The genomic origins of the Bronze Age Tarim Basin mummies.

The identity of the earliest inhabitants of Xinjiang, in the heart of Inner Asia, and the languages that they spoke have long been debated and remain contentious1. Here we present genomic data from 5 individuals dating to around 3000-2800 BC from the Dzungarian Basin and 13 individuals dating to around 2100-1700 BC from the Tarim Basin, representing the earliest yet discovered human remains from North and South Xinjiang, respectively. We find that the Early Bronze Age Dzungarian individuals exhibit a predominantly Afanasievo ancestry with an additional local contribution, and the Early-Middle Bronze Age Tarim individuals contain only a local ancestry. The Tarim individuals from the site of Xiaohe further exhibit strong evidence of milk proteins in their dental calculus, indicating a reliance on dairy pastoralism at the site since its founding. Our results do not support previous hypotheses for the origin of the Tarim mummies, who were argued to be Proto-Tocharian-speaking pastoralists descended from the Afanasievo1,2 or to have originated among the Bactria-Margiana Archaeological Complex3 or Inner Asian Mountain Corridor cultures4. Instead, although Tocharian may have been plausibly introduced to the Dzungarian Basin by Afanasievo migrants during the Early Bronze Age, we find that the earliest Tarim Basin cultures appear to have arisen from a genetically isolated local population that adopted neighbouring pastoralist and agriculturalist practices, which allowed them to settle and thrive along the shifting riverine oases of the Taklamakan Desert.

Fabrication of Hydroxy-Terminated Polybutadiene with Piezoelectric Property by Functionalized Branch Chain Modification.

Hydroxyl-terminated polybutadiene (HTPB)-based piezoelectric polymer (m-HTPB) is prepared for the first time by functionalized branch chain modification strategy. In the presence of HTPB with >98.8% cis-1,4 content, the C=C bond partly breaks down, and functionalized acetylferrocene groups are introduced to the cis-1,4 polybutadiene branch chain, retaining the high cis-1,4 content of HTPB. The whole process is conducted under mild conditions, without complicated manipulations. The microstructure and molecular weight of m-HTPB are characterized by Fourier-transform infrared (FTIR) spectra, 1H or 13C nuclear magnetic resonance spectrum (NMR), and gel permeation chromatography (GPC). The thermal properties of HTPB and m-HTPB are determined by differential scanning calorimetry (DSC). Electrochemical investigations reveal that m-HTPB exhibits higher conductance compared with HTPB. The m-HTPB flexible piezoelectric polymer is further used for in situ and real-time pressure monitoring. This simple and effective strategy provides a promising polymeric material for flexible piezoelectric sensors.

Detection of λ-cyhalothrin by a core-shell spherical SiO2-based surface thin fluorescent molecularly imprinted polymer film.

A fluorescent core-shell molecularly imprinted polymer based on the surface of SiO2 beads was synthesized and its application in the fluorescence detection of ultra-trace λ-cyhalothrin (LC) was investigated. The shell was prepared by copolymerization of acrylamide with allyl fluorescein in the presence of LC to form recognition sites. The experimental results showed that the thin fluorescent molecularly imprinted polymer (FMIP) film exhibited better selective recognition ability than fluorescent molecularly non-imprinted polymer (FNIP). A new nonlinear relationship between quenching rate and concentration was found in this work. In addition, the nonlinear relationship allowed a lower concentration range of 0-5.0 nM to be described by the Stern-Volmer equation with a correlation coefficient of 0.9929. The experiment results revealed that the SiO2@FMIP was satisfactory as a recognition element for determination of LC in soda water samples. Therefore this study demonstrated the potential of MIP for the recognition and detection of LC in food.

A core-shell surface magnetic molecularly imprinted polymers with fluorescence for λ-cyhalothrin selective recognition.

In this study, we report here a general protocol for making core-shell magnetic Fe3O4/SiO2-MPS/MIPs (MPS = 3-(methacryloxyl) propyl trimethoxysilane, MIPs = molecularly imprinted polymers, Fe3O4/SiO2-MPS as core, MIPs as shell) via a surface molecular imprinting technique for optical detection of trace λ-cyhalothrin. The fluorescent molecularly imprinted polymer shell was first prepared by copolymerization of acrylamide with a small quantity of allyl fluorescein in the presence of λ-cyhalothrin to form recognition sites without doping. The magnetic Fe3O4/SiO2-MPS/MIPs exhibited paramagnetism, high fluorescence intensity, and highly selective recognition. Using fluorescence quenching as a detecting tool, Fe3O4/SiO2-MPS/MIPs were successfully applied to selectively and sensitively detect λ-cyhalothrin, and a linear relationship could be obtained covering a wide concentration range of 0-50 nM with a correlation coefficient of 0.9962 described by the Stern-Volmer equation. The experimental results of practical detection revealed that magnetic Fe3O4/SiO2-MPS/MIPs as an attractive recognition element was satisfactory for determination of trace λ-cyhalothrin in honey samples. This study, therefore, demonstrated the potential of MIPs for detection of λ-cyhalothrin in food.

Selective separation of lambdacyhalothrin by porous/magnetic molecularly imprinted polymers prepared by Pickering emulsion polymerization.

Porous/magnetic molecularly imprinted polymers (PM-MIPs) were prepared by Pickering emulsion polymerization. The reaction was carried out in an oil/water emulsion using magnetic halloysite nanotubes as the stabilizer instead of a toxic surfactant. In the oil phase, the imprinting process was conducted by radical polymerization of functional and cross-linked monomers, and porogen chloroform generated steam under the high reaction temperature, which resulted in some pores decorated with easily accessible molecular binding sites within the as-made PM-MIPs. The characterization demonstrated that the PM-MIPs were porous and magnetic inorganic-polymer composite microparticles with magnetic sensitivity (M(s) = 0.7448 emu/g), thermal stability (below 473 K) and magnetic stability (over the pH range of 2.0-8.0). The PM-MIPs were used as a sorbent for the selective binding of lambdacyhalothrin (LC) and rapidly separated under an external magnetic field. The Freundlich isotherm model gave a good fit to the experimental data. The adsorption kinetics of the PM-MIPs was well described by pseudo-second-order kinetics, indicating that the chemical process could be the rate-limiting step in the adsorption of LC. The selective recognition experiments exhibited the outstanding selective adsorption effect of the PM-MIPs for target LC. Moreover, the PM-MIPs regeneration without significant loss in adsorption capacity was demonstrated by at least four repeated cycles.

Removal of cefalexin using yeast surface-imprinted polymer prepared by atom transfer radical polymerization.

The first use of yeast as a support in the molecular imprinting field combined with atom transfer radical polymerization was described. Then, the as-prepared molecularly imprinted polymers were characterized by Fourier transmission infrared spectrometry, scanning electron microscope, thermogravimetric analysis, and elemental analysis. The obtained imprinted polymers demonstrated elliptical-shaped particles with the thickness of imprinting layer of 0.63 µm. The batch mode experiments were adopted to investigate the adsorption equilibrium, kinetics, and selectivity. The kinetic properties of imprinted polymers were well described by the pseudo-second-order kinetic equation, indicating the chemical process was the rate-limiting step for the adsorption of cefalexin (CFX). The equilibrium data were well fitted by the Freundlich isotherm, and the multimolecular layers adsorption capacity of imprinted polymers was 34.07 mg g(-1) at 298 K. The selectivity analysis suggested that the imprinted polymers exhibited excellent selective recognition for CFX in the presence of other compounds with related structure. Finally, the analytical method based on the imprinted polymers extraction coupled with high-performance liquid chromatograph was successfully used for CFX analysis in spiked pork and water samples.

Molecularly imprinted polymer surfaces as solid-phase extraction sorbents for the extraction of 2-nitrophenol and isomers from environmental water.

The novel surface molecularly imprinted polymer (MIP) with 2-nitrophenol (2-NP) as the template has been prepared and used as the adsorbent for the solid-phase extraction (SPE). The selectivity of the polymer was checked toward several selected nitrophenols (NPs) such as 2-NP, 3-nitrophenol (3-NP), 4-nitrophenol (4-NP) and 2,4,6-trichlorophenol (2,4,6-TCP). Under the optimized conditions, high sensitivity (detection limits: 0.07-0.12 ng/mL) and good reproducibility of analytes (2.3-4.8% for four cycles) were achieved. Then, the method was applied for the analysis of selected phenols in spiked tap, lake and river water samples. High recoveries (>83.3%) for nitrophenols (NPs) were obtained, but lower recoveries (<63.4%) were achieved for 2,4,6-TCP. The method was found to be linear in the range of 1-300 ng/mL with correlation coefficients (R(2) ) greater than 0.99 and repeatability relative standard deviation (RSD) below 7.2% in all cases. For analysis of 120 mL water samples, the method detection limits (LODs) ranged from 0.10 to 0.22 ng/mL and the limit of quantification (LOQs) from 0.33 to 0.72 ng/mL. These results showed the suitability of the MIP-SPE method for the selective extraction of a group of structurally related isomeric compounds.

Selective recognition of 4-nitrophenol from aqueous solution by molecularly imprinted polymers with functionalized tetratitanate whisker composites as support.

Three kinds of molecularly imprinted polymers (MIPs) were obtained with surface molecular imprinting technique on functionalized potassium tetratitanate whisker (F-PTW). The results of adsorption experiments indicated that MIP prepared using PTW modified with N-(2-aminoethyl)-3-(trimethoxysilyl)propylamine (AAPTS) (F-PTW A) as support [MIP(1)] was superior to the other two polymers, then MIP(1) was selected to analyze the 4-nitrophenol (4-NP) adsorption process from aqueous solution in this study. AAPTS offered hydrophilic exterior that allowed to self-assemble with the template 4-NP through intermolecular interaction rather than based on the interactions between the functional monomers and template. Equilibrium adsorption data were analyzed by the Langmuir and Freundlich isotherm models at various temperatures. Kinetic properties were successfully investigated by pseudo-first-order model, pseudo-second-order model, intraparticle diffusion equation, initial adsorption rate, half-adsorption time. A diffusion-controlled process as the essential adsorption rate-controlling step was also proposed. The performance of such imprinted polymer was further demonstrated by high-performance liquid chromatography, and the results showed that the selectivity of MIP(1) exhibited higher affinity for template 4-NP over competitive phenolic compounds than that of non-imprinted polymer NIP(1). MIP(1) could be reused four times without significant loss in the adsorption capacity.

Novel Molecular Organic Framework Composite Molecularly Imprinted Nanofibrous Membranes with a Bioinspired Viscid Bead Structure for Selective Recognition and Separation of Atrazine.

In this work, novel atrazine (ATZ) molecularly imprinted nanofibrous membranes (A-MNMs) with a molecular organic framework (MOF)-based viscid bead structure were developed based on a natural spider-web-inspired strategy for selective separation of ATZ. Poly(vinylidene fluoride)/poly(vinyl alcohol) (PVDF/PVA) blended nanofibrous membranes as the basal membrane were synthesized by electrospinning technology combined with a chemical cross-linking procedure. The most critical design is that MOF nanocrystals as the matrix of the viscid bead structure were assembled on the PVDF/PVA blended nanofibrous membrane surface and the specific recognition sites were efficiently constructed on the surface and pores of the MOF-based viscid bead structure by a surface imprinting strategy. Significantly, the as-synthesized MOF-based viscid bead structure has an enhanced specific surface area, which helps to form abundant specific recognition sites in A-MNMs. Therefore, the A-MNMs with a spider-web-like structure presented an enhanced rebinding capacity (37.62 mg g-1) and permselectivity (permselectivity factors ß were 4.21 and 4.31) toward ATZ. Moreover, the A-MNMs display strong practicability in separation of ATZ from simulated environmental water samples. The presented work has shown tremendous potential for preparing natural spider-web-like molecularly imprinted membranes (MIMs) for selective separation of environment pollutants.

Ancient DNA analysis of human remains from the Upper Capital City of Kublai Khan.

Analysis of DNA from human archaeological remains is a powerful tool for reconstructing ancient events in human history. To help understand the origin of the inhabitants of Kublai Khan's Upper Capital in Inner Mongolia, we analyzed mitochondrial DNA (mtDNA) polymorphisms in 21 ancient individuals buried in the Zhenzishan cemetery of the Upper Capital. MtDNA coding and noncoding region polymorphisms identified in the ancient individuals were characteristic of the Asian mtDNA haplogroups A, B, N9a, C, D, Z, M7b, and M. Phylogenetic analysis of the ancient mtDNA sequences, and comparison with extant reference populations, revealed that the maternal lineages of the population buried in the Zhenzishan cemetery are of Asian origin and typical of present-day Han Chinese, despite the presence of typical European morphological features in several of the skeletons.

Synthesis, characterization, and adsorption performance of Pb(II)-imprinted polymer in nano-TiO2 matrix.

Surface ion-imprinted in combination with sol-gel process was applied to synthesis a new Pb(II)-imprinted polymer for selective separation and enrichment of trace PbO(II) from aqueous solution. The prepared material was characterized by using the infrared spectra, X-ray diffractometer, and scanning electron microscopy. The batch experiments were conducted to study the optimal adsorption condition of adsorption trace Pb(II) from aqueous solutions on Pb(II)-imprinted polymer. The equilibrium was achieved in approximately 4.0 h, and the experimental kinetic data were fitted the pseudo second-order model better. The maximum adsorption capacity was 22.7 mg/g, and the Langmuir equation fitted the adsorption isotherm data. The results of selectivity experiment showed that selectively adsorbed rate of Pb(II) on Pb(II)-imprinted polymer was higher than all other studied ions. Desorption conditions of the adsorbed Pb(II) from the Pb(II)-imprinted polymer were also studied in batch experiments. The prepared Pb(II)-imprinted polymer was shown to be promising for the separation and enrichment of trace Pb(II) from water samples. The adsorption and desorption mechanisms were proposed.

Polydopamine nanospheres loaded with l-cysteine-coated cadmium sulfide quantum dots as photoelectrochemical signal amplifier for PSA detection.

A sandwich-type photoelectrochemical (PEC) immunosensor was constructed for sensitive detection of prostate specific antigen (PSA). It was based on electrochemically reduced graphene oxide-TiO2 (ERGO-TiO2) as photoelectrochemical platform to immobilize capture antibody (Ab1). Then, quinone-rich polydopamine nanospheres (PDANS) loaded detection antibody (Ab2) and photocurrent signal label, l-cysteine-coated cadmium sulfide quantum dots (CdSQDs). ERGO-TiO2 displayed greatly improved photocurrent response to white light. CdSQDs conjugated with PDANS further amplified photocurrent signal because of the good conductivity of PDANS and ERGO. The increased photocurrent showed a linear correlation with PSA in the concentration range from 0.02 pg mL-1 to 200 ng mL-1 with the detection limit of 6.8 fg mL-1. It also revealed high selectivity and good stability.

Bioinspired synthesis of multiple-functional nanocomposite platform showing optically and thermally responsive affinity: Application to environmentally responsive separation membrane.

A tremendous effort has been made for the synthesis and multifunction of environmentally responsive and selective separation membranes. With the bioinspired design of polydopamine (pDA)-assisted inorganic film, we proposed a simple, yet efficient, thermo-responsive cell culture substrate. Herein, a Ag/TiO2/pDA-based nanocomposite structure was initially obtained, and the ciprofloxacin-imprinted membranes (MINCMs) with thermo-responsive recognition sites were then synthesized by using NIPAm as backbone monomer. The opto-thermally responsive molecularly imprinted membranes (OT-MIMs) were obtained through in situ reduction of HAuCl4 on membrane surfaces, Au nanoparticles were used as the light-heat converters. The light-switching principle was elaborated as well as the energy conversions that took place in this system. These conformational changes finally allowed the constructions or destructions of ciprofloxacin-imprinted sites. Due to the formation of the opto-thermally responsive ciprofloxacin-imprinted sites, rapid adsorption dynamics and opto-thermally responsive perm-selectivity toward templates were both achieved. Therefore, 58.65 mg/g of adsorption capacity and 4.91 of permselectivity factor from OT-MIMs were successfully obtained. Importantly, the as-designed bioinspired strategy led to a state-of-the-art design that was capable of reversibly controlling the flow rate (J) of ciprofloxacin from 12.10 to 4.93 mg min-1 cm-2 in less than a few minutes using light.

Amperometric hydrogen peroxide biosensor based on horseradish peroxidase-labeled nano-Au colloids immobilized on poly(2,6-pyridinedicarboxylic acid) layer by cysteamine.

A sensitive hydrogen peroxidase (H2O2) amperometric sensor based on horseradish peroxidase (HRP)-labeled nano-Au colloids has been proposed. Nano-Au colloids were immobilized by the thiol group of cysteamine, which was associated with the carboxyl groups of poly(2,6-pyridinedicarboxylic acid) (PPDA). With the aid of the hydroquinone, the sensor displayed excellent electrocatalytical response to the reduction of H2O2. Compared with the non-Au-colloid modified electrode, i.e., PPDA/HRP, the Au-colloid modified electrode exhibited better performance characteristics, including stability, reproducibility, sensitivity and accuracy. The biosensor shows a linear response to H2O2 in the range of 3.0 x 10(-7) - 2 x 10(-3) M. The detection limit was 1.0 x 10(-7) M.

Molecularly imprinted polymer microspheres for optical measurement of ultra trace nonfluorescent cyhalothrin in honey.

In this study, we first present a general protocol for making fluorescent molecularly imprinted polymer microspheres via precipitation polymerisation. We first prepared the fluorescent molecularly imprinted polymer microspheres upon copolymerisation of acrylamide with a small quantity of allyl fluorescein in the presence of cyhalothrin to form recognition sites without doping. The as-synthesised microspheres exhibited spherical shape, high fluorescence intensity and highly selective recognition. Under optical conditions, polymer microspheres were successfully applied to selectively and sensitively detect cyhalothrin, and a linear relationship could be obtained covering the lower concentration range of 0-1.0nM with a correlation coefficient of 0.9936 described by the Stern-Volmer equation. A lower limit of detection was found to be 0.004nM. The results of practical detection suggested that the developed method was satisfactory for determination of cyhalothrin in honey samples. This study therefore demonstrated the potential of molecularly imprinted polymers for detection of cyhalothrin in food.

Microporous Ni-doped TiO2 film photocatalyst by plasma electrolytic oxidation.

Ni-doped TiO2 film catalysts were prepared by a plasma electrolytic oxidation (PEO) method and were mainly characterized by means of SEM, EDS, XRD, XPS, and DRS, respectively. The effects of Ni doping on the structure, composition and optical absorption property of the film catalysts were investigated along with their inherent relationships. The results show that the film catalyst is composed of anatase and rutile TiO2 with microporous structure. Doping Ni changes the phase composition and the lattice parameters (interplanar crystal spacing and cell volume) of the films. The optical absorption range of TiO2 film gradually expands and shifts to the red with increasing dosages. Both direct and indirect transition band gaps of the TiO2 films are deduced consequently. Moreover, the photocatalytic activity of the film catalysts for splitting Na2S+Na2SO3 solution into H2 is enhanced by doping with an appropriate amount of Ni. The as-prepared TiO2 film catalyst doping with 10 g/L of Ni(Ac)2 presents the highest photocatalytic reducing activity.