoassay could be achieved in the range from 0.5 to 100 pg mL-1 with a limit of detection of 0.081 pg mL-1 (3σ). Identical results could be obtained by using the newly proposed SERS immunoassay for the clinical detection of AFP in serum samples of patients to those clinically obtained by chemiluminescence immunoassays, demonstrating the potential applications of the developed method in clinical diagnosis.

Photoinduced Electron Transfer Process Visualized on Single Silver Nanoparticles.

Understanding the photoinduced electron transfer (PET) mechanism is vital to improving the photoelectric conversion efficiency for solar energy materials and photosensitization systems. Herein, we visually demonstrate the PET process by real-time monitoring the photoinduced chemical transformation of p-aminothiophenol (p-ATP), an important SERS signal molecule, to 4,4'-dimercaptoazobenzene on single silver nanoparticles (AgNPs) with a localized surface plasmon resonance (LSPR) spectroscopy coupled dark-field microscopy. The bidirectional LSPR scattering spectral shifts bathochromically at first and hypsochromically then, which are caused by the electron transfer delay of p-ATP, disclose the PET path from p-ATP to O2 through AgNPs during the reaction, and enable us to digitalize the corresponding electron loss and gain on the surface of AgNP at different time periods. This visualized PET process could provide a simple and efficient approach to explore the nature of PET and help to interpret the SERS mechanism in terms of p-ATP.

A graphitic carbon nitride based fluorescence resonance energy transfer detection of riboflavin.

Fluorescence resonance energy transfer (FRET), which occurs between two luminescent chromophores, can greatly improve the selectivity and sensitivity of a fluorescent assay when a ratiometric signaling with the fluorescence enhancement of the acceptor at the expense of the donor is adopted. In this study, a fluorescence ratiometric detection (FRD) of riboflavin (RF) has been made based on FRET, as the strong overlap occurred between the emission spectrum of graphitic carbon nitride (g-C3N4) and absorption spectrum of RF, in which g-C3N4 acts as the energy donor and RF as the energy acceptor. With increasing concentration of RF, the fluorescence intensity of g-C3N4 emission at 444 nm decreased and the fluorescence peak at 523 nm for RF increased regularly, making the fluorescence intensity ratio of 523 nm to 444 nm linearly dependent on the concentration of RF in the range from 0.4 µM to 10 µM, giving a limit of the detection of 170 nM. This method can be used to quantify RF in complex systems such as milk and drink, showing that the novel FRET-based fluorescence ratiometric detection can enable an attractive assay platform for analytes of interest.

[Comparison of clinical efficacy between minimally invasive total hip artliroplasty and traditional total hip arthroplasty: a systematic review].

OBJECTIVE: To systematically review the effectiveness of minimally invasive total hip arthroplasty (MIS-THA) versus traditional total hip arthroplasty (THA) in patients with hip diseases. METHODS: Through a method of combining Free words and keywords,we searched databases including PubMed,The Cochrane Library, EMbase,Web of Science, CBM , CNKI and Wanfang Data for randomized controlled trials (RCTs) on the comparison between MIS-THA and THA for hip disease from inception to June, 2014. Two reviewers independently screened literatures according to the inclusion and exclusion criteria, extracted data and assessed the quality of the included studies according to the "bias risk assessment" tool recommended by Cochrane Handbook 5.0 for Systematic Reviews. Then, meta-analysis was performed using RevMan 5.3 software. RESULTS: Thirteen RCTs involving 1 213 cases of surgeries and total 1 284 hips (MIS-THA: n = 631; THA: n = 653) were identified. The results of meta-analysis showed that statistically significant differences were found in Harris hip score on the 3rd month after operation [MD = 8.37, 95% CI (6.02,10.72)], Hematocrit [MD = 0.02, 95% CI (0.01, 0.03)] and Hemoglobin [MD = 0.50, 95% CI (0.16, 0.85)] at the 48th hour after operation, changed value of femoral offset [MD = 0.30, 95% CI (0.04, 0.56)] between two groups. In the change value of femoral offset, THA was better than MIS-THA; There were no statistically significant differences between two groups in Harris hip score at 1st year after operation [MD = 3.26, 95% CI (-3.25, 9.76)], WOMAC score [MD = -0.53, 95% CI (-3.67, 2.60)] and Oxford score [MD = 1.34, 95% CI (-3.46, 6.13)] at the 6th week after operation, Hematocrit at the 8th hour after operation [MD = -0.01, 95% CI (-0.02, 0.00)], the incidence of hip varus [RR = 0.82, 95% CI (0.45,1.52)] and dislocation [RR = 1.40, 95% CI (0.48, 4.12)]. CONCLUSION: THA brings less trauma, less hemorrhage and better early clinical outcome compared with MIS-THA, but the difference of the complication rates between the two groups is similar.