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Herein, we disclose a RhIII-catalyzed heteroarylation of C(sp3)-H and C(sp2)-H bonds in heterocycles with organoboron reagents. This protocol displays high efficiency and excellent functional group tolerance. A range of heterocyclic boronates with strong coordinating atoms, including pyridine, pyrimidine, pyrazole, thiophene, and furan derivatives, can be extensively served as the coupling reagents. The direct heteroarylation method could supply potential application in terms of the synthesis of drug molecules with multiple heterocycles.

The reactions of (E)-quinoline-2-carbaldehyde oxime (Hqcah) with Ni(ClO4)2·6H2O and NH4SCN and with Ni(CF3SO3)2 and NaN3 led to two solitary metallacrowns (MCs) ([Ni5(qcah)7(Hqcah)(CH3OH)(SCN)(OH)]·ClO4 (1) and [Ni4(qcah)4(N3)4(Py)4] (2), respectively. Complex 1 is a pentanuclear nickel cluster that exhibits two "fused" 9-MC-3 structural units with both rings possessing Ni2–N–O–Ni1–N–O–Ni5–O–N and Ni3–N–O–Ni4–O–Ni5–O–N connectivities. Complex 2 consists of four [Ni(qcah)(N3)(Py)] units with adjacent nickel atoms linked together through N–O groups to construct a tetranuclear 12-MC-4 metallacrown. The ligands exhibit μ3:η2:η1:η1, μ2:η2:η1 and μ1:η2 coordination modes in 1 and μ2:η2:η1 coordination mode in 2. Magnetic property measurements and the fitting of various temperature magnetic susceptibilities revealed antiferromagnetic coupling between metal centers with the negative coupling parameters in both 1 and 2.

RhIII-catalyzed sp2 C-H cross-coupling of acrylamides with organoboron reactants has been accomplished using a commercially available N-2,6-difluoroaryl acrylamide auxiliary. A broad range of aryl and vinyl boronates as well as a variety of heterocyclic boronates with strong coordinating ability can serve as the coupling partners. This transformation proceeds under moderate reaction conditions with excellent functional group tolerance and high regioselectivity.

This paper reports two closely related heteropentanuclear manganese complexes, namely, {Na2Mn3(opch)3(μ4-O)(μ2-N3) (μ2-AcO)(μ2-MeO)}·6CH3OH·0.5H2O (1) and {Na2Mn3(opch)3(μ4-O)(μ2-N3)2(μ2-AcO)}·2.5CH3OH·2H2O (2), where H2opch is (E)-N′-(2-hydroxy-3-methoxybenzylidene)pyrazine-2-carbohydrazide. Single-crystal X-ray diffraction analysis reveals that the trigonal bipyramidal skeletons in both complexes are comparable, where a perfect triangular Mn3 motif occupies the equatorial plane. Magnetic investigations suggest that overall antiferromagnetic coupling is present within the triangles of 1 and 2. However, their dynamic magnetic properties are drastically distinct. Indeed, complexes 1 and 2 show two kinds of dual slow magnetic relaxation processes that correspond to anisotropy barriers (Δ) of 9.2 cm−1 (11.4 cm−1 for 2) and 12.8 cm−1 (30.0 cm−1 for 2) for the low- and high-frequency domains, respectively. More importantly, a further comparative study of the structure and magnetism indicates that the coordination sphere of these two model complexes with the homologous hydrazone-based coordination sites undergoes an alteration from methoxide-O to azide-N upon a subtle change of the auxiliary anion accompanied by modulating octahedron geometries, leading to a further influence on different relaxation dynamics.

{Dy16(μ6-C10H7PO3)2(μ5-C10H7PO3)8(spch)8(μ3-OH)2(μ2-OH)2(μ2-AcO)6(μ3-COO)2(DMF)2(H2O)6}·0.5CH3OH·4.5H2O (1) and {Dy16(μ5-C10H7PO3)4(μ3-C10H7PO3)12(μ2-C10H7PO3H)8(opch)4(DMF)8(MeOH)4}·2.5CH3OH·3H2O (2), where H2spch is ((E)-N'-(2-hydroxybenzylidene)pyrazine-2-carbohydrazide, C10H7PO3H2 is 1-naphthylphosphonic acid and H2opch is (E)-N'-(2-hydroxy-3-methoxybenzylidene)pyrazine-2-carbohydrazide, were successfully synthesized by varying the hydrazone ligands in the Dy-phosphonate system. It is important that the ellipsoidal core experiences a ring forming structural transformation to the supramolecular square motif upon the incorporation of an ortho-methoxy substituent into the hydrazone. Alternating-current (ac) magnetic susceptibility studies of 1 and 2 suggest that similar single molecule magnet behaviors occur for these two complexes. The result represents an effective molecular assembly tactic to develop highly complicated lanthanide coordination clusters through the multicomponent self-assembly of the coalescence of phosphonate- and hydrazone-based ligands and metal salts.

Microwave ablation (MWA) is an effective treatment option for patients with primary liver cancer. However, it has been reported that the MWA procedure induces a hepatic inflammatory response and injury, which may negatively affect the efficacy of MWA. As such, the discovery of reliable markers to monitor the patient's response to MWA is needed. Golgi protein 73 (GP73) has been shown to be associated with chronic liver disease. To date, the potential value of serum GP73 in the dynamic monitoring during MWA of liver cancer remains unclear.To examine the effects of MWA on the serum levels of GP73 in patients with primary liver cancer.A total of 150 primary liver cancer patients with a single small lesion (≤ 3 cm in diameter) were retrospectively enrolled spanning the period between January 2016 and October 2018. All of the patients received MWA for the treatment of primary liver cancer. Serum GP73, alpha-fetoprotein (AFP), and widely used liver biochemical indicators [serum albumin, total bilirubin (TBIL), alanine aminotransferase (ALT), and aspartate aminotransferase (AST)] were compared before MWA and at different time points, including 1, 2, and 4 wk following the ablation procedure.Complete tumor ablation was achieved in 95.33% of the patients at 1 mo after MWA. The 1-, 2-, and 3-year disease-free survival rates were 74.67%, 59.33%, and 54.00%, respectively. The serum AFP levels were significantly decreased at 1, 2, and 4 wk after MWA; they returned to the normal range at 12 wk after MWA; and they remained stable thereafter during follow-up in those cases without recurrence. In contrast, the serum GP73 levels were significantly increased at 1 and 2 wk after MWA. The serum GP73 levels reached the peak at 2 wk after MWA, started to decline after hepatoprotective treatment with glycyrrhizin and reduced glutathione, and returned to the pretreatment levels at 12 and 24 wk after MWA. Notably, the changes of serum GP73 in response to MWA were similar to those of TBIL, ALT, and AST.Serum GP73 is markedly increased in response to MWA of liver cancer. Thus, serum GP73 holds potential as a marker to monitor MWA-induced inflammatory liver injury in need of amelioration.

The nature of source rocks and the pressure-temperature-hydration (P-T-H2O) condition are the two main factors that control the geochemical properties of granites. Therefore, the evolution of P-T-H2O conditions can be used to deduce the tectonic setting of granites. In this paper, we report on three Paleozoic granite plutons along the Shangdan suture that revealed increasing melting temperature and decreasing pressure from 437 to 403 Ma, suggesting a crustal thinning process. The Tieyupu granodiorites (437 ± 4 Ma) display Na-rich adakite affinity, i.e., SiO2 = 69.1–70.1 wt%, Na2O/K2O = 1.9–2.26, positive zircon εHf(t) values (+4.29 to +12.04), and high Sr/Y (137–160) and Y/Yb (9.89–10.25) ratios, implying a garnet-rich residue in their source. In combination with moderate zircon saturation temperatures (814–822 °C), we infer that the Tieyupu granodiorites were formed by melting of Neoproterozoic metabasites under high-pressure (>1.5 GPa) and moderate-temperature (HP-MT) conditions. The Liangchahe granodiorites (415 ± 8 Ma) also display Na-rich adakite affinity, i.e., higher Na2O/K2O (2.16–3.11) and lower Sr/Y (77–88) ratios, and higher zircon saturation temperatures (854–874 °C), and they are interpreted to have been derived from melting of metabasites under moderate-pressure (>1.0 GPa) and high-temperature (MP-HT) conditions. Their variable zircon εHf(t) values (−14.97 to +9.80) and the existence of zircon xenocrysts suggest that the primitive adakitic melts were assimilated by evolved crustal components. The Yaogou monzogranites (403 ± 4 Ma) have the highest K2O/Na2O (0.81–1.00) ratios and total rare earth element (ΣREE; 105–191 ppm) contents, lowest Sr/Y (14–43) ratios, positive zircon εHf(t) values (+6.79 to +12.22), and highest zircon saturation temperatures (891–973 °C), showing they were formed by high-temperature melting of intermediate rocks under low-pressure conditions (

Herein, we disclose a Rh

The Mesoproterozoic Hongshuizhuang Formation in Liaoxi sag, northern China, is an important hydrocarbon source unit having good potentials to generate oil and gas. The total organic carbon (TOC) content ranges from 0.54% to 4.07% in the Chaoyang area. Trace element geochemistry was utilized to study the primary productivity and basin redox conditions during the deposition of Hongshuizhuang Formation black shales. The results suggest that primary productivity during the deposition of the Hongshuizhuang Formation was relatively high. The redox-sensitive elements results indicate that the Hongshuizhuang Formation was deposited under euxinic or anoxic bottom water conditions. The degree of environment restriction, diagenesis, reoxygenation, and the presence of free H2S can make some of the redox-sensitive elements proxies and primary productivity proxies not applicable. The high TOC content of the Hongshuizhuang Formation is contributed by high primary productivity in the surface water combined with euxinic/anoxic in the bottom water.

The results of petro- and paleomagnetic studies of the volcanic and sedimentary rocks of the Linxi and Xingfuzhilu formations (Solonker Zone, Inner Mongolia, China) are reported. The direction of an ancient prefold magnetization component is determined (Dec = 157.8°, Inc =–43.5°, K = 10.0, α95 = 5.8°) and the coordinates of the corresponding paleomagnetic pole at ~250 Ma are calculated (Plat = 64.2°, Plong = 350.6°, dp = 4.5°, dm = 7.2°). The obtained and published paleomagnetic, geochronological, and geochemical data permit palinspatic reconstructions, according to which (1) a paleobasin ~500 km wide existed between the Late Permian and beginning of the Early Triassic (250 Ma); and (2) its closure occurred not in the Permian as previously thought, but at the beginning of the Early Triassic.

The initiation time and tectonic responses of paleo–Pacific plate subduction beneath the Eurasian continent remain controversial. In this paper we report on Early Jurassic (201–198 Ma) monzogranite-tonalite association from the southern Zhangguangcai Range, northeastern China. Zircon laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) U-Pb dating indicates that the monzogranite and tonalite have identical 206Pb/208U ages of 201 ± 2 (mean square of weighted deviates, MSWD = 1.2, 2σ) and 198 ± 3 Ma (MSWD = 3.2, 2σ), respectively. The monzogranite and tonalite display different geochemical features, suggesting that they were derived from two distinct source regions. The monzogranite displays high SiO2, K2O, and Rb contents, as well as depleted whole-rock Sr-Nd-Pb isotopic compositions, i.e., eNd(t) = +8.3 to +11.7, with single-stage Nd model ages of 0.30–0.05 Ga. Zircons from the monzogranite also have depleted Lu-Hf isotopic compositions, and these contradictory geochemical features suggest that the monzogranite may be derived from melting of mid-oceanic ridge basalt (MORB)–sediment melanges in subduction zone. The Na-rich tonalite has lower SiO2 and higher TiO2 contents. In combination with their relatively evolved Sr-Nd-Pb isotopic compositions and zircon Lu-Hf isotopic compositions, it can be considered that the tonalite was derived from juvenile basaltic crust in an active continental margin. Considering other Triassic to Jurassic mafic intrusive rocks and I-type granites in the Zhangguangcai Range, we propose that the Early Jurassic monzogranite-tonalite association in the Shihe area was caused by the westward subduction of the paleo–Pacific plate beneath northeastern China.

Intracellular viscosity is an essential microenvironmental parameter and H

Methylenetetrahydrofolate reductase (MTHFR) is an important enzyme involved in folate metabolism, which is essential for DNA synthesis and methylation. Genetic variations in the MTHFR gene seem to contribute to a decreased activity of MTHFR, ultimately confer increased susceptibility to cancer. As the most extensively studied polymorphism, MTHFR C677T polymorphism was shown to contribute to cancer susceptibility but the results were inconsistent. The authors performed a meta-analysis including 134 studies (46,207 cases and 69,160 controls) to address the issue. Odds ratios (ORs) with corresponding 95 % confidence intervals (CIs) were used to assess the association. Overall, a significant elevated risk of cancer was associated with the MTHFR C677T polymorphism in T-allele versus C-allele comparison (OR = 1.06, 95 % CI 1.02–1.11, P heterogeneity

A novel ratiometric and colorimetric fluorescent chemosensor based on tricarbocyanine (1) for Ag+ has been designed and synthesized. In comparison with Ag+ chemosensors reported, our chemosensor can detect Ag+ in aqueous solution by both color changes and fluorescent ratio changes with long emission wavelength. Upon addition of Ag+ to solutions of 1, observable color change from blue to light red and remarkable shift from 758 nm to 565 nm in emission spectra occur. Under optimized experimental conditions, the chemosensor exhibits a stable response to Ag+ over a concentration range from 5.0 × 10−7 to 2.0 × 10−5 M, with a detection limit to 2.0 × 10−7 M. Most importantly, the fluorescence changes of the chemosensor are remarkably specific for Ag+ over other metal ions. In addition, the proposed chemosensor has been successfully applied for the determination of Ag+ in real water samples which demonstrates its value of practical applications in environment.

Detailed petrology and zircon U–Pb dating data indicate that the Wulong pluton is a zoned granitic intrusive, formed from successive increments of magmas. An age range of at least 30 Ma is recorded from the 225–235 Ma quartz diorite on the pluton margin, the ca. 218 Ma granodiorite in the intermediate zone, and the ca. 207 Ma monzogranite at the pluton center. All the granitoids display evolved Sr–Nd–Pb isotopic compositions, with 87 Sr/ 86 Sr(i) of 0.7044–0.7062, unradiogenic Nd (e Nd (t) values of − 6.1 to − 3.0, Nd model ages of 1.1–1.3 Ga, and moderately radiogenic Pb compositions ( 206 Pb/ 204 Pb(i) = 17.500–17.872, 207 Pb/ 204 Pb(i) = 15.513–15.549, 208 Pb/ 204 Pb(i) = 37.743–38.001), in combination with variations in zircon Hf isotopic compositions (with e Hf (t) values in each stage span 12 units) and the Hf isotopic model ages of 800–1600 Ma. These features suggest that the granitoids might have been derived from the reworking of an old lower crust, mixed with Paleozoic and Proterozoic materials. The rocks also display an adakitic affinity with Sr (479–973 ppm), high Sr/Y ratios (mostly > 60) and negligible Eu anomalies (Eu/Eu* = 0.78–0.97) but low Rb/Sr ratios, low Y (4.6–17 ppm), HREE (Yb = 0.95–1.7 ppm), Yb/Lu (6–7) and Dy/Yb (1.9–2.4) ratios, suggesting the absence of plagioclase and presence of garnet + amphibole in their residue. Considering a large gap among their crystallization ages, we propose that the geochemical evolution from pluton margin to center was controlled mainly by melting conditions and source compositions rather than fractional crystallization. Mafic enclaves that were hosted in the quartz diorite and granodiorite are mainly syenogabbroic to syenodioritic in composition, and are metaluminous and enriched in LREE and LILEs, but are depleted in HFSE, and display an evolved Sr–Nd–Pb isotopic composition, suggesting that they may have been derived from the partial melting of an enriched mantle lithosphere, which was metasomatized by adakitic melts and fluids from a subducted continental crust. In combination with the results of the Triassic ultra-high pressure metamorphic rocks in the Dabie orogenic belt, we apply a model involving the exhumation of subducted continental crust to explain the formation of the Wulong pluton. At the first stage, a dense and refractory mafic lower crust that was trapped at mantle depth by continental subduction witnessed melting under high temperature conditions to produce the quartz diorite magma, characterized by low SiO 2 (60.65–63.98 wt.%) and high TiO 2 (0.39–0.86 wt.%). The magma subsequently interacted with mantle peridotite, leading to high Mg# (57–67) and the metasomatism of the overriding mantle wedge. At the second stage, an asthenosphere upwelling that was probably caused by slab break-off at ca. 220 Ma melted the enriched sub-continental lithospheric mantle (SCLM) to produce mafic magmas, represented by the mafic enclaves that are hosted in the quartz and granodiorite, resulting in the partial melting of the shallower subducted crust, and generating the granodiorite that is distinguished by high SiO 2 (69.16–70.82 wt.%), high Al 2 O 3 (15.33–16.22 wt.%) and A/CNK values (mostly > 1.05). At the third stage, the final collapse of the Triassic Qinling–Dabie Orogenic Belt at ca. 215–205 Ma caused extensive partial melting of the thickened orogenic lower crust to produce the monzogranite, which is characterized by high SiO 2 (67.68–70.29 wt.%), low TiO 2 (mostly

The synthesis of functionalized naphthalimide (compound 1) and its application for the preparation of pH chemosensor was described. The fluorescence enhancement of compound 1 with the increase of hydrogen ion concentration is based on the hindering of photo-induced electron transfer (PET) from aliphatic amine group to the naphthalimide. The comparison of this method with some other fluorescence methods based on naphthalimide for the measurement of pH indicated that the method can be applied in aqueous solutions rather than organic solutions. The analytical performance characteristics of the proposed pH chemosensor were also investigated. The chemosensor can be applied to the determination of pH between 3.20 and 7.80. Common inorganic ions do not show obvious interference for pH measurements. Moreover, the response of the chemosensor for pH is fast (response time less than 3 min). In addition, the chemosensor has been used for determination of pH in urine samples with satisfactory results.

Naphthalimide derivative (compound 1) containing hydrophilic hexanoic acid group was synthesized and used to recognize Hg(2+) in aqueous solution. The fluorescence enhancement of 1 is attributed to the formation of a complex between 1 and Hg(2+) by 1:1 complex ratio (K=2.08×10(5)), which has been utilized as the basis of fabrication of the Hg(2+)-sensitive fluorescent chemosensor. The comparison of this method with some other fluorescence methods for the determination of Hg(2+) indicated that the method can be applied in aqueous solution rather than organic solution. The analytical performance characteristics of the proposed Hg(2+)-sensitive chemosensor were investigated. The chemosensor can be applied to the quantification of Hg(2+) with a linear range covering from 2.57×10(-7) to 9.27×10(-5) M and a detection limit of 4.93×10(-8) M. The experiment results show that the response behavior of 1 toward Hg(2+) is pH independent in medium condition (pH 4.0-8.0). Most importantly, the fluorescence changes of the chemosensor are remarkably specific for Hg(2+) in the presence of other metal ions, which meet the selective requirements for practical application. Moreover, the response of the chemosensor toward Hg(2+) is fast (response time less than 1 min). In addition, the chemosensor has been used for determination of Hg(2+) in hair samples with satisfactory results, which further demonstrates its value of practical applications.

The source characteristics of the widespread Permian high Ti/Y basalts in the Emeishan Large Igneous Province (LIP) constitute important themes to evaluate the possible connection with a mantle plume beneath the Yangtze Block in southwestern China. Here we investigate the geochemical and isotopic signature of basalts from the Guangxi and Guizhou regions in the eastern margin of the Emeishan LIP and report the occurrence of high Ti/Y basalts in Guangxi. The zircons separated from Guangxi basalts yield a U–Pb concordia age of 257 Ma, which is consistent with the age of the plume-related eruption of the Emeishan LIP. Both the Guangxi and Guizhou basalts studied here display evolved Sr–Nd isotopic composition and DUPAL Pb isotopic composition, with (87Sr/86Sr)i = 0.705231 to 0.706147, positive to slightly negative eNd(t) values of −0.13 to +0.68, and △7 = 5–11, △8 = 70–84. The Guangxi basalts possess low SiO2 (44.82–49.71 wt.%), and TiO2 (2.29–3.54 wt.%), but are enriched in LREE and LILE with (La/Sm)N values of 2.2–2.6, high Ce/Yb ratios (19.6–30.0) and slightly negative Nb and Ta anomalies. The Guizhou basalts display higher SiO2 (47.49–50.27 wt.%), TiO2 (3.93–4.92 wt.%), Zr, Nb and La contents. They also show higher Ce/Yb (30.2–37.8) and Sm/Yb (3.56–4.19) ratios as compared to those of the Guangxi basalts, and do not possess negative Nb and Ta anomalies. The distinct differences between the Guangxi and Guizhou basalts may be caused by different degrees of partial melting of the garnet peridotite in their source region. We propose that the Guizhou basalts were derived from partial melting of metasomatized veins in the Yangtze continental lithosphere which were heated by the upwelling Emeishan plume, and the Guangxi basalts represent higher degrees of partial melting of the sub-continental lithospheric mantle and undergone minor crustal contamination during their ascent.

The paper studied polymerization of rac-lactide catalyzed by a diketiminato aluminum alkoxide complex. The aluminum alkoxide complex bearing bulky isopropyl ortho substituents showed moderate activity for the rac-lactide polymerization. Microstructural study of polymer generated with the aluminum catalyst reveals that syndiotactic polylactide were produced. Results have shown that the conversion of lactide depend on the monomer/catalyst feed ratio and the reaction temperature.

Lactide polymerization were carried out by using diketiminato iron (II) alkoxide complexes HC(C(CH3)N-2,6-iPr2C6H3)2FeOiPr as catalyst. The iron (II) alkoxide complex bearing bulky isopropyl ortho substituents showed moderate activity for the rac-lactide polymerization, and gave the polylactide (PLA) with high molecular weight. In the microstructures of polymers generated with the iron (II) catalyst, no stereoslective polymerization of rac-lactide has been detected. Results have shown that the conversion of lactide depend on the iron complex/monomer feed ratio and the reaction temperature.

Naphthalimide derivative (compound 1) containing hydrophilic hexanoic acid group was synthesized and used to recognize cysteine (Cys) in aqueous solution. The fluorescence enhancement of 1 was attributed to the cyclization reaction of 1 with Cys by 1:1 binding stoichiometry, which has been utilized as the basis of fabrication of the Cys-sensitive fluorescent chemosensor. The comparison of this method with some other fluorescence methods for the determination of Cys indicated that the methods can be applied in aqueous solution rather than organic solution. The analytical performance characteristics of the proposed Cys-sensitive chemosensor were investigated. The chemosensor can be applied to the quantification of Cys with a linear range covering from 3.9 × 10−8 to 1.4 × 10−5 M and a detection limit of 7.8 × 10−9 M. And the chemosensor shows excellent selectivity for Cys over other amino acids. Moreover, the response of the chemosensor toward Cys is fast (response time less than 3 min). In addition, the chemosensor has been used for determination of Cys in serum samples with satisfactory results.

As the Internet becomes more pervasive, it is very important that the security mechanisms of a system are designed so as to prevent unauthorized access to system resources and data. The paper proposes a clustering algorithm that exploits enhanced DBScan algorithm in anomaly detection. The algorithm that can be used for mass data processing turns into the hot research point of anomaly detection, to form normal behavior profile on the audit records and adjust the profile timely as the program behavior changed. The experimental result shows that the anomaly detecting based on enhanced DBScan algorithm can a higher detection rate and a low rate of false positives of DARPA data sets.

The origin of high-Mg adakitic granitoids in collisional orogens can provide important information about the nature of the lower crust and upper mantle during the orogenic process. Late-Triassic high-Mg adakitic granite and its mafic enclaves from the Dongjiangkou area, the Qinling orogenic belt, central China, were derived by partial melting of subducted continental crust and underwent interaction with the overlying mantle wedge peridotite. Adakitic affinity of the different facies of the Dongjiangkou granite body are: high Sr, Ba, high La/Yb and Sr/Y, low Y,Yb, Yb/Lu and Dy/Yb, and no significant Eu anomalies, suggesting amphibole + garnet and plagioclase-free restite in their source region. Evolved Sr-Nd-Pb isotopic compositions [( 87 Sr/ 86 Sr) i = 0.7050 to 0.7055,e Nd (t) = –6.6 to –3.3; ( 206 Pb/ 204 Pb) i = 17.599 to 17.799, ( 207 Pb/ 204 Pb) i = 15.507 to 15.526, ( 208 Pb/ 204 Pb) i = 37.775 to 37.795] and high K 2 O, Rb, together with a large variation in zircon Hf isotopic composition (e Hf (t) = −9.8 to + 5.0), suggest that the granite was derived from reworking of the ancient lower continental crust. CaO, P 2 O 5 , K 2 O/Na 2 O, Cr, Ni, Nb/Ta, Rb/Sr and Y increase, and SiO 2 , Sr/Y and Eu/Eu* decrease with increasing MgO, consistent with interaction of primitive adakitic melt and overlying mantle peridotite. Zircons separated from the host granites have U-Pb concordia ages of 214 ± 2 Ma to 222 ± 2 Ma, compatible with exhumation ages of Triassic UHP metamorphic rocks in the Dabie orogenic belt. Mafic microgranular enclaves and mafic dykes associated with the granite have identical zircon U-Pb ages of 220 Ma, and are characterized by lower SiO 2 , high TiO 2 , Mg# and similar evolved Sr-Nd-Pb isotopic composition. Zircons from mafic microgranular enclaves (MMEs) and mafic dykes also show a large variation in Hf isotopic composition with e Hf (t) between −11.3 and + 11.3. It is inferred that they were formed by partial melting of enriched mantle lithosphere and contaminated by the host adakitic granite magma. In combination with the regional geology, high-Mg# adakitic granitoid rocks in the Dongjiangkou area are considered to have resulted from interaction between subducted Yangtze continental crust and the overlying mantle wedge. Triassic continental collision caused detachment of the Yangtze continental lithosphere subducted beneath the North China Craton, at ca. 220 Ma causing asthenosphere upwelling and exhumation of the continental crust. Triassic clockwise rotation of the Yangtze Craton caused extension in the Dabie area which led to rapid exhumation of the subducted continental lithosphere, while compression in the Qinling area and high-P partial melting (amphibole ± garnet stability field) of the subducted continental crust produced adakitic granitic magma that reacted with peridotite to form Mg-rich hybrid magma.

Random number is widely used in computer application. What is used commonly in practice is pseudo-random number generated by mathematical algorithm. Several useful pseudo-random number generating algorithm and random testing methods are discussed. And according to the disadvantage of traditional algorithm, improvement of pseudo-random number generating algorithm and some new methods to generate real-random number are summarized and analyzed.

Whole-rock major-trace elements and Sr–Nd isotopes, mineral chemistry, and zircon U–Pb and Lu–Hf isotope compositions are reported for I-type monzogranite and its mafic microgranular enclaves from the Triassic Mishuling granite in the Qinling orogen, central China. Zircon U–Pb dating yields an age of 212 ± 5 Ma for the mafic enclaves and 213 ± 3 Ma for the host monzogranite. Whole-rock major-trace elements, Sr–Nd isotopes and zircon Hf isotopes preclude simple crystal fractionation or restite unmixing for a genetic link between the enclaves and the monzogranite. Mixing between mafic and felsic magmas is compatible with the geochemical data. The monzogranite displays an enriched LILE and LREE pattern, high (87Sr/86Sr)i ratios of 0.7068 to 0.7071 and low eNd(t) values of − 9.2 to − 5.7, suggesting a crustal origin. Its high Mg# (47.6 to 50.7), Cr and Ni contents clearly indicate its derivation from mafic refractory lower crust. Most of the zircons in the monzogranite have negative eHf(t) values of − 12.5 to − 0.1 and two-stage Hf model ages of 1049 to 1683 Ma, and some zircons in the host monzogranite have positive eHf(t) values of 0.3 to 4.8 and single-stage Hf model ages of 665 to 845 Ma. This indicates that the monzogranite is most likely to be formed by partial melting of a Proterozoic lower continental crust. The mafic enclaves have fine-grained igneous textures and contain abundant acicular apatite that indicates rapid cooling. They also have a high (87Sr/86Sr)i ratio of 0.7071 and a low eNd(t) value of − 6.5, suggesting a derivation from ancient subcontinental lithosphere mantle (SCLM). Zircons in the mafic microgranular enclaves have eHf(t) values of − 1.6 to 5.1 and single-stage Hf model ages of 700 to 910 Ma, suggesting a possible origin from partial melting of the Neoproterozoic SCLM that may form in association with contemporaneously supercontinental rifting in the South China Block. Therefore, the Mishuling I-type granite may form by anatexis of Meso-Neoproterozoic lower crust, with mixing between the mafic and felsic magmas. In particular, we interpret the positive eHf(t) values as being derived from reworking of Neoproterozoic juvenile lithosphere in response to tectonic extension in the late stage of the Triassic continental collision between the South China Block and the North China Block.

Petrogenesis of high Mg# adakitic rocks in intracontinental settings is still a matter of debate. This paper reports major and trace element, whole-rock Sr–Nd isotope, zircon U–Pb and Hf isotope data for a suite of adakitic monzogranite and its mafic microgranular enclaves (MMEs) at Yangba in the northwestern margin of the South China Block. These geochemical data suggest that magma mixing between felsic adakitic magma derived from thickened lower continental crust and mafic magma derived from subcontinental lithospheric mantle (SCLM) may account for the origin of high Mg# adakitic rocks in the intracontinental setting. The host monzogranite and MMEs from the Yangba pluton have zircon U–Pb ages of 207 ± 2 and 208 ± 2 Ma, respectively. The MMEs show igneous textures and contain abundant acicular apatite that suggests quenching process. Their trace element and evolved Sr–Nd isotopic compositions [(87Sr/86Sr)i = 0.707069–0.707138, and eNd(t) = −6.5] indicate an origin from SCLM. Some zircon grains from the MMEs have positive eHf(t) values of 2.3–8.2 with single-stage Hf model ages of 531–764 Ma. Thus, the MMEs would be derived from partial melts of the Neoproterozoic SCLM that formed during rift magmatism in response to breakup of supercontinent Rodinia, and experience subsequent fractional crystallization and magma mixing process. The host monzogranite exhibits typical geochemical characteristics of adakite, i.e., high La/Yb and Sr/Y ratios, low contents of Y (9.5–14.5 ppm) and Yb, no significant Eu anomalies (Eu/Eu* = 0.81–0.90), suggesting that garnet was stable in their source during partial melting. Its evolved Sr–Nd isotopic compositions [(87Sr/86Sr)i = 0.7041–0.7061, and eNd(t) = −3.1 to −4.3] and high contents of K2O (3.22–3.84%) and Th (13.7–19.0 ppm) clearly indicate an origin from the continental crust. In addition, its high Mg# (51–55), Cr and Ni contents may result from mixing with the SCLM-derived mafic magma. Most of the zircon grains from the adakitic monzogranite show negative eHf(t) values of −9.4 to −0.1 with two-stage Hf model ages of 1,043–1,517 Ma; some zircon grains display positive eHf(t) of 0.1–3.9 with single-stage Hf ages of 704–856 Ma. These indicate that the source region of adakitic monzogranite contains the Neoproterozoic juvenile crust that has the positive eHf(t) values in the Triassic. Thus, the high-Mg adakitic granites in the intracontinental setting would form by mixing between the crustal-derived adakitic magma and the SCLM-derived mafic magma. The mafic and adakitic magmas were generated coevally at Late Triassic, temporally consistent with the exhumation of deeply subducted continental crust in the northern margin of the South China Block. This bimodal magmatism postdates slab breakoff at mantle depths and therefore is suggested as a geodynamic response to lithospheric extension subsequent to the continental collision between the South China and North China Blocks.

Triassic granites in the Qinling orogen of central China provide insights into regional tectonomagmatic events and tectonic evolution. Zircon LA-ICP-MS U-Pb dating shows that the Yangba, Xichahe, Wulong, and Guangtoushan plutons have magmatic crystallization ages of 209 ± 2 Ma, 212 ± 2 Ma, and 208 ± 2 Ma, respectively, slightly younger than the time of collision between the Yangtze and North China cratons (242 Ma). Major- and trace-element geochemistry indicate that the granitoids have adakitic signatures, suggesting that they were generated by partial melting of a thickened lower crust. Geochemistry and petrology of mafic microgranular enclaves in some of the plutons indicate that they were derived from partial melting of the subcontinental lithospheric mantle (SCLM) and are genetically related to the host adakitic granites. We proposed that slab-breakoff explains the spatial, age and geochemistry characters of Triassic magmatism in the Qinling orogen. In summary, Triassic collision between the Yangtze a...

The Xichahe tonalite emplaced into the Proterozoic Foping metamorphic complex, south Qinling Mountains, central China, has been dated at 213.6 ± 2.2 Ma using the LA-ICP MS zircon U-Pb method, indicating that it is post-orogenic (≤242 ± 21 Ma). With the exception of higher Mg# (52.94-67.59) values, the tonalite has compositional similarities to high-silica adakites from suprasubduction-zone tectonic settings. Chondrite-normalized rare-earth element patterns of the tonalite are characterized by high (La/Yb)N ratios and concave-upward shapes of HREE, and without a significant Eu anomaly (δEu = 0.65-1.10). In conjunction with high Ba (877.13-1963.52 ppm) and Sr (820.76-1252.75 ppm), low Y (10.58-18.30 ppm) and HREE, e.g., Yb = 0.79-1.51 ppm), trace elements, and REE patterns suggest that the tonalite magma protolith was most likely a feldsparpoor, garnet ± amphibole-rich eclogite assemblage. Isotopic values of 87Sr/86Sr = 0.7065-0.7069, I sr = 0.7054-0.7064, 143Nd/144Nd = 0.5123-0.5124, ∊Nd(t) = -1.52 to -3.6...

The Dongjiahe ophiolite complex occurring in the western Bikou terrane that is composed chiefly of serpentinite, listwanitizational peridotite, gabbro, cumulus gabbro, and sub-alkaline meta-basalt, pos-sesses a rock association of typical ophiolite sequence. The metaperidotite is depleted in light rare earth element (LREE), whereas the gabbro and meta-basalt from the studied ophiolite sequence, gen-erated by the same parental magmas those have close affinity to the MORB (Mid-ocean ridge basalt), their REE and immobile elements patterns imply an ocean in the northern margin of the Yangtze plate during the Neoproterozoic period. The zircon LA-ICP-MS U-Pb dating for the gabbro yields a weighted mean age of 839.2±8.2Ma, suggesting that the basin occurred during the Neoproterozoic period.

The Madang Cenozoic sodic alkaline basalt occurred in the eastern margin of the Tibetan Plateau, where is a key tectonic transform region of Tibet, North China, and Yangtze blocks. The basalts are characterized by the variation in SiO2=42%–51%, Na2O/K2O>4, belonging to the sodic alkaline basalt series. The rocks are enriched in Ba, Th, Nb, Ta, relative to a slight depletion in K, Rb in the trace and rare earth element (REE) spider diagrams that are similar to the typical oceanic island alkaline basalt. The Sr-Nd-Pb isotopic compositions suggest that they are derived from a mixed mantle reservoir. The western Qinling-Songpan tectonic region was controlled by Tibet, North China and Yangtze blocks since Cenozoic, therefore, the region was in the stage of the substance converge from the mantle to upper crust, producing a mixed mantle reservoir in the studied area. The Madang basalts occurred in the specific tectonic background, they result from partial melting of a mixed asthenospheric mantle reservoir in the western Qinling-Songpan tectonic node.

Major and trace elements and Sr-Nd-Pb isotopic data are presented for the Late Paleogene to Neogene age (9.4-26.9 Ma) adakitic volcanic rocks from the northern Qiangtang region, Tibetan Plateau. Lacking Eu depletion, this group of rocks exhibits high SiO2 (>58%), Sr (>350 ppm) and La/Yb (>22) ratios, and low Y (

The aerobic oxidative cleavage of styrene C=C double bonds catalyzed by simple manganese porphyrin is reported. Under the catalysis of chloro(tetraphenylporphinato)manganese, the oxidative cleavage of the carbon-carbon double bond of the styrene with air yields benzaldehyde. Our results show that the oxidative cleavage and the epoxidation of the styrene double bond are the competition reactions in the styrene-manganese porphyrin-air system. The reaction temperature decided the product distribution. Under the conditions of 0.4 MPa air and 30 ppm of chloro(tetraphenylporphinato)manganese, the styrene conversion was 20.0% and the selectivity of benzaldehyde and styrene oxide was 81.7% and 12.7% respectively when the reaction temperature was 110°C. Styrene conversion was 92.5% and the selectivity of benzaldehyde and styrene oxide was 48.1% and 41.2% respectively when the reaction temperature was 120°C.

Neutral nickel(II) and palladium(II) complexes bearing β-ketoiminato ligand have been synthesized. The two complexes have been investigated as catalyst for the polymerization. Using methylaluminoxane (MAO) as a cocatalyst, both complexes produce vinyl-addition polynorbornenes, but palladium(II) complex displays much higher activity up to 8.0 × 107 g/(molPd h). Furthermore, both Ni(II) and Pd(II)/MAO system can efficiently copolymerize norbornene and 5-norbornene-2-yl acetate (NB-OCOMe) in moderate yields and in relatively high molecular weights. The analyses of the product by FTIR, 1H NMR and 13C NMR spectra give the verification of vinyl addition copolymer. The copolymers show narrow molecular weight distribution and good solubility in common organic solvents.

After we present some basic definitions and results on non-commutative residuated lattice and several kinds of filters of it, we extend the concept of fuzzy filter to non-commutative residuated lattice. We introduce and investigate the properties of fuzzy weak Boolean filters of residuated lattice and further characterize the fuzzy weak Boolean filters.

Ligands for a leukocyte adhesion molecule, L-selectin, are expressed not only in the specific vascular endothelium in lymph nodes and Peyer's patches but also in the extravascular tissues such as the brain white matter, choroid plexus and the kidney distal straight tubuli. However, the biological significance of these extravascular ligands is currently unknown. We now report the purification and characterization of a novel extravascular ligand for L-selectin in the kidney using a tubule-derived cell line, ACHN. Binding of L-selectin-IgG chimera (LEC-IgG) to the isolated ligand was specifically blocked with either (i) anti-L-selectin mAb, (ii) EDTA, (iii) fucoidan, (iv) chondroitin sulfate (CS) B or CS E, or (v) treatment with chondroitinases. Partial amino acid sequencing, Western blotting and immunoprecipitation analyses showed that a major ligand for L-selectin in ACHN cells is versican of 1600 kDa. Histochemical as well as biochemical analyses verified that a versican subspecies in the kidney was indeed reactive with L-selectin. Studies with cell lines including those derived from the kidney indicated that a certain glycoform and/or splice form of versican is reactive with L-selectin. Under pathological conditions such as those induced by unilateral ureteral obstruction, versican was shed from the distal straight tubuli and became localized in the adjacent vascular bundles around which a substantial leukocyte infiltration was concomitantly observed. Possible involvement of versican in leukocyte trafficking into the kidney under diseased conditions is discussed.

Ligands for the leukocyte adhesion molecule L-selectin are expressed not only in lymph node high endothelial venules (HEV) but also in the renal distal tubuli. Here we report that L-selectin-reactive molecules in the kidney are chondroitin sulfate and heparan sulfate proteoglycans of 500–1000 kDa, unlike those in HEV bearing sialyl Lewis X-like carbohydrates. Binding of L-selectin to these molecules was mediated by the lectin domain of L-selectin and required divalent cations. Binding was inhibited by chondroitinase and/or heparitinase but not sialidase. Thus, L-selectin can recognize chondroitin sulfate and heparan sulfate glycosaminoglycans structurally distinct from sialyl Lewis X-like carbohydrates.

In the present study we identified a 180 kDa molecule (p180) in rat lymph nodes (LN) apparently reactive with silkworm derived recombinant L-selectin (LEC-IgG) in a Ca2+-dependent manner. Analysis of amino acid sequence revealed that p180 has a strong homology to the macrophage mannose receptor (MMR), which was corroborated by the observation that p180 reacted with polyclonal anti-alveolar MMR antibody and mannosyl-BSA-agarose. In agreement with this notion, the binding of p180 to the silkworm LEC-IgG was inhibited by α-methyl-D-mannoside. However, in sharp contrast to its reactivity against the silkworm LEC-IgG, p180 failed to bind LEC-IgG produced by COS-7 cells, suggesting that p180 reacted with the silkworm LEC-IgG through the recognition of oligomannose-type oligosaccharides expressed on the silkworm products and that the lectin activity of L-selectin was not involved in the interaction. These results, together with the immunohistochemical studies showing that p180 was absent from the majority of high endothelial venules (HEV) but present in medullary macrophages, led us to conclude that p180 obtained from LN lysates by the use of the silkworm LEC-IgG is not a physiological ligand for L-selectin, warning against the use of recombinant proteins expressed in the baculovirus/silkworm expression system for the detection of carbohydrate ligands. Abbreviations: BSA, bovine serum albumin; EDTA, ethylenediamine-N,N,N,N-tetraacetic acid; ELISA, enzyme-linked imunosorbent assay; HEV, high endothelial venule; IgG, immunoglobulin G; LN, lymph node; NP-40, Nonidet P-40; PBS, phosphate-buffered saline; PMSF, phenylmethylsulfonyl fluoride; PVR, poliovirus receptor; SDS, sodium dodecylsulfate; SDS-PAGE, SDS-polyacrylamide gel electrophoresis; sLeX, sialyl Lewis X; WGA, wheat germ agglutinin

Requirements on encryption of web-based examination system were analyze, and different encryption technologies were used to meet the needs on three levels, including important data, core processing logic and some restricted functions. For important data, its confidentiality and integrity were realized. The core processing logic in ASP script was built in COM component. And some restricted functions were protected with hardware key. Encryption which protected data, code and function provided necessary safety for the web-based examination system. Keywords-web-based examination; data encryption; COM component; three-level encryption