A series of ionic liquids (ILs) based on nitrile-functionalized imidazolium, pyridinium, and quaternary ammonium as cations and chlorides and tetrafluoroborate, hexafluorophosphate, dicyanamide, and bis(trifluoromethanesulfonyl)imide as anions have been prepared and characterized. The physicochemical properties such as spectroscopic, thermal, solubility, surface, electrochemical, tribological, and toxic properties were comparatively studied. The results showed that the incorporation of a CN group to cations could result in remarkable changes in these properties. The reason resulting in such remarkable differences in the properties may be attributed to the conformational changes in the imidazolium groups caused by the interaction between the CN group with other neighboring cations or anions and the enhancement in hydrogen-bonding interactions due to the incorporation of a CN group.

Most cyanobacteria harvest light with large antenna complexes called phycobilisomes. The diversity of their constituting phycobiliproteins contributes to optimize the photosynthetic capacity of these microorganisms. Phycobiliprotein biosynthesis, which involves several post-translational modifications including covalent attachment of the linear tetrapyrrole chromophores (phycobilins) to apoproteins, begins to be well understood. However, the biosynthetic pathway to the blue-greenabsorbing phycourobilin ( max ϳ 495 nm) remained unknown, although it is the major phycobilin of cyanobacteria living in oceanic areas where blue light penetrates deeply into the water column. We describe a unique trichromatic phycocyanin, R-PC V, extracted from phycobilisomes of Synechococcus sp. strain WH8102. It is evolutionarily remarkable as the only chromoprotein known so far that absorbs the whole wavelength range between 450 and 650 nm. R-PC V carries a phycourobilin chromophore on its ␣-subunit, and this can be considered an extreme case of adaptation to blue-green light. We also discovered the enzyme, RpcG, responsible for its biosynthesis. This monomeric enzyme catalyzes binding of the green-absorbing phycoerythrobilin at cysteine 84 with concomitant isomerization to phycourobilin. This reaction is analogous to formation of the orange-absorbing phycoviolobilin from the red-absorbing phycocyanobilin that is catalyzed by the lyase-isomerase PecE/F in some freshwater cyanobacteria. The fusion protein, RpcG, and the heterodimeric PecE/F are mutually interchangeable in a heterologous expression system in Escherichia coli. The novel R-PC V likely optimizes rod-core energy transfer in phycobilisomes and thereby adaptation of a major phytoplankton group to the blue-green light prevailing in oceanic waters.To perform photosynthesis, the main energetic basis for life on earth, phototrophic organisms have to cope with large spatial and temporal variations of light conditions. A major evolutionary step in meeting this challenge was the development of light-harvesting complexes, the most variable part of the photosynthetic apparatus (1). By binding a large number of chromophores, these antennas can considerably enhance the photon absorption capacity of reaction centers that are responsible for the conversion of solar energy into chemical energy. Pigmented proteins associated with light-harvesting complexes also fill (at least partially) the large gap between the absorption bands of reaction center chlorophylls (e.g. ϳ440 and 680 nm for chlorophyll a found in most oxygenic organisms). Antennas also transport the excitons with minimal loss and transduce high energy excitons into the low energy ones required by the reaction centers (1, 2). They do not only vary among the different organisms but also with time within individual organisms, thereby providing the flexibility needed by the photosynthetic apparatus to work efficiently under varying ambient conditions. Cyanobacteria, which contribute a substantial fraction of global photosynthesis (...

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We show that the microstructures and phase transition behavior of vinylidene fluoride−trifluoroethylene−chlorofluoroethylene terpolymer, P(VDF−TrFE−CFE), with composition of 61.5/30.3/8.2 mol %, can be varied dramatically via different processing conditions. In the well-annealed sample, the polymer exhibits typical relaxor ferroelectric behavior with the nonpolar crystalline phase having a chain structure of random sequence of TT/TG/TG‘ conformations. In contrast, by lowering the crystallization temperature in the solution-cast films, the polar crystal phase with all-trans (T m >4) planar zigzag conformation (similar to the ferroelectric phase in the corresponding copolymer) can appear or even become a dominating phase. Four types of transitions can be detected in this terpolymer, besides the crystal melting, the glass transition in amorphous region, and the transition between the ferroelectric-like and paraelectric crystals (30−90 °C), an additional transition appears near 10 °C which can be attributed to the crystalline domains with all-trans sequence randomly disrupted by defects, and the coherence length of these domains is estimated to be less than 4.7 nm (polar nanodomains). The large dielectric response of the terpolymer comes from the two crystalline phases:  the ferroelectric-like crystals and polar nanodomains. The former is responsible for the frequency-independent dielectric maxima while the latter generates the strong frequency dependence in the dielectric spectra, a typical feature of relaxor ferroelectrics, which we suggest to come from the short-range molecular motion in the polar nanodomains.

Diverse immune cells in the tumor microenvironment form a complex ecosystem, but our knowledge of their heterogeneity and dynamics within hepatocellular carcinoma (HCC) still remains limited. To assess the plasticity and phenotypes of immune cells within HBV/HCV-related HCC microenvironment at single-cell level, we performed single-cell RNA sequencing on 41,698 immune cells from seven pairs of HBV/HCV-related HCC tumors and non-tumor liver tissues. We combined bio-informatic analyses, flow cytometry, and multiplex immunohistochemistry to assess the heterogeneity of different immune cell subsets in functional characteristics, transcriptional regulation, phenotypic switching, and interactions. We identified 29 immune cell subsets of myeloid cells, NK cells, and lymphocytes with unique transcriptomic profiles in HCC. A highly complex immunological network was shaped by diverse immune cell subsets that can transit among different states and mutually interact. Notably, we identified a subset of M2 macrophage with high expression of CCL18 and transcription factor CREM that was enriched in advanced HCC patients, and potentially participated in tumor progression. We also detected a new subset of activated CD8+ T cells highly expressing XCL1 that correlated with better patient survival rates. Meanwhile, distinct transcriptomic signatures, cytotoxic phenotypes, and evolution trajectory of effector CD8+ T cells from early-stage to advanced HCC were also identified. Our study provides insight into the immune microenvironment in HBV/HCV-related HCC and highlights novel macrophage and T-cell subsets that could be further exploited in future immunotherapy.

BackgroundPatient adherence is an important issue for health service providers and health researchers. However, the knowledge structure of diverse research on treatment adherence is unclear. This study used co-word analysis and social network analysis techniques to analyze research literature on adherence, and to show their knowledge structure and evolution over time.MethodsPublished scientific papers about treatment adherence were retrieved from Web of Science (2000 to May 2011). A total of 2308 relevant articles were included: 788 articles published in 2000–2005 and 1520 articles published in 2006–2011. The keywords of each article were extracted by using the software Biblexcel, and the synonym and isogenous words were merged manually. The frequency of keywords and their co-occurrence frequency were counted. High frequency keywords were selected to yield the co-words matrix. Finally the decomposition maps were used to comb the complex knowledge structures.ResultsResearch themes were more general in the first period (2000 to 2005), and more extensive with many more new terms in the second period (2006 to 2011). Research on adherence has covered more and more diseases, populations and methods, but other diseases/conditions are not as hot as HIV/AIDS and have not become specialty themes/sub-directions. Most studies originated from the United States.ConclusionThe dynamic of this field is mainly divergent, with increasing number of new sub-directions of research. Future research is required to investigate specific directions and converge as well to construct a general paradigm in this field.

Genes all5292 (cpcS2) and alr0617 (cpcS1) in the cyanobacterium Nostoc PCC7120 are homologous to the biliprotein lyase cpcS, and genes all5339 (cpcT1) and alr0647 (cpcT2) are homologous to the lyase cpcT. The functions of the encoded proteins were screened in vitro and in a heterologous Escherichia coli system with plasmids conferring biosynthesis of the phycocyanobilin chromophore and of the acceptor proteins ␤-phycoerythrocyanin (PecB) or ␤-phycocyanin (CpcB). CpcT1 is a regioselective biliprotein lyase attaching phycocyanobilin exclusively to cysteine ␤155 but does not discriminate between CpcB and PecB. The in vitro reconstitutions required no cofactors, and kinetic constants were determined for CpcT1 under in vitro conditions. No lyase activity was found for the lyase homologues CpcS2 and CpcT2, but complexes are formed in vitro between CpcT1 and CpcS1, CpcT2, or PecE (subunit of phycoviolobilin:␣-phycoerythrocyanin isomerase lyase). The genes coding the inactive homologues, cpcS2 and cpcT2, are transcribed in N-starved Nostoc. In sequential binding experiments with CpcT1 and CpcS1, a chromophore at cysteine 84 inhibited the subsequent attachment to cysteine 155, whereas the inverse sequence generates subunits carrying both chromophores.

SYNOPSIS Big Data now pervades every sector and function of the global economy. This paper focuses on the gaps between Big Data and the current capabilities of data analysis in continuous auditing (CA). It identifies four dimensions of Big Data and five subsequent gaps: namely, data consistency, integrity, aggregation, identification, and confidentiality. For each gap, the paper outlines challenges and possible solutions derived from traditional data systems, which can be further applied to CA systems in an era of Big Data.