A poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)-based electrochemical sensor for tert.-butylhydroquinone.

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a readily available copolymer that comes as an aqueous dispersion with good processability. A flexible voltammetric sensor for the widely used food stabilizer tert.-butylhydroquinone (TBHQ) was constructed by using a film of PEDOT:PSS. The electron transfer efficiency of the electrode was enhanced by doping with dimethyl sulfoxide (DMSO), and mass transport at the electrode-electrolyte interface was increased by adding the cationic surfactant cetyltrimethylammonium bromide (CTAB) which acts as a sorbent for TBHQ. SEM, AFM, XPS, UV - vis and electrochemical analysis were conducted to characterize the properties of the electrode. After optimization of the experimental conditions, the electrode operated at a working potential of 0.17 V (vs. SCE) has a linear response in the 0.5-200 µM TBHQ concentration range and a lower detection limit of 0.15 µM (at S/N = 3). It was applied for the determination of TBHQ in spiked real samples, and recoveries ranged between 96.85 and 103.41%. Graphical abstractSchematic representation of an electrochemical flexible electrode for the determination of tert.-butylhydroquinone based on the use of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate).

Self-assembled dielectric microsphere array enhanced Raman scattering for large-area and ultra-long working distance confocal detection.

Here we report enhanced confocal Raman detection with large-area and ultra-long working distance by capping dielectric microsphere array. Microspheres have been found to provide three channels for Raman scattering enhancement, including localized photonic nanojets, directional antenna effects, and whispering-gallery modes. The maximum enhancement ratio of Raman intensity is up to 14.6 using 4.94-µm-diameter polystyrene (PS) microspheres. Investigation on the directional antenna effect of microsphere reveals that the microsphere array confines electromagnetic (EM) waves to a narrow distribution with small divergent angles, by which the signal-to-noise ratio is retained and the offset of focal plane position from sample surface can be up to ± 7.5 mm. The present work reduces the requirement of focusing in confocal Raman detection and hence makes the large-area detection possible via rapid mapping. It opens up a simple approach for high-sensitivity Raman detection of 3D-structured surface.

A genetically modified broad-spectrum strain of Bacillus thuringiensis toxic against Holotrichia parallela, Anomala corpulenta and Holotrichia oblita.

Cry8Ea1 from Bacillus thuringiensis strain Bt185 has insecticidal activity against Holotrichia parallela. Cry8Ca2 from strain HBF-1 is effective against Anomala corpulenta. Cry8Ga1 from strain HBF-18 is toxic to H. oblita. Given the need to broaden the spectrum of B. thuringiensis, a broad-spectrum coleopteran active strain of B. thuringiensis, BIOT185, engineered to express multiple cry genes, including cry8Ea1, cry8Fa1 and cry8Ca2, was created by homologous recombination introducing the cry8Ca2 into the B. thuringiensis strain Bt185 by Liu et al. (Appl Microbiol Biotechnol 87:243-249, 2010). To further broaden the spectrum, an engineered B. thuringiensis strain BIOT1858G was constructed by introducing the recombinant plasmid pSTK-8G containing cry8Ga1 into the engineered B. thuringiensis strain BIOT185. PCR and Southern blotting demonstrated that the cry8Ga1 gene was transferred to the novel strain BIOT1858G. SDS-PAGE and RT-PCR confirmed the normal expression and transcription of the cry8Ga1 gene in addition to the cry8Ea1, cry8Fa1 and cry8Ca2 genes. Bioassays of BIOT1858G indicated that the recombinant strain broadened the spectrum against not only H. parallela susceptible to the Cry8E protein and A. corpulenta susceptible to the Cry8C protein but also H. oblita susceptible to the Cry8G protein. The pesticide could also decrease the cost of production and field labor.

[Subtype classification of ceftriaxone sodium and its influence on the quality of product].

Powder X-ray diffraction (PXRD) technology combined with cluster analysis method was used to classify 75 batches of crystalline ceftriaxone sodium into subtypes, the crystalline characteristics of each subtype were measured with scanning electron microscope (SEM). By comparing some parameters of these subtypes correlated to crystallization process of ceftriaxone sodium, such as salification rate, water content in different subtypes, as well as by studying different lattice stabilities, different compatibilities with rubber closures during accelerated stability tests, the key point to improve the quality of domestic ceftriaxone sodium was disclosed. The results of this paper indicated that the fine structure of the products could be controlled well by improving the salification and crystallization process. As a result, the subtype II of ceftriaxone sodium with high stability can be produced.

Band-like transport in solution-processed perylene diimide dianion films with high Hall mobility.

It is crucial to prepare high-mobility organic polycrystalline film through solution processing. However, the delocalized carrier transport of polycrystalline films in organic semiconductors has rarely been investigated through Hall-effect measurement. This study presents a strategy for building strong intermolecular interactions to fabricate solution-crystallized p-type perylene diimide (PDI) dianion films with a closer intermolecular π-π stacking distance of 3.25 Å. The highly delocalized carriers enable a competitive Hall mobility of 3 cm2 V-1 s-1, comparable to that of the reported high-mobility organic single crystals. The PDI dianion films exhibit a high electrical conductivity of 17 S cm-1 and typical band-like transport, as evidenced by the negative temperature linear coefficient of mobility proportional to T-3/2. This work demonstrates that, as the intermolecular π-π interactions become strong enough, they will display high mobility and conductivity, providing a new approach to developing high-mobility organic semiconductor materials.

Chemical doping of unsubstituted perylene diimide to create radical anions with enhanced stability and tunable photothermal conversion efficiency.

N-doping of perylene diimides (PDIs) to create stable radical anions is significant for harvesting photothermal energy due to their intensive absorption in the near-infrared (NIR) region and non-fluorescence. In this work, a facile and straightforward method has been developed to control the doping of perylene diimide to create radical anions using organic polymer polyethyleneimine (PEI) as a dopant. It was demonstrated that PEI is an effective polymer-reducing agent for the n-doping of PDI toward the controllable generation of radical anions. In addition to the doping process, PEI could suppress the self-assembly aggregation and improve the stability of PDI radical anions. Tunable NIR photothermal conversion efficiency (maximum 47.9%) was also obtained from the radical-anion-rich PDI-PEI composites. This research provides a new strategy to tune the doping level of unsubstituted semiconductor molecules for varying yields of radical anions, suppressing aggregation, improving stability, and obtaining the highest radical anion-based performance.

SlMBP22 overexpression in tomato affects flower morphology and fruit development.

MADS-domain transcription factors have been identified as key regulators involved in proper flower and fruit development in angiosperms. As members of the MADS-box subfamily, Bsister (Bs) genes have been observed to play an important role during the evolution of the reproductive organs in seed plants. However, their effects on reproductive development in fruit crops, such as tomato (Solanum lycopersicum), remain unclear. Here, we found that SlMBP22 overexpression (SlMBP22-OE) resulted in considerable alterations in floral morphology and affected the expression levels of several floral homeotic genes. Further analysis by yeast two-hybrid (Y2H) and bimolecular fluorescence complementation (BiFC) assays demonstrated that SlMBP22 forms dimers with class A protein MACROCALYX (MC) and SEPALLATA (SEP) floral homeotic proteins TM5 and TM29, respectively. In addition, pollen viability and cross-fertilization assays suggested that the defect in female reproductive development was responsible for the infertility phenotype observed in the strong overexpression transgenic plants. Transgenic fruits with mild overexpression exhibited reduced size as a result of reduced cell expansion, rather than impaired cell division. Additionally, SlMBP22 overexpression in tomato not only affected proanthocyanidin (PA) accumulation but also altered seed dormancy. Taken together, these findings may provide new insights into the knowledge of Bs MADS-box genes in flower and fruit development in tomato.

Room-Temperature Ferromagnetism in Perylene Diimide Organic Semiconductor.

The development of pure organic magnets with high Curie temperatures remains a challenging task in material science. Introducing high-density free radicals to strongly interacting organic molecules may be an effective method to this end. In this study, a solvothermal approach with excess hydrazine hydrate is used to concurrently reduce and dissolve rigid-backbone perylene diimide (PDI) crystallites into the soluble dianion species with a remarkably high reduction potential. The as-prepared PDI powders comprising radical anion aggregates are fabricated by a subsequent self-assembly and spontaneous oxidation process. The results of magnetic measurements show that the PDI powders exhibit room-temperature ferromagnetism and a Curie temperature higher than 400 K, with a vast saturation magnetization that reaches ≈1.2 emu g-1 . Elemental analysis along with the diamagnetic signal of the ablated residue are used to rule out the possibility that the magnetism is due to metal contamination. The findings suggest that the long-range ferromagnetic ordering can survive at room-temperature in organic semiconductors, and offers a new optional way to create room-temperature magnetic semiconductors.

A training set selection strategy for a universal near-infrared quantitative model.

The purpose of this article is to propose an empirical solution to the problem of how many clusters of complex samples should be selected to construct the training set for a universal near infrared quantitative model based on the Naes method. The sample spectra were hierarchically classified into clusters by Ward's algorithm and Euclidean distance. If the sample spectra were classified into two clusters, the 1/50 of the largest Heterogeneity value in the cluster with larger variation was set as the threshold to determine the total number of clusters. One sample was then randomly selected from each cluster to construct the training set, and the number of samples in training set equaled the number of clusters. In this study, 98 batches of rifampicin capsules with API contents ranging from 50.1% to 99.4% were studied with this strategy. The root mean square errors of cross validation and prediction were 2.54% and 2.31% for the model for rifampicin capsules, respectively. Then, we evaluated this model in terms of outlier diagnostics, accuracy, precision, and robustness. We also used the strategy of training set sample selection to revalidate the models for cefradine capsules, roxithromycin tablets, and erythromycin ethylsuccinate tablets, and the results were satisfactory. In conclusion, all results showed that this training set sample selection strategy assisted in the quick and accurate construction of quantitative models using near-infrared spectroscopy.

[Effect of thunder-fire moxibustion combined with electroacupuncture on urodynamics in patients with neurogenic bladder after spinal cord injury].

OBJECTIVE: To investigate the effect of electroacupuncture combined with thunder-fire moxibustion on urodynamics in patients with neurogenic bladder (NB) after spinal cord injury(SCI). METHODS: A total of 60 patients with NB after SCI were divided into control group and observation group using a random number table, with 30 patients in each group. Bladder management protocol was performed for both groups. The patients in the control group were given electroacupuncture at Shangliao (BL31), Zhongliao (BL33), Xialiao (BL34), and Ciliao (BL32) at both sides, and those in the observation group were given thunder-fire moxibustion as mild-warm moxibustion at Yaoyangguan (GV3), Mingmen (CV4), Qihai (CV6), Guanyuan (CV4), and Zhongji (CV3) in addition to the treatment in the control group; electroacupuncture or moxibustion was performed for 20 min each time, once a day, with 10 times as one course of treatment, and both groups were treated for 3 courses. Number of times of voluntary urination, maximum single urine volume, and number of times of urethral catheterization were recorded at 3 d before and after treatment; maximum urinary flow rate during urination, maximum bladder capacity during urination, bladder pressure during the bladder filling period, and residual urine volume were recorded before and after treatment, and bladder compliance was calculated; clinical outcome was evaluated for both groups. RESULTS: After treatment, both groups had significant reductions in the numbers of times of urination and urethral catheterization (P<0.05) and a significant increase in maximum single urine volume (P<0.05), and the observation group had significantly better results than the control group (P<0.05). After treatment, both groups had significant reductions in residual urine volume and bladder pressure during the bladder filling period, and the observation group had significantly greater reductions than the control group (P<0.05); both groups had significant increases in bladder compliance, maximum bladder capacity during urination, and maximum urinary flow rate during urination, and the observation group had significantly higher values than the control group (P<0.05). The observation group had a significantly higher response rate than the control group ï¼»90.00% (27/30) vs 63.33% (19/30), P<0.05ï¼½. CONCLUSION: Thunder-fire moxibustion combined with electroacupuncture can effectively improve bladder urodynamics and has a marked clinical effect in patients with NB after SCI.

Wearable Thermoelectric Materials and Devices for Self-Powered Electronic Systems.

The emergence of artificial intelligence and the Internet of Things has led to a growing demand for wearable and maintenance-free power sources. The continual push toward lower operating voltages and power consumption in modern integrated circuits has made the development of devices powered by body heat finally feasible. In this context, thermoelectric (TE) materials have emerged as promising candidates for the effective conversion of body heat into electricity to power wearable devices without being limited by environmental conditions. Driven by rapid advances in processing technology and the performance of TE materials over the past two decades, wearable thermoelectric generators (WTEGs) have gradually become more flexible and stretchable so that they can be used on complex and dynamic surfaces. In this review, the functional materials, processing techniques, and strategies for the device design of different types of WTEGs are comprehensively covered. Wearable self-powered systems based on WTEGs are summarized, including multi-function TE modules, hybrid energy harvesting, and all-in-one energy devices. Challenges in organic TE materials, interfacial engineering, and assessments of device performance are discussed, and suggestions for future developments in the area are provided. This review will promote the rapid implementation of wearable TE materials and devices in self-powered electronic systems.

Anthocyanin Accumulation and Transcriptional Regulation of Anthocyanin Biosynthesis in Purple Pepper.

Pepper (Capsicum annuum) is among the important horticultural crops with economic value, and more and more colorful varieties have been marketed. The purple pepper is becoming increasingly popular on the consumer market because of its anthocyanin richness. Here, two cyanidin-based anthocyanins were separated and identified from peels of purple cultivars by HPLC-LC-MS. To study the molecular mechanism of anthocyanin accumulation, the differential expression of genes related to anthocyanin biosynthesis was examined by qRT-PCR and RNA-Seq in peel from green and purple cultivars. These results show that CaANT1, CaANT2, CaAN1, and CaTTG1 are involved in anthocyanin accumulation of pepper. Further investigation suggested that CaANT1, CaANT2, CaAN1, and CaTTG1 can activate anthocyanin accumulation via forming a new MMBW transcription complex.

Fused Heterocyclic Molecule-Functionalized N-Doped Reduced Graphene Oxide by Non-Covalent Bonds for High-Performance Supercapacitors.

Indole molecules with fused heteroaromatic structures can be adsorbed on the N-doped graphene surface through the π-π interaction. Therefore, the indole-functionalized N-doped graphene (InFGN) with mesopores is successfully fabricated by a simple hydrothermal method and subsequent vacuum freeze-drying process. The microstructure, thickness, element composition, pore structure, and electrochemical performance of InFGN are analyzed via SEM, TEM, AFM, BET, UV-vis, FT-IR, XPS, Raman, XRD, and electrochemical technologies. Since the five-membered aromatic heterocycles are electron-rich, the indole molecules fixed on the N-doped graphene surface can repair the structural defects generated by N doping. Electrochemical measurements show that the InFGN electrode highlights an excellent capacitance of 622.3 F g-1 at 2 A g-1 and a durable cycling life of 100.5% after 5000 charging/discharging cycle times. For further practical application, a symmetric device has been assembled by using InFGN electrodes, which realizes high-power and energy densities (18.8-20.6 Wh kg-1 at 800-8000 W kg-1). This study provides a shortcut for building green supercapacitors with enhanced energy storage performance.

Roles of Polyethylenimine Ethoxylated in Efficiently Tuning the Thermoelectric Performance of Poly(3,4-ethylenedioxythiophene)-Rich Nanocrystal Films.

The regulation of oxidation levels is of great importance as an efficient way to optimize the thermoelectric (TE) performance of conducting polymers. Many efforts have been devoted to the acquisition of a high TE performance for poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) by oxidation/reduction post treatment to achieve an effective compromise. However, a strong oxidant/reductant is usually employed to tune the TE performance of PEDOT:PSS with high electrical conductivity (σ) and Seebeck coefficient ( S), and it also presents a number of operational challenges depending on a fast reaction rate. Herein, nontoxic polyethylenimine ethoxylated (PEIE) served as a reductant to successfully realize an enhanced S for PEDOT:PSS, besides playing a significant anion-blocking role in enabling the efficient modulation of the oxidation level by sulfuric acid (H2SO4) with a longer operating time. Eventually, a good PEDOT-rich nanocrystal is achieved by a sequential dipping process in PEIE/ethylene glycol and H2SO4 solutions. The large TE power factor of 133 µW m-1 K-2 can be ascribed to the good formation of PEDOT-rich nanocrystals and an effective compromise between σ and S of PEDOT:PSS films. A mechanism was elucidated for the efficient regulation of σ and S enabling high performance of organic TE materials.

Efficient DMSO-Vapor Annealing for Enhancing Thermoelectric Performance of PEDOT:PSS-Based Aerogel.

Conducting polymer-based composite aerogel film is desired to be used as thermoelectric (TE) materials due to its good flexibility and ultralow thermal conductivity. Here, we proposed the simple freeze drying method to fabricate free-standing poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS)-based aerogel films without any crosslinker addition. The evolutions of morphology and TE performance were systemically investigated with various organic solvent addition. Furthermore, a series of the PEDOT:PSS/tellurium nanowires (Te-NWs) composite aerogel films was prepared, and the relationship between the structure and the charge-transport mechanism of the binary complex system was explored based on series and parallel models. Finally, an efficient dimethyl sulfoxide-vapor annealing was employed to further optimize the TE performance of PEDOT:PSS/Te-NWs composite aerogel films. The ZT value was estimated to be 2.0 × 10-2 at room temperature. On the basis of the flexibility and highly enhanced TE performance, a prototype TE generator consisting of p-type PEDOT:PSS/Te-NWs aerogel films and n-type carbon nanotube fibers as legs has been fabricated with an acceptable output power of 1.28 µW at a temperature gradient of 60 K, which could be potentially applied in wearable electronics.

Isolation, characterization and genome sequencing of phage MZTP02 from Bacillus thuringiensis MZ1.

A lysogenic phage, MZTP02, was produced via induction by mitomycin C from Bacillus thuringiensis (B. thuringiensis) strain MZ1. Plaques were about 3 mm in diameter with a small inner zone consisting of new B. thuringiensis colonies. Electron microscopic analysis showed that MZTP02 had a long tail (220 nm x 18 nm) and an icosahedral head (82 nm x 85 nm). MZTP02 was insensitive to organic solvents such as chloroform, and infected six B. thuringiensis strains. Its complete genome contained 15,717 base pairs (bp) with 37.55% G + C content. Two inverted terminal repeats consisting of 40 bp were 65% identical. Twenty putative open reading frames (ORFs) were found in the MZTP02 genome, and nine predicted proteins, including two terminase subunits, portal protein, minor head protein, scaffold protein, two putative membrane proteins, tail component, and minor structural protein, showed similarity to other phage proteins. But six ORFs were unique. The presence of a terminal protein at the 5'-terminus was demonstrated using proteinase K, lambda exonuclease and E. coli exonuclease III to digest the genome DNA. A TMP phylogenetic tree was constructed based on amino acid sequences from ten phages.

[Cloning, prokaryotic expression and functional analysis of pep gene from Bacillus thuringiensis lysogenic bacteriophage].

OBJECTIVE: Random outbreak of lysogenic bacteriophage from Bacillus thuringiensis was very harmful to the production of Bacillus thuringiensis insecticide. We clarified the background of the phage from Bacillus thuringiensis MZ1 at the molecular level to solve the problem of random outbreak. METHODS: After the strain MZ1 from a company in Meixian County of Guangdong Province was induced, we obtained phage particles. Then phage DNA was extracted and pep gene was cloned, expressed and analyzed. RESULTS: We obtained a lysogenic bacteriophage MZTP01with clear plaque and 1 mm diameter. Fragment D with 2362bp (Genebank No. AY639599) was obtained after the phage DNA hydrolyzed by HindIII/EcoR I. Among fragment D, the pep gene with molecular weight of 47 kDa and length of 1101bp was cloned and expressed. Recombinant M15 (pQE30pep) was built and overexpressed in Escherichia coli with a 47kDa clear band. At the same place a clear band was observed by Western blot. Judging from the time course expression, we could conclude that PEP protein produced at 1 hour after induction and then increased gradually. PEP protein was mainly in the form of inclusion body in the recombinant and slowed the growth speed of host. Homologous comparison of PEP protein from phage MZTP01 with other PEPs from BLAST were that phage MZTP01 PEP protein had 100% homologe with that of Escherichia coli K12, and most of others took the similarity in the range between 37%-84%. CONCLUSION: PEP protein had ability to hydrolyze casein with the enzyme activity of 0.3 mg/ml trypsin. PEP protein may be a kind of trypsin.

Highly Conductive Hydrogel Polymer Fibers toward Promising Wearable Thermoelectric Energy Harvesting.

The requirement of a portable electron is functioning as a driving force for a wearable energy instrument. Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), as one of the most promising organic electron materials, has been widely studied in energy conversion devices. However, the efforts for PEDOT:PSS fibers are insufficient to boost the development of wearable thermoelectric energy harvesting. Here, a highly conductive p-type PEDOT:PSS fiber was produced by gelation process, which was 3 orders of magnitude higher than that of previous hydrogel fibers. Surprisingly, a post-treatment with organic solvents such as ethylene glycol and dimethyl sulfoxide tripled their electrical conductivity with an only 5% decreased Seebeck coefficient, consequently leading to an optimized thermoelectric power factor. Furthermore, we assembled a p-n-type thermoelectric device connecting five pairs of p-type PEDOT:PSS fibers and n-type carbon nanotube fibers. This fiber-based device displayed an acceptable output voltage of 20.7 mV and a power density of 481.2 µW·cm-2 with a temperature difference of ∼60 K, which might pave the way for the development of organic thermoelectric fibers for wearable energy harvesting.

Assessing the biological activities of xanthone derivatives from Swertia macrosperma C.B. Clark.

The anti-microbial and anti-oxidant effects of xanthones extract from Swertia macrosperma C.B. Clark were investigated using extracts from whole plant and partitioned by petroleum ether, ethyl acetate and n-butanol, respectively. Anti-microbial and anti-oxidant activities were detected among different fractions. High-performance liquid chromatography was performed to separate and purify the elutions. The compounds were elucidated by 1H, 13C NMR and LCMS. The ethyl acetate extract showed maximum inhibitory activity in fungal organisms and Gram-positive bacteria, and had the highest anti-oxidant capacity. Eight xanthones were isolated in ethyl acetate fraction from S. macrosperma. Moreover, compounds IV-VI and VIII were isolated from the plant for the first time, and compound VII had the strongest anti-oxidant effect.