Study on the process of mass transfer and deterioration of limestone under dynamic dissolution of CO2 solution.

The long-term erosion of rock by solution can induce a series of karst problems. Therefore, this study focused on limestone and conducted dynamic dissolution experiments under deionized water and CO2 solution conditions to study the deterioration mechanism of limestone under nonequilibrium conditions. The results showed that the degree of degradation of the mechanical properties of the samples in a CO2 solution was obviously greater. In a deionized water environment, the degradation of the mechanical properties of the sample is mainly controlled by the physical softening action of the solution. In the CO2 solution environment, the degradation process can be divided into two stages. In the early stage of the experiment (10 days to 20 days), the degradation of mechanical properties of the sample is also controlled by the physical softening action of the solution. With increasing soaking time, the main rock-forming minerals of limestone gradually react with the CO2 solution, the degradation of the sample is controlled mainly by the chemical corrosion of the CO2 solution, and its degradation rate is much greater than that of physical softening. The results can be used as a reference for assessing the long-term stability of underground engineering in limestone karst development areas.

Direct Write Printing of Ultraviolet-Curable Bulk Superhydrophobic Ink Material.

Although superhydrophobic surfaces have various promising applications, their fabrication methods are often limited to 2D plane surfaces that are vulnerable to abrasion and have limited adhesion to the substrate. Herein, an ultraviolet (UV) curable ink with bulk superhydrophobicity, consisting of poly(dimethylsiloxane) (PDMS) resins, hydrophobic silica, and solvent (porogen), was successfully developed for UV-assisted direct write printing processing. After UV curing of the ink followed by solvent evaporation, the generated porous structure cooperates with silica particles to form a self-similar and hierarchical structure throughout the bulk material, which can keep its original morphology even after cyclic abrasion (over 1000 times) and thus exhibits durable superhydrophobicity. With this unique ink, UV-assisted direct write printing can not only create 2D superhydrophobic surfaces on various substrates (e.g., paper and wire mesh) but also fabricate self-supporting 3D superhydrophobic objects for various applications such as waterproofing and oil-water separation. The printed objects exhibited a stable superhydrophobicity against liquid corrosion and mechanical damage. In addition, the 3D printing approach can be used to optimize the oil-water separation performance of the superhydrophobic porous materials by tuning the pore size, thus presenting promising applications.

PagDET2 promotes cambium cell division and xylem differentiation in poplar stem.

Secondary growth of the woody tree stem is governed by meristematic cell division and differentiation in the vascular cambium. Multiple hormonal signals and endogenous developmental programs regulate vascular cambium activity. Brassinosteroids (BRs) significantly promote secondary stem growth and wood formation in poplar trees. However, the underlying regulatory mechanisms of BRs within the vascular tissue remain unclear. Genetic and anatomical approaches were used here to elucidate the role of PagDET2, the rate-limiting enzyme for BRs biosynthesis, in regulating secondary vascular cambium activity in Populus. This study showed that the elevated endogenous castasterone (CS) levels in tree stems through overexpressing PagDET2 could enhance cambium meristem cell activity and xylem (XY) differentiation to promote secondary stem growth. RNA-seq analysis revealed that genes involved in BRs response, vascular cambium cell division, XY differentiation, and secondary cell wall synthesis were up-regulated.

Flow characteristics in partially vegetated channel with homogeneous and heterogeneous layouts.

This study presents the experimental results of the flow characteristics, such as the flow adjustment, velocity profiles, mixing layer, and the momentum exchange, in the partially vegetated channel with homogeneous and heterogeneous layouts. Three cases are considered, including two homogeneous canopies with uniform sparse and dense vegetation patches respectively, and a heterogeneous canopy consisting of alternating patches of both densities. Results show that heterogeneous canopy requires a longer adjustment distance to reach the quasi-equilibrium region, compared with the homogenous canopy of the same density. In heterogeneous canopy flow, the mixing layer width and the momentum thickness fluctuates with the alternation of vegetation density. The increased values for these two parameters compared to those values for the homogeneous canopies indicate that the greater resistance and momentum loss occur for the heterogeneous layout. A wavy region of the enhanced in-plane turbulence kinetic energy (TKE) is observed in the heterogeneous canopy, suggesting a comparatively more chaotic flow condition, whereas the contours of in-plane TKE are smooth in homogeneous canopies. The presence of the coherent structures in heterogeneous canopy is identified by spectral analysis and the quasi-periodic fluctuations of velocities. The Reynolds stress associated with the coherent structures is found to be the dominator of the contribution to the total Reynolds stress. The comparison between the homogenous canopies of different density is also conducted. These results will be of practical importance for the design of vegetation layouts in water ecological restoration projects and for river management.

Oncolytic adenovirus programmed by synthetic gene circuit for cancer immunotherapy.

Improving efficacy of oncolytic virotherapy remains challenging due to difficulty increasing specificity and immune responses against cancer and limited understanding of its population dynamics. Here, we construct programmable and modular synthetic gene circuits to control adenoviral replication and release of immune effectors selectively in hepatocellular carcinoma cells in response to multiple promoter and microRNA inputs. By performing mouse model experiments and computational simulations, we find that replicable adenovirus has a superior tumor-killing efficacy than non-replicable adenovirus. We observe a synergistic effect on promoting local lymphocyte cytotoxicity and systematic vaccination in immunocompetent mouse models by combining tumor lysis and secretion of immunomodulators. Furthermore, our computational simulations show that oncolytic virus which encodes immunomodulators can exert a more robust therapeutic efficacy than combinatorial treatment with oncolytic virus and immune effector. Our results provide an effective strategy to engineer oncolytic adenovirus, which may lead to innovative immunotherapies for a variety of cancers.

Infrared induced repeatable self-healing and removability of mechanically enhanced graphene-epoxy flexible materials.

A repeatable self-healing epoxy composite mechanically enhanced by graphene nanosheets (GNS) was prepared from an epoxy monomer with Diels-Alder (DA) bonds, octanediol glycidyl ether (OGE) and polyether amine (D230). The GNS/epoxy composites, with a maximum tensile modulus of 14.52 ± 0.45 MPa and elongation at break more than 100%, could be healed several times under Infrared (IR) light with the healing efficiency as high as 90% through the molecule chain mobility and the rebonding of reversible DA bonds between furan and maleimide. Also, they displayed excellent recyclable ability by transforming into a soluble polymer, which offers a wide range of possibilities to produce epoxy flexible materials with healing and removable abilities.

What will happen when thermoresponsive poly(N-isopropylacrylamide) is tethered on poly(ionic liquid)s?

The thermoresponsive ionic liquid diblock copolymer of poly[1-(4-vinylbenzyl)-3-methylimidazolium tetrafluoroborate]-block-poly(N-isopropylacrylamide) (P[VBMI][BF4]-b-PNIPAM) containing a hydrophilic poly(ionic liquid) block of P[VBMI][BF4] is prepared by sequential reversible addition-fragmentation chain transfer (RAFT) polymerization. This P[VBMI][BF4]-b-PNIPAM exhibits an abnormal thermoresponsive phase transition at a temperature above the phase transition temperature (PTT) of the PNIPAM block. For P[VBMI][BF4]-b-PNIPAM including a short P[VBMI][BF4] block, its aqueous solution becomes turbid at a temperature above the PTT of the thermoresponsive PNIPAM block, whereas for P[VBMI][BF4]-b-PNIPAM containing a relatively long P[VBMI][BF4] block even in the case of a relatively long PNIPAM block, the aqueous solution remains transparent at a temperature far above the PTT of the PNIPAM block, although a soluble-to-insoluble phase transition of the PINIPAM block is confirmed by dynamic light scattering (DLS) analysis and variable temperature 1H NMR analysis. The reason that P[VBMI][BF4]-b-PNIPAM exhibits an abnormal thermoresponse is discussed and ascribed to the highly hydrophilic and charged poly(ionic liquid) block of P[VBMI][BF4] leading to the formation of small-sized micelles at a temperature above the PTT.

Identifying and characterizing SCRaMbLEd synthetic yeast using ReSCuES.

SCRaMbLE is a novel system implemented in the synthetic yeast genome, enabling massive chromosome rearrangements to produce strains with a large genotypic diversity upon induction. Here we describe a reporter of SCRaMbLEd cells using efficient selection, termed ReSCuES, based on a loxP-mediated switch of two auxotrophic markers. We show that all randomly isolated clones contained rearrangements within the synthetic chromosome, demonstrating high efficiency of selection. Using ReSCuES, we illustrate the ability of SCRaMbLE to generate strains with increased tolerance to several stress factors, such as ethanol, heat and acetic acid. Furthermore, by analyzing the tolerant strains, we are able to identify ACE2, a transcription factor required for septum destruction after cytokinesis, as a negative regulator of ethanol tolerance. Collectively, this work not only establishes a generic platform to rapidly identify strains of interest by SCRaMbLE, but also provides methods to dissect the underlying mechanisms of resistance.

Crystal structure and electrochemical properties of [Ni(bztmpen)(CH3CN)](BF4)2 {bztmpen is N-benzyl-N,N',N'-tris-[(6-methyl-pyridin-2-yl)meth-yl]ethane-1,2-di-amine}.

The mononuclear nickel title complex (acetonitrile-κN){N-benzyl-N,N',N'-tris-[(6-methyl-pyridin-2-yl)meth-yl]ethane-1,2-di-amine}-nickel(II) bis-(tetra-fluor-ido-borate), [Ni(C30H35N5)(CH3CN)](BF4)2, was prepared from the reaction of Ni(BF4)2·6H2O with N-benzyl-N,N',N'-tris-[(6-methyl-pyridin-2-yl)meth-yl]ethane-1,2-di-amine (bztmpen) in aceto-nitrile at room temperature. With an open site occupied by the aceto-nitrile mol-ecule, the nickel(II) atom is chelated by five N-atom sites from the ligand and one N atom from the ligand, showing an overall octa-hedral coordination environment. Compared with analogues where the 6-methyl substituent is absent, the bond length around the Ni2+ cation are evidently longer. Upon reductive dissociation of the acetro-nitrile mol-ecule, the title complex has an open site for a catalytic reaction. The title complex has two redox couples at -1.50 and -1.80 V (versus Fc+/0) based on nickel. The F atoms of the two BF4- counter-anions are split into two groups and the occupancy ratios refined to 0.611 (18):0.389 (18) and 0.71 (2):0.29 (2).

Crystal structure of [Cu(tmpen)](BF4)2 {tmpen is N,N,N',N'-tetra-kis-[(6-methyl-pyridin-2-yl)meth-yl]ethane-1,2-di-amine}.

The mononuclear copper title complex {N,N,N',N'-tetra-kis-[(6-methyl-pyridin-2-yl)meth-yl]ethane-1,2-di-amine-κ6N}copper(II) bis-(tetra-fluorido-borate), [Cu(C30H36N6)](BF4)2, is conveniently prepared from the reaction of Cu(BF4)2·6H2O with N,N,N',N'-tetra-kis-[(6-methyl-pyridin-2-yl)meth-yl]ethane-1,2-di-amine (tmpen) in aceto-nitrile at room temperature in air. The complex shows a distorted octa-hedral environment around the CuII cation (site symmetry 2) and adopts the centrosymmetric space group C2/c. The presence of the 6-methyl substituent hinders the approach of the pyridine group to the CuII core. The bond lengths about the CuII atom are significantly longer than those of analogues without the 6-methyl substituents.

Engineering the ribosomal DNA in a megabase synthetic chromosome.

We designed and synthesized a 976,067-base pair linear chromosome, synXII, based on native chromosome XII in Saccharomyces cerevisiae SynXII was assembled using a two-step method, specified by successive megachunk integration and meiotic recombination-mediated assembly, producing a functional chromosome in S. cerevisiae. Minor growth defect "bugs" detected in synXII, caused by deletion of tRNA genes, were rescued by introducing an ectopic copy of a single tRNA gene. The ribosomal gene cluster (rDNA) on synXII was left intact during the assembly process and subsequently replaced by a modified rDNA unit used to regenerate rDNA at three distinct chromosomal locations. The signature sequences within rDNA, which can be used to determine species identity, were swapped to generate a Saccharomyces synXII strain that would be identified as Saccharomyces bayanus by standard DNA barcoding procedures.

YeastFab: the design and construction of standard biological parts for metabolic engineering in Saccharomyces cerevisiae.

It is a routine task in metabolic engineering to introduce multicomponent pathways into a heterologous host for production of metabolites. However, this process sometimes may take weeks to months due to the lack of standardized genetic tools. Here, we present a method for the design and construction of biological parts based on the native genes and regulatory elements in Saccharomyces cerevisiae. We have developed highly efficient protocols (termed YeastFab Assembly) to synthesize these genetic elements as standardized biological parts, which can be used to assemble transcriptional units in a single-tube reaction. In addition, standardized characterization assays are developed using reporter constructs to calibrate the function of promoters. Furthermore, the assembled transcription units can be either assayed individually or applied to construct multi-gene metabolic pathways, which targets a genomic locus or a receiving plasmid effectively, through a simple in vitro reaction. Finally, using ß-carotene biosynthesis pathway as an example, we demonstrate that our method allows us not only to construct and test a metabolic pathway in several days, but also to optimize the production through combinatorial assembly of a pathway using hundreds of regulatory biological parts.