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In the production of novel biological products, plasmids are often engineered into delivery vectors for target genes, which can be used directly as vaccines or as intermediate products for gene/cell therapy. Plasmid DNA exists in several topological forms such as supercoiled, linear, and open circular. As supercoiled plasmid shows the highest efficiency in transfecting eukaryotic cells, the content of supercoiled plasmids becomes an important indicator of plasmid quality. CGE is an effective analysis method for separating different topological structures of plasmids. For the purpose of providing plasmid manufacturers and regulatory agencies with an efficient and readily used tool for monitoring the quality of plasmids, this article identifies the optimal separation and detection conditions of CGE, presents a platform-based plasmid analytical method, and uses plasmid of different sizes to verify the feasibility of this method. In terms of detector, the LIF detector has obvious advantages over the ultraviolet detector in sensitivity and resolution. Using the optimal CE condition (10× gel buffer), baseline separation of different topological forms and impurities can be achieved for different plasmid sizes (5.9, 7.8, 15.4 kb). In addition, 6.5 kb plasmid was used to compare the different separation technologies such as CGE-LIF, ion exchange chromatography and agarose gel electrophoresis. The result shows that CGE-LIF can provide better resolution and quantitation accuracy than ion exchange chromatography and agarose gel electrophoresis. CGE-LIF, as a quick and convenient method to separate and quantify plasmids, has the advantages of high sensitivity, high resolution, and high quantitative accuracy. Therefore, it is ideal for analysis of plasmids with different sizes, and it can also be used as a platform method for manufacturers and regulatory agencies to monitor the purity and stability of plasmids.

The southeastern Central Asian Orogenic Belt (CAOB) records the assembly process between several micro-continental blocks and the North China Craton (NCC), with the consumption of the Paleo-Asian Ocean (PAO), but whether the S-wards subduction of the PAO beneath the northern NCC was ongoing during Carboniferous–Permian time is still being debated. A key issue to resolve this controversy is whether the Carboniferous magmatism in the northern NCC was continental arc magmatism. The Alxa Block is the western segment of the northern NCC and contiguous to the southeastern CAOB, and their Carboniferous–Permian magmatism could have occurred in similar tectonic settings. In this contribution, new zircon U–Pb ages, elemental geochemistry and Sr–Nd isotopic analyses are presented for three early Carboniferous granitic plutons in the southwestern Alxa Block. Two newly identified aluminous A-type granites, an alkali-feldspar granite (331.6 ± 1.6 Ma) and a monzogranite (331.8 ± 1.7 Ma), exhibit juvenile and radiogenic Sr–Nd isotopic features, respectively. Although a granodiorite (326.2 ± 6.6 Ma) is characterized by high Sr/Y ratios (97.4–139.9), which is generally treated as an adikitic feature, this sample has highly radiogenic Sr–Nd isotopes and displays significantly higher K2O/Na2O ratios than typical adakites. These three granites were probably derived from the partial melting of Precambrian continental crustal sources heated by upwelling asthenosphere in lithospheric extensional setting. Regionally, both the Alxa Block and the southeastern CAOB are characterized by the formation of early Carboniferous extension-related magmatic rocks but lack coeval sedimentary deposits, suggesting a uniform lithospheric extensional setting rather than a simple continental arc.

Parkinson's disease (PD) is a neurodegenerative disease characterized by dyskinesia and related to microglia-mediated pyroptosis. Stem cell-derived exosomes have small size, low immunogenicity, and the ability of transferring the effective substances of stem cells freely. In this study, exosomes were isolated from human umbilical cord mesenchymal stem cells (hucMSCs) and injected into PD rats induced by 6-hydroxydopamine (6-OHDA). We found that the exosomes were absorbed by dopaminergic neurons and microglia in the affected side and exosome treatment inhibited microglia activation and prevented nigral-striatal dopamine neuron damage. Furthermore, pretreatment cultured BV2 cells with exosomes inhibited TLR4/NF-κB/NLRP3 inflammasome induced by LPS/ATP. Therefore, exosomes inhibited pyroptosis and reduced the secretion of supernatant IL-1β and IL-18, improved the survival rate of SH-SY5Y. In addition, the potential targets of hucMSCs- exosomes treatment of PD was further identified by miRNA high throughput sequencing and protein spectrum sequencing.

The determination of erythropoietin (EPO) isoforms by using capillary zone electrophoresis (CZE) has been a key study in the quality control of erythropoietin products. However, the current Europea...

Snake venom is a complex mixture mainly consisting of proteins and peptides which varies with different species. These variations lead to different toxic mechanisms and different anti-venom serums for treatment and the determination of their use as drugs. Hence, it is important to develop a sensitive and reliable method to identify the species of snakes from venoms. Herein, we present a novel strategy based on the sheathless capillary electrophoresis-electrospray ionization-mass spectrometry (CESI-MS) system to characterize snake venom proteins. Through the determination of peptides, we found the characteristic peptides of 8 different snakes with high sensitivity (1 μg mL−1) and high selectivity, which provided a reliable method for the species identification and purity detection of snake venom samples.

Alzheimer’s disease (AD), the most common cause of dementia, is a neurodegenerative disorder characterized by amyloid plaque accumulations, intracellular tangles and neuronal loss in certain brain regions. It has been shown that a disturbance of normal iron metabolism contributes to the pathophysiology of AD. However, the mechanism underlying abnormal iron load in the brain of AD patients is unclear. The frontal cortex, an important brain structure for executive function, is one of the regions affected by AD. We investigated the beneficial effects of active compounds of Epimedium, Astragaoside and Puerarin on iron metabolism in the frontal cortex of six-month-old APPswe/PS1ΔE9 (APP/PS1) double transgenic mouse, a model of AD. Treatment with the active compounds reduced cognitive and memory deficits and damaged cell ultrastructure in APP/PS1 mice. These beneficial effects were associated with changes in expression levels of iron metabolism proteins in the frontal cortex, including divalent metal transporter with iron response element (DMT1-with IRE), divalent metal transporter without iron response element (DMT1-without IRE), transferrin (TF) and transferring receptor 1 (TfR1); three release proteins including the exporter ferroportin 1 (Fpn1), ceruloplasmin (CP) and hephaestin (HEPH), one increased storage iron protein ferritin and one iron regulating hormone hepcidin. These findings suggest that the active compounds improve cognition and memory in brain neurodegenerative disorders and these beneficial effects are associated with reduced impairment of iron metabolism. This study may provide a new strategy for developing novel drugs to treat AD.

Cobratide is a peptide drug extracted from the venom of Chinese cobra, and has been widely used in the clinical treatment of chronic, intractable and persistent pain. In a recent study, it was reported that it has the potential to treat COVID-19. In order to control the quality of commercial cobratide drugs, a protocol was established for the separation, identification and quantification of cobratide and its associated impurities, in which sheathless capillary electrophoresis-mass spectrometry (CE-MS) was used for identification and a rapid capillary electrophoresis-ultraviolet-visible detector (CE-UV) method was developed for accurate quantification. Separation conditions that affect the resolution and MS intensities of cobratide and its associated impurities were investigated, including pH value, concentration of background electrolyte (BGE), ratio of organic additive and sample solution. The optimized CE conditions (BGE: 50 mM NH4Ac, pH 4.0; sample solution: deionized water) were used for both sheathless CE-MS and CE-UV methods. Three associated impurities were separated and identified for the first time by sheathless CE-MS. Then, a rapid CE-UV method was validated and used for accurate quantification of cobratide and its associated impurities. The CE-UV method showed good linearity between concentration and corrected peak area of cobratide in the concentration range of 5.36-536.30 μg mL-1. The limit of quantification of the CE-UV method was 4.16 μg mL-1. The relative standard deviations of migration time were less than 1% for both intra-day and inter-day experiments, and those of corrected peak area were less than 5%. Finally, different cobratide drugs were analyzed to evaluate the batch-to-batch consistency. This established protocol combining sheathless CE-MS and CE-UV methods would provide useful information for both quality control and process analysis of peptide drugs.

Garnet-bearing mafic granulites occur as lenses within TTG gneiss or metapelite in the Fuping Complex, middle Palaeoproterozoic Trans-North China Orogen. They are composed mainly of garnet, clinopyroxene, orthopyroxene, hornblende, plagioclase, quartz and accessary zircon and titanite. Four stages of metamorphic mineral assemblages have been found in these mafic granulites: (a) the prograde assemblages (M1) are inclusions preserved in the garnet porphyroblasts, including clinopyroxene, hornblende, plagioclase and quartz; (b) the metamorphic peak assemblages (M2) consist of garnet porphyroblasts plus matrix minerals clinopyroxene + orthopyroxene + hornblende + plagioclase + quartz + zircon + titanite; (c) the first retrograde assemblages (M3) are represented by clinopyroxene + orthopyroxene + plagioclase + quartz symplectites rimming the garnets; and (4) the final retrograde assemblages (M4) are hornblende + plagioclase + quartz symplectites rimming or adjacent to the garnets. The retrieved metamorphic P-T paths pass from 530–600 °C/6.5–7.0 kbar (M1) through 680–820 °C/7.2–11.7 kbar (M2) to 730–760 °C/3.2–3.9 kbar (M3) and finally to 600–640 °C/3.2–3.7 kbar (M4). All the P-T paths of the mafic granulites are clockwise, two of these even contain near isothermal decompression (ITD) and subsequent near isobaric cooling (IBC) segments. SHRIMP U-Pb dating of metamorphic zircons of the mafic granulites yields a mean weighted age of ∼1849 ± 9Ma, which is consistent with the metamorphic time of surrounding TTG gneisses. Therefore, the Fuping Complex records the collision event between the Eastern and Western Blocks of the North China Craton that led to the final assembly of this craton during the late Paleoproterozoic.

Geothermobarometry and phase equilibria modeling were conducted for garnet-bearing amphibolite of the Inyoni Shear Zone (ISZ), southwestern Barberton Greenstone Belt, South Africa. The prograde (M1), metamorphic peak (M2) and retrograde (M3) metamorphic P-T conditions were estimated to be ∼560 °C/∼8 kbar, 660–730 °C/7–9.5 kbar and 570–630 °C/5–6 kbar, respectively. The amphibolite records clockwise P-T paths, and the metamorphic peak P-T conditions belong to the medium P/T facies series. The retrograde segment of the P-T path documents near isothermal decompression which may reflect relative fast exhumation. The estimated apparent geotherm is 20–30 °C/km. SIMS U-Pb dating of metamorphic zircon suggests that the metamorphism of the ISZ amphibolite have occurred during ∼3.26–3.22 Ga, and the metamorphic peak might occur at ∼3.24 Ga. Furthermore, 40Ar/39Ar dating of hornblende indicates that the cooling stage might occur at ∼3.20 Ga. It is anticipated that the protolith of the amphibolite of the ISZ may have been involved in a subduction-like tectonic process along with the TTG plutons and was metamorphosed during 3.26–3.22 Ga, then uplifted from within the surrounding TTG plutons at ∼3.20 Ga.

Aminoglycosides (AGs) are an important class of antibiotics that have a good bactericidal effect on Gram-positive and Gram-negative bacteria. Long-term consumption of AGs may cause many allergic reactions due to their high affinity to tissue. It is necessary to develop a sensitive and reliable analytical method for trace-level AGs in food. A capillary electrophoresis-electrospray ionization-tandem mass spectrometry (CE-ESI-MS/MS) method was established for the determination of AGs. High sensitivity was achieved by using a sheathless CE-MS interface and transient isotachophoresis. Under the optimized conditions, four AGs were separated by CE and quantified by MS detection with high sensitivity. The limit of quantitation for the four AGs in milk was 0.67 μg kg−1. The recoveries of the four AGs in spiked milk ranged from 76.20 to 110.00% with relative standard deviations of 7.25–13.73%. The results indicated that sheathless CE-ESI-MS/MS would be a sensitive and effective platform for AG detection in food.

Parkinson’s disease (PD) is a progressively debilitating neurodegenerative condition that leads to motor and cognitive dysfunction. At present, clinical treatment can only improve symptoms, but cannot effectively protect dopaminergic neurons. Several reports have demonstrated that human umbilical cord mesenchymal stem cells (hucMSCs) afford neuroprotection, while their application is limited because of their uncontrollable differentiation and other reasons. Stem cells communicate with cells through secreted exosomes (Exos), the present study aimed to explore whether Exos secreted by hucMSCs could function instead of hucMSCs. hucMSCs were successfully isolated and characterized, and shown to contribute to 6-hydroxydopamine (6-OHDA)-stimulated SH-SY5Y cell proliferation; hucMSC-derived Exos were also involved in this process. The Exos were purified and identified, and then labeled with PKH 26, it was found that the Exos could be efficiently taken up by SH-SY5Y cells after 12 h of incubation. Pretreatment with Exos promoted 6-OHDA-stimulated SH-SY5Y cells to proliferate and inhibited apoptosis by inducing autophagy. Furthermore, Exos reached the substantia nigra through the blood–brain barrier (BBB) in vivo, relieved apomorphine-induced asymmetric rotation, reduced substantia nigra dopaminergic neuron loss and apoptosis, and upregulated the level of dopamine in the striatum. These results demonstrate that hucMSCs-Exos have a treatment capability for PD and can traverse the BBB, indicating their potential for the effective treatment of PD.

Amphibolites in the Shuixiakou area of the southern Dunhuang Orogenic Belt, southernmost Central Asian Orogenic Belt (CAOB), occur as lenses within hornblende-biotite-plagioclase gneiss or pelitic schist, exhibiting block-in-matrix feature of tectonic mélange. Three generations of metamorphic mineral assemblages (M1, M2, and M3) have been recognized in the garnet-bearing amphibolite lenses. The metamorphic prograde assemblage (M1) is documented with inclusion trails (hornblende + plagioclase + quartz) within garnet porphyroblasts, and are estimated to be formed under 610–690 °C and 6.5–10.2 kbar. The metamorphic peak assemblage (M2) consists of garnet + hornblende + clinopyroxene + plagioclase + quartz in the matrix and records metamorphic peak P-T conditions of 720–750 °C and 13.4–14.7 kbar. The retrograde assemblage (M3) is represented by the symplectic assemblage (hornblende + plagioclase + quartz ± biotite ± magnetite) rimming the garnet porphyroblast, formed in the decompression stage under P-T conditions of 630–730 °C and 3.8–7.2 kbar. The derived metamorphic P-T paths show similar tight clockwise loops including nearly isothermal decompression processes, typical of orogenic metamorphism. SIMS dating of metamorphic zircons from the amphibolites confirm that the high-pressure metamorphism (M2) occurred at ca. 438–398 Ma.

The discrete mafic granulite and amphibolite enclaves within the Pingyang trondhjemitic pluton, Fuping metamorphic terrane, middle Trans-North China Orogen, ubiquitously record three stages of metamorphic assemblages. For the mafic granulite enclaves, the prograde metamorphic assemblage (M1) is represented by mineral inclusions (clinopyroxene + hornblende + plagioclase + quartz ± apatite) preserved in the garnet porphyroblast, the metamorphic peak (M2) assemblage consists of garnet and matrix minerals of clinopyroxene + orthopyroxene + hornblende + plagioclase + quartz ± magnetite ± ilmenite ± zircon, and the retrograde (M3) stage is represented by symplectite assemblage of orthopyroxene + plagioclase ± clinopyroxene ± hornblende ± quartz rimming the garnet porphyroblast. The metamorphic P-T paths of the mafic granulite enclaves are defined to pass from 560–750 °C/6–9 kbar (M1) through 740–880 °C/11–14 kbar (M2) to 720–800 °C/6–8 (M3), indicative of a collisional orogenic process. The metamorphic P-T path of the amphibolite enclave experienced from 670–730 °C/9.3–11.8 kbar to 710–730 °C/3.9–5.5 kbar, further certify such metamorphic feature of an orogenic belt. SIMS U-Pb dating of zircons of the trondhjemitic gneiss yields the magmatic crystallization age of ∼2.52 Ga, and both the trondhjemitic gneiss and the mafic granulite enclaves yield the metamorphic age of ∼1.89–1.86 Ga. Therefore, it can be concluded that the Fuping terrane was involved in the late Palaeoproterozoic subduction-collision-uplifting tectonic process caused by amalgamation of the Eastern and Western Blocks of the North China Craton along the Trans-North China Orogen.

The Hongliuxia tectonic melange of the southern Dunhuang terrane, northwestern China, southernmost Central Asian Orogenic Belt (CAOB), consists of eclogite, mafic granulite, and amphibolite as puddingstones within a matrix of metapelitic gneiss and marble; these rocks are interpreted to be part of an ancient subduction zone setting. Secondary ion mass spectrometry U-Pb dating of metamorphic zircons obtained from the puddingstones and matrix metapelite suggests that the metamorphism occurred at ca. 428–391 Ma. The metamorphic rocks all record similar clockwise metamorphic pressure-temperature-time ( P - T - t ) paths of the western Alpine type. However, remarkable differences between metamorphic peak P - T conditions ranging from 830 °C and 24.2 kbar for the eclogite puddingstone to 700 °C and 10.2 kbar for the metapelite matrix were found in the melange rocks. This indicates the mixing of rocks from significantly different depths to create a tectonic melange in a subduction channel, possibly juxtaposed during the uplift stage. These data suggest that the southernmost CAOB underwent subduction and subsequent exhumation caused by subduction of the Paleozoic Hongliuxia ocean during the middle Silurian to middle Devonian.

Garnet-bearing mafic granulites and amphibolites from the Hongliuxia area of the southern Dunhuang orogenic belt, northwestern China, commonly occur as lenses or boudinages enclosed within metapelite or marble, which represent the block-in-matrix feature typical of orogenic melange. Three to four generations of metamorphic mineral assemblages are preserved in these rocks. In the high-pressure amphibolites, prograde mineral assemblages (M1) occur as inclusions (hornblende + plagioclase + quartz ± chlorite ± epidote ± ilmenite) preserved within garnet porphyroblasts, and formed at 550–590 °C and 7.7–9.2 kbar based on geothermobarometry. The metamorphic peak mineral assemblages (M2) are composed of garnet + hornblende + plagioclase + quartz + clinopyroxene, as well as titanite + zircon + rutile + apatite as accessory minerals in the matrix, and are estimated to have formed at 640–720 °C and 14.1–16.0 kbar. The first retrograde assemblages (M3) are characterized by “white-eye socket” symplectites (hornblende + plagioclase + quartz ± biotite ± epidote ± magnetite) rimming garnet porphyroblasts, which formed at the expense of the garnet rims and adjacent matrix minerals during the decompression stage under P – T conditions of 610–630 °C and 5.6–11.8 kbar. The second retrograde assemblages (M4) are intergrowths of actinolite and worm-like quartz produced by the breakdown of the matrix hornblendes, and formed under P – T conditions of ∼490 °C and ∼2.8 kbar. For the high-pressure mafic granulites, the prograde assemblages (M1) are represented by plagioclase + quartz preserved within the garnet porphyroblasts. The metamorphic peak assemblages (M2) are garnet + matrix minerals (clinopyroxene + plagioclase + quartz + hornblende + rutile + zircon) and were estimated to have formed at ∼680 °C and ∼15.4 kbar. The retrograde assemblages (M3) are characterized by fine-grained patches of hornblende + plagioclase + quartz rimming the garnet porphyroblasts, as well as hornblende rimming clinopyroxene in the matrix, and were inferred to have formed at ∼620 °C and ∼4.2 kbar. For the metapelitic gneiss, the metamorphic peak assemblages are the garnet porphyroblasts plus the matrix minerals (biotite + plagioclase + quartz + ilmenite + zircon), which were estimated to have formed at ∼630 °C and ∼8.9 kbar. The mafic granulites and amphibolites record fairly similar clockwise P–T paths that include nearly isothermal decompression processes, which suggest that they experienced subduction and subsequent rapid tectonic exhumation. SIMS and LA-ICP-MS U–Pb dating of zircons and 40Ar/39Ar dating of hornblende suggest that the metamorphism occurred at ∼430–390 Ma. Field occurrences, different protolith ages of the mafic granulites and amphibolites, and the considerable gap in peak P – T conditions between the amphibolite and mafic granulite boudinages and their country rock may suggest a melange accumulation process during the Paleozoic caused by the Silurian–Devonian orogeny, which is possibly associated with the closure of the Liuyuan ocean, a branch of the Paleo-Asian ocean near the southern Central Asian Orogenic Belt.

Metamorphic evolution and geochronology of pelitic granulites were reported for the first time in the Taihua metamorphic complex, Mts. Huashan area, southern segment of the trans-North China Orogen (TNCO). Three generations of metamorphic mineral assemblages are recognized: (1) the prograde metamorphic mineral assemblages (M1) are represented by mineral inclusions within the garnet porphyroblasts; (2) the metamorphic peak assemblage (M2) are the garnet porphyroblasts and minerals in the matrix (biotite + orthopyroxene + plagioclase + quartz + K-feldspar + ilmenite + zircon + magnetite); and (3) the retrograde metamorphic mineral assemblages (M3) are represented by the symplectic assemblages around the garnet porphyroblasts, resulted from decomposition reactions between garnet rims and neighboring minerals in the matrix. Calculated by both conventional thermobarometry and pseudosection modeling in the NCKFMASHT system using the Perple_X technique, the P–T conditions of these three metamorphic stages are constrained to be of 4–5 kbar/520–530 °C for the M1 stage, 6.8–8.6 kbar/730–810 °C for the M2 stage and 4.1–6.4 kbar/570–740 °C for the M3 stage, respectively. The derived clockwise P–T paths imply that the Mts. Huashan terrane involved in the subduction and subsequent collision between the Eastern and Western Blocks of the North China Craton (NCC) along the Palaeoproterozoic Trans-North China Orogen (TNCO). High resolution SIMS U–Pb dating of metamorphic zircons reveals the metamorphic ages of 1.85–1.82 Ga. Combined with geochronological data from the literature, it is concluded that the tectonothermal evolution between the Eastern and Western Blocks started as early as ∼1.97 Ga and lasted as late as 1.80 Ga. Furthermore, the eastern Taihua complex records older metamorphic ages and higher peak metamorphic pressures than those of the western Taihua complex, possibly suggesting an eastward subduction model for the TNCO.

The Taihua metamorphic complex in the southern part of the North China Craton is composed of tonalite-trondhjemite-granodiorite (TTG) gneisses, amphibolites, metapelitic gneisses, marbles, quartzites, and banded iron formations (BIFs). The protoliths of the complex have ages ranging from ∼2.1 to ∼2.9 Ga and was metamorphosed under the upper amphibolite to granulite facies conditions with NWW-SEE-striking gneissosity. Metapelitites from the Wugang area have three stages of metamorphic mineral assemblages. The prograde metamorphic mineral assemblage (M1) includes biotite + plagioclase + quartz + ilmenite preserved as inclusions in garnet porphyroblasts. The peak mineral assemblage (M2) consists of garnet porphyroblasts and matrix minerals of sillimanite + biotite + plagioclase + quartz + K-feldspar + ilmenite + rutile + pyrite. The retrograde mineral assemblage (M3), biotite + plagioclase + quartz, occurs as symplectic assemblages surrounding embayed garnet porphyroblasts. Garnet porphyroblasts are chemically zoned. Pseudosection calculated in the NCKFMASHTO model system suggests that mantles of garnet porphyroblasts define high-pressure granulites facies P–T conditions of 12.2 kbar and 830 °C, whereas garnet rims record P–T conditions of 10.2 kbar and 840 °C. Integrating the prograde mineral assemblages, zoning of garnet porphyroblasts with symplectic assemblages, a clockwise metamorphic P–T path can be retrieved. High resolution SIMS U−Pb dating and LA−ICP−MS trace element measurements of the metamorphic zircons demonstrate that metapelites in Wugang possibly record the peak or near peak metamorphic ages of ∼1.92 Ga. Furthermore, 40Ar/39Ar dating of biotite in metapelites suggests that the cooling of the Taihua complex may have lasted until ∼1.83 Ga. Therefore, a long-lived Palaeoproterozoic metamorphic event may define a slow exhumation process. Field relationship and new metamorphic data for the Taihua metamorphic complex does not support the previous model in which the Tran-North China Craton (TNCO) was formed through the collision between the East and West blocks.

Tonalite-trondhjemite-granodiorite (TTG) suite and potassic granite volumetrically expose in the Neoarchean to Paleoproterozoic Taihua complex, Mts. Huashan region, southernmost segment of the Trans-North China Orogen (TNCO). Zircon U–Pb dating on the trondhjemite, granitic gneiss, K-feldspar granite and coarse-grained granite samples show three episodes of magmatism (2.55–2.49 Ga, 2.33–2.25 Ga and 1.87–1.80 Ga) with distinct geochemical features in this area during the Paleoproterozoic. The trondhjemite samples have high SiO2 (67.46–71.73 wt%), Na2O (4.83–5.95 wt%), low Mg# (31–40) and HREE contents, with moderate (La/Yb)N values (16.8 to 35.3) and Sr/Y ratios (15.8 to 34). The potassic granite samples show high SiO2 (65.2–75.43 wt%), K2O (3.9–8.6), low Na2O (1.74–4.17 wt%), Mg# (2–46) and HREE contents, with moderate to high (La/Yb)N values (10.3 to 226) and Sr/Y ratios (12.8 to 208). All these granitoid samples are characterized by high SiO2 and low Mg#, Cr, Ni with moderate to high (La/Yb)N values and Sr/Y ratios. The absence of evidence of any pre-existing high Sr/Y and La/Yb sources in this region led to that the granitoids probably generated from partial melting of hydrous mafic rocks with garnet and amphibole in the residue. Therefore, partial melting of thickened lower curst is the most likely origin. Combined with previous studies, the first episodic magmatism (2.55–2.49 Ga) represented by TTG and granitic gneisses with positive whole rock ƐNd(t) and zircon ƐHf(t) values is interpreted as melts from partial melting of juvenile thickened lower crust. The second episodic magmatism (2.33–2.25 Ga) represented by TTG, granitic gneisses and K-feldspar granite with positive to negative whole rock ƐNd(t) and zircon ƐHf(t) values is suggested as the product of partial melting of both juvenile and pre-existing crustal material. The third episodic magmatism (1.87–1.80 Ga) is represented by these potassic granites, which is synchronism with the metamorphism recorded in this region and probably resulted from partial melting of pre-existing crustal materials in a syn-orogenic or post-orogenic setting during the collision between the Eastern and Western Blocks of the North China Craton. Multistage continental accretion (at 2.84–2.72 Ga, 2.57–2.43 Ga and 2.36–2.25 Ga) and reworking (at 2.36–2.25 Ga, 2.19–2.07 Ga and 1.87–1.80 Ga) occurred in the southern segment of the TNCO from Neoarchean to Paleoproterozoic. Transformation from an Andean-type continental margin arc setting on the western margin of the Eastern Block to continent-arc-continent collision in the southern TNCO during Late Neoarchean to Late Paleoproterozoic is suggested in this paper.

The Taihua metamorphic complex exposes in the southern Trans-North China Orogen (TNCO) and records at least three episodes of magmatism. The Shanxian TTG gneisses obtained at 2.54–2.48 Ga have high SiO 2 , variable Mg# with high (La/Yb) N and Sr/Y ratios (15.08–93.26 with average of 37.31 and 7.33–115.05 with average of 49.59, respectively). They show negative Nb and Ta but positive Zr and Hf anomalies with low Nb/Ta and Gd/Yb, and high Zr/Hf and Zr/Sm ratios (4.97–18.8, 1.92–6.37, 23.71–50.26, and 29.18–75.23, respectively), and have positive e Hf (t) values (+1.7 to +7.9) and e Nd (t) values (+0.72 to +2.55), indicating that they were possibly produced by partial melting of lower crust derived from metasomatized lithospheric mantle with the residue of minor garnet. The Sihe granitic gneisses recorded at 2.35–2.30 Ga are enriched in silica, Al 2 O 3 contents (13.59–15.33), K 2 O/Na 2 O ratios (1.13–1.7), defined as high-Al TTG. They exhibit high Sr/Y, Zr/Sm and Zr/Hf ratios and low Nb/Ta and Gd/Yb ratios (44.71–83.09, 47.79–62.58, 36.05–37.43, 12.04–16.36, and 2.95–3.68, respectively) with negative Eu anomaly. Combined with Hf and Nd isotopes (−2.5 to +4.7 and −0.74 to +0.36), the Sihe granitic gneiss was possibly generated from partial melting of lower crust with minor ancient material contributions, leaving residual amphibole and minor garnet in the source. The Muce monzonitic gneisses emplaced at 2.17–2.16 Ga have high Mg#, Ni and Cr contents, constant Sr/Y and (La/Yb) N (42.39–50.33, 19.8–41.4, 33.6–74.2, 31.32–34.14, and 15.32–16.7, respectively), with relatively low and constant Dy/Yb ratio (1.82–1.85). Together with Hf and Nd isotopes (−6.5 to −0.9 and −2.07 to −2.86), the Muce monzonitic gneisses might be derived from partial melting of Neoarchean pre-existing crustal materials, possibly in an arc setting. It is therefore found that four episodes of crustal growth and/or reworking in the southern segment of the TNCO have occurred at 2.85–2.72 Ga, 2.57–2.48 Ga, 2.35–2.30 Ga and 2.2–2.0 Ga, respectively, likely to connect with the subduction–collision between the Eastern and Western Blocks along the TNCO in the North China Craton.

Garnet-bearing mafic granulite and amphibolite exposed as lenses, boudins, or interlayers within metasediments in the Qingshigou area, Dunhuang block, southernmost Central Asian orogenic belt, record important information for understanding the tectono-metamorphic evolution of subduction and collision zones in the southern Central Asian orogenic belt during the mid-Paleozoic. Three stages of metamorphic assemblages (M1, M2, M3) are recognized in the high- and medium-pressure mafic granulite and amphibolite. In the high-pressure mafic granulite, the prograde assemblage (M1) is represented by inclusion minerals (hornblende + plagioclase + quartz) preserved in garnet porphyroblasts; the metamorphic peak assemblage (M2) is characterized by garnet porphyroblasts and matrix minerals (garnet + clinopyroxene + plagioclase + quartz ± zircon ± titanite); and the retrograde assemblage (M3) is marked by coronitic symplectite (hornblende + plagioclase + quartz ± magnetite) rimming the garnet porphyroblasts. In the medium-pressure mafic granulite, the prograde assemblage (M1) of hornblende + plagioclase + quartz is included in the garnet porphyroblasts; the peak assemblage (M2) consists of garnet + orthopyroxene + clinopyroxene + plagioclase + quartz ± zircon ± titanite (M2) in the matrix; and the retrograde assemblage (M3) of hornblende + orthopyroxene + plagioclase + quartz (M3) surrounds the garnet porphyroblasts. In the amphibolite, the prograde assemblage (hornblende + plagioclase + quartz + ilmenite) is preserved as inclusions in garnet (M1); the peak assemblage (M2) is composed of garnet + hornblende + plagioclase + quartz ± zircon ± titanite; and the retrograde assemblage (M3), consisting of hornblende + biotite + plagioclase + quartz + epidote + magnetite, rings the garnet porphyroblasts. Geothermobarometric calculations suggest that the metamorphic pressure-temperature paths pass from 568 °C and 8.8 kbar through 607 °C and 10.6 kbar and 861 °C and 16.9 kbar and finally to 598 °C and 4.4 kbar for the high-pressure mafic granulite; from 756 °C and 9.0 kbar through 750–874 °C and 9.3–11.6 kbar to 675 °C and 4.7 kbar for the medium-pressure mafic granulite; and from 686 °C and 7.6 kbar through 715–766 °C and 10.6–11.2 kbar to 671 °C and 5.6 kbar for the amphibolite, and the paths show clockwise pressure-temperature loops typical of an orogenic process. The metamorphic peak of the high-pressure mafic granulite lies in the eclogite facies, which is indicative of a subduction zone environment. High-resolution secondary ion mass spectrometry (SIMS) U-Pb dating of metamorphic zircon indicates that the metamorphism occurred in the Early Silurian (ca. 430 Ma) and lasted for at least 65 m.y. This study reveals a possible southward subduction history of a branch of the Paleo–Asian Ocean, the Liuyuan Ocean, from the Silurian to Late Devonian, which may be an important event in the accretionary history of the Central Asian orogenic belt.

To improve electrochemical performance of Li ion battery , we synthesis flower-like V6O13 in oxalic acid solvent with HCl. The composition and morphology of the V6O13 were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements, respectively. The synthesized flowers-like V6O13 are less than 600nm in the width of the ribbon and have purity phase of the V6O13.The electrochemical performance of the flowers-like V6O13 were characterized by charge and discharge performance, EIS and CV. The flowers-like V6O13 exhibited high electrochemical performance.

As a key accessory mineral in metapelite, monazite forms in the metamorphic event and therefore, places important direct constraint on the timing of the tectono-metamorphic event. In this study, we investigate four representative metapelites from different metamorphic terranes in the central-south Trans-North China Orogen (TNCO), applying secondary ion mass spectrometry (SIMS) U–Th–Pb dating on monazite. The dating results reveal that monazite collected from the Huashan, Luoning, Zanhuang and Wutai metamorphic complexes record the metamorphic ages of ~1.83 Ga, ~1.95 Ga, ~1.85 Ga and ~1.91 to 1.83 Ga, respectively. Combined with the literature data of metamorphic geochronology on the discrete terranes within the TNCO, it is suggested that the amalgamation between the Western and Eastern Blocks of the North China Craton along the nearly NS-trending TNCO stared as earlier as ~1.97 Ga and continued to as late as ~1.80 Ga, which was in fact a long-lived tectono-metamorphic event.

Garnet-bearing amphibolites and metapelites of the Luoning metamorphic terrane, Taihua metamorphic complex, southern terminal of the Palaeoproterozoic Trans-North China Orogen (TNCO), preserve different metamorphic mineral assemblages formed at three metamorphic stages in the Palaeoproterozoic. The prograde mineral assemblages (M1) comprise of hornblende + plagioclase + quartz ± biotite inclusions preserved in the garnet porphyroblasts in the amphibolites or quartz + biotite + plagioclase inclusions preserved in the garnet porphyroblasts in the metapelites. The metamorphic peak mineral assemblages (M2) are represented by the garnet porphyroblasts as well as the matrix minerals plagioclase + hornblende ± biotite + quartz in the amphibolites or quartz + biotite + plagioclase ± hornblende in the metapelites, respectively. The retrograde mineral assemblages (M3) are the worm-like, fine-grained “white-eye socket” symplectitic assemblages formed between the relict garnet porphyroblasts and the matrix minerals, consisting of plagioclase + hornblende ± biotite intergrowths in the amphibolites or plagioclase + biotite + quartz intergrowths in the metapelites, respectively. Geothermobarometric computation shows that the Luoning terrane records clockwise P – T trajectories including near isothermal decompression (ITD) processes, from 630–790 °C/5.3–8.9 kbar through 720–820 °C/8.9–10.7 kbar to 690–740 °C/7.1–7.7 kbar. SIMS U–Pb dating of zircons separated from the amphibolites and metapelites presents that the age of the protolith of the amphibolites is ∼2.32 Ga and the metamorphism occurred during 1.97–1.94 Ga, suggesting that the subduction–collision and the subsequent exhumation occurred in the late Palaeoproterozoic. Combined with the literature data of the different discrete terranes within the Trans-North China Orogen, it is further deciphered that the tectono-metamorphic event of the Trans-North China Orogen started as early as 1.97 Ga and lasted as late as 1.80 Ga, suggesting that the tectono-metamorphic event of the orogen is a long and complex history.

In the present study, the Ti-in-biotite geothermometer was revised using more than 300 natural rutile- or ilmenite-bearing metapelites collected worldwide. The formulation was empirically calibrated as \\( \\ln [T\\,(^\\circ {\\text{C}})] = 6.313 + 0.224\\ln (X_{\\text{Ti}} ) - 0.288\\ln (X_{\\text{Fe}} ) - 0.449\\ln (X_{\\text{Mg}} ) + 0.15P\\,({\\text{GPa}}) \\) , with \\( X_{j} = {{j}}/({\\text{Fe}} + {\\text{Mg}} + {\\text{Al}}^{\\text{VI}} + {\\text{Ti}}) \\) in biotite, assuming ferric iron content of 11.6 mol% of the total iron in biotite. This thermometer is consistent with the well-calibrated garnet-biotite thermometer within error of ±50 °C for most of the calibrant samples and can successfully distinguish systematic temperature changes of different metamorphic zones in both prograde and inverted metamorphic terranes as well as thermal contact aureoles. Thus, the thermometer truthfully reflects real geologic conditions and can be applied to TiO2-saturated metapelites metamorphosed at the crustal level within the calibration ranges (450-840 °C, 0.1-1.9 GPa, XTi = 0.02-0.14 in biotite).

The Ti-in-muscovite geothermometer was empirically calibrated as ln[T(oC)] = 7.258 + 0.289 ln(Ti) + 0.158[Mg/(Fe + Mg)] + 0.031 ln[P(kbar)] using ilmenite- and Al2SiO5-bearing assemblages in metapelites under P–T conditions of 450–800 °C and 0.1–1.4 GPa. The calibration was conducted for muscovites containing Ti = 0.01–0.07, Fe = 0.03–0.16, Mg = 0.01–0.32 and Mg/(Fe + Mg) = 0.05–0.73, respectively, on the basis of 11 oxygen per formula unit. Such compositional range covers more than 90% natural muscovites, and the random error of this thermometer is estimated to be of ± 65 °C. The geothermometer was validated against a set of independently determined temperature conditions between different degrees in samples from different prograde, inverted and contact metamorphic terranes. Application of this thermometer beyond the calibration conditions is not encouraged.

A newly developed sheathless interface for capillary electrophoresis-mass spectrometry, using a porous tip sprayer, was first applied for highly sensitive determination of cytosine modifications. The system performed well in identification and quantification of both 5-methylcytosine and 5-hydroxymethylcytosine using only 125 pg (∼20 cells) genomic DNA samples.

High-resolution SIMS U–Pb dating of metamorphic zircons of the TTG gneisses, gneissic granitoid and amphibolites of the Lushan terrane, Taihua metamorphic complex, suggests that the metamorphism had taken place at least as early as ~1.96–1.86 Ga. These new dates, along with reference data, demonstrate that the southern and middle terranes of the Trans-North China Orogen had been involved in the continent–continent collision between the Western Block and the Eastern Block of the North China Craton. This orogenic process started as early as 1.96 Ga and lasted as late as 1.80 Ga.

Exposed in the southernmost terminal of the Palaeoproterozoic Trans-North China Orogen (TNCO), the garnet-bearing amphibolites in the Mts. Huashan metamorphic complex preserve three generations of mineral assemblages including the prograde, peak and retrograde metamorphic stages. The prograde metamorphic stage (M1) is recognized as inclusion-type mineral assemblages (hornblende + plagioclase + quartz ± biotite ± ilmenite) preserved in the garnet porphyroblasts. The peak metamorphic assemblages (M2) are represented by the garnet porphyroblasts and matrix minerals (hornblende + plagioclase + quartz ± biotite ± ilmenite). The retrograde metamorphic assemblages (M3) are characterized by the symplectitic intergrowth minerals (hornblende + plagioclase + quartz ± orthopyroxene ± biotite ± ilmenite) rimming decomposed, relict garnet porphyroblasts, known as the “white-eye socket” reaction textures. Calculated by geothermometers and geobarometers, the P–T conditions of these three metamorphic stages are estimated to be of 5.7–6.0 kbar/660–760 °C for the prograde stage (M1), 6.6–7.7 kbar/700–820 °C for the peak stage (M2) and 4.5–6.7 kbar/720–760 °C for the retrograde stage (M3), respectively. Therefore, these three metamorphic stages define clockwise P–T paths including nearly isothermal decompression (ITD) processes. Geochronological studies of zircons from the amphibolites indicate that the protolith of the amphibolites formed at ∼2.3 Ga, and the metamorphism occurred at ∼1.87–1.85 Ga, and the metamorphic period was further deciphered to be of 1.96–1.80 Ga when considering our previous reports. It is therefore proposed that the southernmost terminal of the TNCO was also involved in the subduction and collision processes between the Eastern and Western Blocks of the North China Craton at least as early as 1.96 Ga and continued as late as 1.80 Ga, followed by rapid uplift and exhumation. The available data suggest that the Palaeoproterozoic tectono-metamorphic event of the southernmost terminal of the Trans-North China Orogen not only started earlier but also continued longer than the other terranes in the middle and northern sections elsewhere in the orogen.

Central hepatectomy is amongst the most difficult surgeries of liver tumors. For the routine local excision of a tumor, if the tumor has invaded the blood vessels or bile duct of the liver, then half of the liver or three lobes of the liver are resected. This results in two major drawbacks, one of which is that the residual hepatic lobe may not compensate for the damage, so it is not possible to perform conventional partial resection. The other is that the volume of normal liver tissue removed may be much more than the volume of tumor removed, causing substantial waste. In the present study, surgery was performed to resect a central liver tumor. In that surgery, the V segment and parts of the IV, VI and VIII segments were resected, and the blood supply and biliary drainage of the left hepatic lobe were kept intact. However, for the remaining VI, VII and VIII segments of the right hepatic lobe, only the blood supply from the portal vein was maintained and no arterial blood supply or biliary drainage was kept so that the patient had the opportunity to undergo radical resection and successful rehabilitation. The reason these opportunities may be possible is that the residual right liver is a temporary replacement therapy in the perioperative period. Therefore, for central hepatic tumors, particularly tumors that have invaded the neighboring bile ducts or blood vessels, if the blood supply and biliary drainage on one side is maintained and the blood supply to the other side from the portal vein is kept intact, then it is possible to perform radical resection. This provides a novel approach to the clinical resection of central liver tumors.

A novel pH-responsive coating technique was developed and applied to CE successfully in this paper. The coating was formed by bonding mixed opposite charge poly(acrylic acid) and poly(2-vinylpyridine) randomly onto the inner wall of a silica capillary. The coating processes were first characterized by ellipsometry and atomic force microscopy at macroscale and microscale, respectively. Measurements of EOF were implemented to confirm the coating. Direction and velocity of EOF became controllable from negative to positive, showing a perfect sigmoidal curve as the coating net charges alternated by the pH of BGE. The control of the EOF makes it possible to analyze different kinds of small molecules, peptides, and proteins successfully in the same capillary. Results showed that the stability and reproducibility for separations of fluoroquinolone standards were satisfactory for more than a hundred separations. A series of basic and acidic protein standards were separated with admirable efficiency and minimal adsorption using both polarities. The separation of tryptic BSA digest showed that the prepared capillary has immense potential in analyzing a single sample with both acidic and basic separations, which achieved the expectation in proteomics study by CE-MS.

With the combination of high separation ability of capillary electrophoresis (CE) and strong identification ability of mass spectrometry (MS), CE/MS is becoming a powerful tool for polar and ionic analytes analysis. Different interfaces have been developed to enhance the sensitivity and reliability since the first introduction of CE/MS in 1987. A sheathless porous interface based on a new ions transferring electric connection technique was reported to be with high sensitivity and reliability. In this work, a series of optical and electrochemical experiments were designed to study the electric connection process. The results indicated that closing CE electrical circuit and applying MS spray voltage were achieved by the small ions transferring through the interface porous wall. The new electric connection method significantly enhanced the sensitivity, resolution and stability of the CE/MS analysis. The interface was applied in CE/MS detection of morphine and 6-monoacetylmorphine in urine sample and showed an equal sensitivity to LC/MS. With the significant improvement of sensitivity and stability, the CE/MS with the new interface showed strong potential for the determination of low abundance analytes.

Protein A-coated magnetic beads (0.3 mum) have been trapped in a small portion of a neutrally coated capillary (50 mum id). Anti-beta-lactoglobulin (beta-LG) antibodies have then been immobilized on the beads through strong affinity with protein A to subsequently capture beta-LG from model or real samples. Once the immunocomplexes formed at physiological pH, a discontinuous buffer system has been used to release the partners and preconcentrate them by transient ITP. The antigens and antibodies have finally been separated by CZE and detected by UV absorbance. An LOQ of 55 nM has been achieved. This methodology has been applied to quantify native beta-LG in pasteurized and ultra-high-temperature-treated bovine milk. All the described procedures, including immunosorbent preparation, sample extraction, cleanup, preconcentration, and separation are completely automated on a commercial CE instrument. As this CE immunoassay method is simple, rapid, selective, and sensitive, it should be a practical and attractive technology for the analysis of complicated biological samples.

Background Few studies have examined seizures in pediatric brain arteriovenous malformation. In our study, risk factors associated with seizure occurrence and long-term seizure control outcomes after different treatments in pediatric arteriovenous malformation patients were investigated. Methods A retrospective analysis was conducted with clinical data from a cohort of 89 pediatric brain arteriovenous malformation patients acquired between 2008 and 2013. Univariate and multivariate analyses were used to assess risk factors associated with seizure incidence. Patients who presented with seizure before treatment were evaluated using the Engel classification during the follow-up period. Results A higher risk of seizure occurrence was observed in large size and unruptured brain arteriovenous malformations using multivariate logistic regression analysis (p

Characteristics and seizure outcomes of the 22 pediatric brain arteriovenous malformation patients. EVE, endovascular embolization; MS, microsurgery; SRS, stereotactic radiosurgery; NA, not clear. 18*: This patient underwent the combination of EVE and SRS as an initial therapy and postoperative angiograms showed obliteration rates of about 60Â %. When he exhibited rebleeding, MS therapy was taken, and post-operation DSA examination showed no residual bAVM. (DOCX 18 kb)

Rational:To investigate the clinical and MRI characteristics of spinal cord nerve Behcet's disease.Patient concerns:One patient with spinal cord nerve Behcet's disease was admitted to our hospital at October 20, 2015.Diagnose:Spinal cord nerve Behcet's disease.Interventions:Retrospective ana

A lab prototype CE-nanospray-MS platform with a high sensitivity porous sprayer was successfully applied in differential identification of Rhizoma coptidis in this paper. To obtain a stable and reliable nanospray, detailed optimizations about emitter geometry, buffer composition, emitter position, and spray voltage, as well as emitter cleanliness were discussed. Results showed that the reproducibility and sensitivity for separations of alkaloid standards were satisfactory using CE-nanospray-MS, which were also compared to ultra-HPLC (UHPLC)-MS. Their signal responds were at the same order of magnitude (intensities: 0.8 - 1.5 × 10(8) vs. 3.8 - 6.2 × 10(8) ), even though a 2 nL injection for CE was 2500-fold lower than UHPLC (5 μL injection). The absolute LOD results of CE-MS showed a remarkable superiority (18-24 fg), equal to 1000-fold lower than that of UHPLC-MS. Principal component analysis (PCA) of adulterated R. coptidis showed that this protocol had the ability to profile and qualify complex herb medicines, which also created a great potential for evaluation and qualification of rare and valuable Chinese medicines in future.

With the combination of high separation ability of capillary electrophoresis (CE) and strong identification ability of mass spectrometry (MS), CE/MS is becoming a powerful tool for polar and ionic analytes analysis. Different interfaces have been developed to enhance the sensitivity and reliability since the first introduction of CE/MS in 1987. A sheathless porous interface based on a new ions transferring electric connection technique was reported to be with high sensitivity and reliability. In this work, a series of optical and electrochemical experiments were designed to study the electric connection process. The results indicated that closing CE electrical circuit and applying MS spray voltage were achieved by the small ions transferring through the interface porous wall. The new electric connection method significantly enhanced the sensitivity, resolution and stability of the CE/MS analysis. The interface was applied in CE/MS detection of morphine and 6-monoacetylmorphine in urine sample and showed an equal sensitivity to LC/MS. With the significant improvement of sensitivity and stability, the CE/MS with the new interface showed strong potential for the determination of low abundance analytes.

A novel pH-responsive coating technique was developed and applied to CE successfully in this paper. The coating was formed by bonding mixed opposite charge poly(acrylic acid) and poly(2-vinylpyridine) randomly onto the inner wall of a silica capillary. The coating processes were first characterized by ellipsometry and atomic force microscopy at macroscale and microscale, respectively. Measurements of EOF were implemented to confirm the coating. Direction and velocity of EOF became controllable from negative to positive, showing a perfect sigmoidal curve as the coating net charges alternated by the pH of BGE. The control of the EOF makes it possible to analyze different kinds of small molecules, peptides, and proteins successfully in the same capillary. Results showed that the stability and reproducibility for separations of fluoroquinolone standards were satisfactory for more than a hundred separations. A series of basic and acidic protein standards were separated with admirable efficiency and minimal adsorption using both polarities. The separation of tryptic BSA digest showed that the prepared capillary has immense potential in analyzing a single sample with both acidic and basic separations, which achieved the expectation in proteomics study by CE-MS.

A pseudo-homogeneous immunoextraction method based on gold-coated magnetic nanoparticles (MNPs) for the specific extraction and quantitative analysis of epitestosterone (17α-hydroxy-4-androsten-3-one, abbreviated as “ET”) from human urine samples by high-performance liquid chromatography (HPLC) has been developed. Half-IgG of anti-ET monoclonal antibodies were covalently immobilized onto (Fe 3 O 4 ) core -Au shell (Fe 3 O 4 @Au) MNPs. An external magnetic field was applied to collect the MNPs which were then rinsed with distilled water followed by elution with absolute methanol to obtain ET as the analyte. The obtained extraction solution was analyzed by HPLC with UV detection (244 nm) within 12 min. The standard calibration curve for ET showed good linearity in the range of 20–200 ng mL −1 in phosphate-buffered saline (PBS) solutions with acceptable accuracy and precision. Limit of detection for ET was 0.06 ng mL −1 due to an enrichment factor of 100-fold was achieved. The results obtained by the present method for spiked human urine samples were in agreement with those from indirect competitive enzyme-linked immunoadsorbent assays (ELISAs). The antibody-conjugated Fe 3 O 4 @Au MNPs are novel materials for immunoaffinity extraction. Compared with the conventional technique using immunoaffinity column, the method described here for sample pretreatment was fast, highly specific, and easy to operate.

Finite element numerical simulations were carried out in 2D geometries to map the magnetic field and force distribution produced by rectangular permanent magnets as a function of their size and position with respect to a microchannel. A single magnet, two magnets placed in attraction and in repulsion have been considered. The goal of this work is to show where magnetic beads are preferentially captured in a microchannel. These simulations were qualitatively corroborated, in one geometrical case, by microscopic visualizations of magnetic bead plug formation in a capillary. The results show that the number of plugs is configuration dependent with: in attraction, one plug in the middle of the magnets; in repulsion, two plugs near the edges of the magnets; and with a single magnet, a plug close to the center of the magnet. The geometry of the magnets (h and l are the height and length of the magnets respectively) and their relative spacing s has a significant impact on the magnetic flux density. Its value inside a magnet increases with the h/l ratio. Consequently, bar magnets produce larger and more uniform values than flat magnets. The l/s ratio also influences the magnetic force value in the microchannel, both increasing concomitantly for all the configurations. In addition, a zero force zone in the middle appears in the attraction configuration as the l/s ratio increases, while with a single magnet, the number of maxima and minima goes from one to two, producing two focusing zones instead of only one.

An immunoaffinity capillary column has been made with poly (2-vinyl-4, 4-dimethylazlactone-co-2-hydroxyethyl methacrylate-co-ethylene dimethacrylate) (VDA-co-HEMA-co-EDMA) monolith as a support for the immobilized antibody. The monolith is prepared by UV-initiated in situ polymerization, followed by immobilizing anti-testosterone polyclonal antibody through the rapid reaction with VDA. Fluorescence labeled testosterone at C3 is designed as a tracer to estimate the extraction ability of this immunoaffinity column, and to optimize the immunoextraction process, such as washing, eluting, incubation and injection. The performance in a more realistic application is then demonstrated successfully for the rapid extraction of testosterone (T) by competitive immunoassay and on-line laser-induced fluorescence (LIF) detection. This immunoaffinity monolith is easily prepared, with high mechanical strength and low flow resistance. It is a satisfactory material as an immunoextractor to detect small molecular compounds specifically and rapidly with high sensitivity (sub ng/mL level).