Preparation of a Polycarboxylate Superplasticizer with Different Monomer Regulations and Its Effect on Fluidity, Rheology, and Strength of Cement.

Polycarboxylate superplasticizers (PCEs) are indispensable functional ingredients in modern construction, and their usage is extensive. Herein, a polyether macromonomer (VPEG) with high reactivity was used to prepare VAPCEs with different interfacial adsorption properties (acid-ether ratio) at low temperatures and reacted in 30 min. The effects of various VAPCEs on the fluidity, rheology, and strength of cement were investigated with a w/c (water/cement) ratio of 0.35. Results showed that VAPCE-3 (acid-ether ratio is 3) exhibited the best dispersion, and the fluidity of cement slurry with VAPCE-3 (280 mm) is 278.38% higher than that of the control sample (74 mm). The reason is summarized as VAPCE-3 having good adsorption performance on the surface of cement particles and having a large steric hindrance between particles. The compressive strength of cement with VAPCE-3 was enhanced by 8.29% compared with pure cement in 3 days of curing age due to its densification on microstructure and lowest R orientation index of calcium hydroxide. With the amount of acrylic acid in VAPCE increasing, the flexural strength enhanced because a more cross-linking network was formed with Ca2+ in cement with the increase of COO- content in VAPCEs.

Engineered Organic Nanorockets with Light-Driven Ultrafast Transportability for Antitumor Therapy.

Nanomedicines confront various complicated physiological barriers limiting the accumulation and deep penetration in the tumor microenvironment, which seriously restricts the efficacy of antitumor therapy. Self-propelled nanocarriers assembled with kinetic engines can translate external energy into orientated motion for tumor penetration. However, achieving a stable ultrafast permeability at the tumor site remains challenging. Here, sub-200 nm photoactivated completely organic nanorockets (NRs), with asymmetric geometry conveniently assembled from photothermal semiconducting polymer payload and thermo-driven macromolecular propulsion through a straightforward nanoprecipitation process, are presented. The artificial NRs can be remotely manipulated by 808 nm near-infrared light to trigger the photothermal conversion and Curtius rearrangement reaction within the particles for robustly pushing nitrogen out into the solution. Such a two-stage light-to-heat-to-chemical energy transition effectively powers the NRs for an ultrafast (≈300 µm s-1 ) and chemical medium-independent self-propulsion in the liquid media. That endows the NRs with high permeability against physiological barriers in the tumor microenvironment to directionally deliver therapeutic agents to target lesions for elevating tumor accumulation, deep penetration, and cellular uptake, resulting in a significant enhancement of antitumor efficacy. This work will inspire the design of advanced kinetic systems for powering intelligent nanomachines in biomedical applications.

Development of Terminator-Promoter Bifunctional Elements for Application in Saccharomyces cerevisiae Pathway Engineering.

The construction of a genetic circuit requires the substitution and redesign of different promoters and terminators. The assembly efficiency of exogenous pathways will also decrease significantly when the number of regulatory elements and genes is increased. We speculated that a novel bifunctional element with promoter and terminator functions could be created via the fusion of a termination signal with a promoter sequence. In this study, the elements from a Saccharomyces cerevisiae promoter and terminator were employed to design a synthetic bifunctional element. The promoter strength of the synthetic element is apparently regulated through a spacer sequence and an upstream activating sequence (UAS) with a ~5-fold increase, and the terminator strength could be finely regulated by the efficiency element, with a ~5-fold increase. Furthermore, the use of a TATA box-like sequence resulted in the adequate execution of both functions of the TATA box and the efficiency element. By regulating the TATA box-like sequence, UAS, and spacer sequence, the strengths of the promoter-like and terminator-like bifunctional elements were optimally fine-tuned with ~8-fold and ~7-fold increases, respectively. The application of bifunctional elements in the lycopene biosynthetic pathway showed an improved pathway assembly efficiency and higher lycopene yield. The designed bifunctional elements effectively simplified pathway construction and can serve as a useful toolbox for yeast synthetic biology.

Photoactivated Organic Nanomachines for Programmable Enhancement of Antitumor Efficacy.

Limited permeability in solid tumors significantly restricts the anticancer efficacy of nanomedicines. Light-driven nanomotors powered by photothermal converting engines are appealing carriers for directional drug delivery and simultaneous phototherapy. Nowadays, it is still a great challenge to construct metal-free photothermal nanomotors for a programmable anticancer treatment. Herein, one kind of photoactivated organic nanomachines is reported with asymmetric geometry assembled by light-to-heat converting semiconducting polymer engine and macromolecular anticancer payload through a straightforward nanoprecipitation process. The NIR-fueled polymer engine can be remotely controlled to power the nanomachines for light-driven thermophoresis in the liquid media and simultaneously thermal ablating the cancer cells. The great manipulability of the nanomachines allows for programming of their self-propulsion in the tumor microenvironment for effectively improving cellular uptake and tumor penetration of the anticancer payload. Taking the benefit from this behavior, a programmed treatment process is established at a low drug dose and a low photothermal temperature for significantly enhancing the antitumor efficacy.

Redox stimulus disulfide conjugated polyethyleneimine as a shuttle for gene transfer.

Redox-responsive cationic polymers have gained considerable attention in gene delivery due to low cytotoxicity and spatio-temporal release of DNA into the cells. Here, we reported the synthesis of reducible disulfide conjugated polyethyleneimine (1.8 kDa) (denoted as SS-PEI) and its application to transfer pEGFP-ZNF580 plasmid (pZNF580) into EA.hy926 cell. This reducible SS-PEI polymer was prepared by one-step polycondensation reaction of low molecular weight PEI with bis-(p-nitrophenyl)-3,3'-dithiodipropionate. The SS-PEI successfully condensed pZNF580 into nano-sized complexes (170 ± 1.5 nm to 255 ± 1.6 nm) with zeta potentials of 3 ± 0.4 mV to 17 ± 0.9 mV. The complexes could be triggered to release pZNF580 when exposed to the reducing environment of 5 mM dithiothreitol. Besides, the SS-PEI exhibited low cytotoxicity. In vitro transfection results showed that SS-PEI exhibited good transfection efficiency comparable to PEI25kDa. Thus, the SS-PEI could act as an reducible gene carrier with good transfection efficiency and low cytotoxicity.

Multifunctional Gene Carriers Labeled by Perylene Diimide Derivative as Fluorescent Probe for Tracking Gene Delivery.

Multifunctional carriers with both gene transfection property and fluorescent tracking function have attracted significant attention in recent years. Herein, a kind of perylene diimide derivative (PDI-C10C8) is conjugated onto the polyethylenimine-g-poly(lactide-co-glycolide)-g-polyethylenimine (PLGA-PEI) polymer to obtain fluorescent multifunctional polymer and micelles (abbreviated as MP). Then, the REDV-G-TAT-G-NLS (TP-G) peptide sequence is grafted onto this MP to obtain multifunctional micelles labeled by perylene diimide derivative (MP-TP-G). These micelles exhibit enhanced photobleaching stability compared with the reference Cy5-labeled micelles, and the fluorescent images of cellular uptake show bright red emission without any background noise. Confocal laser scanning microscope (CLSM) experiments show that gene complexes can deliver gene into nucleus. MP-TP-G carriers do not enter into the cell nucleus, which proves that the nuclear localization signal sequence may not exert its nucleus accumulation ability via conjugating to the amphiphilic polymers. The high transfection efficiency and the enhanced photobleaching stability, combined with the ability to monitor the detailed process of cellular uptake and gene delivery, make these multifunctional micelles have great potential application for endothelialization of artificial blood vessels and gene delivery process study.

Oligohistidine and targeting peptide functionalized TAT-NLS for enhancing cellular uptake and promoting angiogenesis in vivo.

BACKGROUND: Gene therapy has been developed and used in medical treatment for many years, especially for the enhancement of endothelialization and angiogenesis. But slow endosomal escape rate is still one of the major barriers to successful gene delivery. In order to evaluate whether introducing oligohistidine (Hn) sequence into gene carriers can promote endosomal escape and gene transfection or not, we designed and synthesized Arg-Glu-Asp-Val (REDV) peptide functionalized TAT-NLS-Hn (TAT: typical cell-penetrating peptide, NLS: nuclear localization signals, Hn: oligohistidine sequence, n: 4, 8 and 12) peptides with different Hn sequence lengths. pEGFP-ZNF580 (pZNF580) was condensed by these peptides to form gene complexes, which were used to transfect human umbilical vein endothelial cells (HUVECs). RESULTS: MTT assay showed that the gene complexes exhibited low cytotoxicity for HUVECs. The results of cellular uptake and co-localization ratio demonstrated that the gene complexes prepared from TAT-NLS-Hn with long Hn sequence (n = 12) benefited for high internalization efficiency of pZNF580. In addition, the results of western blot analysis and PCR assay of REDV-TAT-NLS-H12/pZNF580 complexes showed significantly enhanced gene expression at protein and mRNA level. Wound healing assay and transwell migration assay also confirmed the improved proliferation and migration ability of the transfected HUVECs by these complexes. Furthermore, the in vitro and in vivo angiogenesis assay illustrated that these complexes could promote the tube formation ability of HUVECs. CONCLUSION: The above results indicated that the delivery efficiency of pZNF580 and its expression could be enhanced by introducing Hn sequence into gene carriers. The Hn sequence in REDV-TAT-NLS-Hn is beneficial for high gene transfection. These REDV and Hn functionalized TAT-NLS peptides are promising gene carriers in gene therapy.

Correction: Surface modification and endothelialization of biomaterials as potential scaffolds for vascular tissue engineering applications.

Correction for 'Surface modification and endothelialization of biomaterials as potential scaffolds for vascular tissue engineering applications' by Xiangkui Ren et al., Chem. Soc. Rev., 2015, DOI: .

Surface modification and endothelialization of biomaterials as potential scaffolds for vascular tissue engineering applications.

Surface modification and endothelialization of vascular biomaterials are common approaches that are used to both resist the nonspecific adhesion of proteins and improve the hemocompatibility and long-term patency of artificial vascular grafts. Surface modification of vascular grafts using hydrophilic poly(ethylene glycol), zwitterionic polymers, heparin or other bioactive molecules can efficiently enhance hemocompatibility, and consequently prevent thrombosis on artificial vascular grafts. However, these modified surfaces may be excessively hydrophilic, which limits initial vascular endothelial cell adhesion and formation of a confluent endothelial lining. Therefore, the improvement of endothelialization on these grafts by chemical modification with specific peptides and genes is now arousing more and more interest. Several active peptides, such as RGD, CAG, REDV and YIGSR, can be specifically recognized by endothelial cells. Consequently, graft surfaces that are modified by these peptides can exhibit targeting selectivity for the adhesion of endothelial cells, and genes can be delivered by targeting carriers to specific tissues to enhance the promotion and regeneration of blood vessels. These methods could effectively accelerate selective endothelial cell recruitment and functional endothelialization. In this review, recent developments in the surface modification and endothelialization of biomaterials in vascular tissue engineering are summarized. Both gene engineering and targeting ligand immobilization are promising methods to improve the clinical outcome of artificial vascular grafts.

Electrospun scaffolds of silk fibroin and poly(lactide-co-glycolide) for endothelial cell growth.

Electrospun scaffolds of silk fibroin (SF) and poly(lactide-co-glycolide) (PLGA) were prepared to mimic the morphology and chemistry of the extracellular matrix. The SF/PLGA scaffolds were treated with ethanol to improve their usability. After ethanol treatment the scaffolds exhibited a smooth surface and uniform fibers. SF transformed from random coil conformation to ß-sheet structure after ethanol treatment, so that the SF/PLGA scaffolds showed low hydrophilicity and dissolving rate in water. The mechanical properties and the hydrophilicity of the blended fibrous scaffolds were affected by the weight ratio of SF and PLGA. During degradation of ethanol-treated SF/PLGA scaffolds in vitro, the fibers became thin along with the degradation time. Human umbilical vein endothelial cells (HUVECs) were seeded onto the ethanol-treated nanofibrous scaffolds for cell viability, attachment and morphogenesis studies. These SF/PLGA scaffolds could enhance the viability, spreading and attachment of HUVECs. Based on these results, these ethanol-treated scaffolds are proposed to be a good candidate for endothelial cell growth.

Defoaming and Toughening Effects of Highly Dispersed Graphene Oxide Modified by Amphoteric Polycarboxylate Superplasticizer on Oil Well Cement.

The aggregation of graphene oxide (GO) during the hydration process limits its wide application. Polymer superplasticizers have been used to improve the dispersion state of GO due to their adsorption and site-blocking effects, though the formation of a large amount of foam during the mixing process weakens the mechanical properties of cement. A highly dispersed amphoteric polycarboxylate superplasticizer-stabilized graphene oxide (APC/GO) toughening agent was prepared by electrostatic self-assembly. Results demonstrate that the APC/GO composite dispersed well in a cement pore solution due to the steric effect offered by the APC. Additionally, the well-dispersed GO acted as an antifoaming agent in the cement since GO nanosheets can be absorbed at the air-liquid interface of APC foam via electrostatic interactions and eliminate the air-entraining effect. The well-dispersed APC/GO sheets promoted cement hydration and further refined its pore structure owing to the nucleation effect. The flexural and compressive strength of the cement containing the APC/GO composite were enhanced by 21.51% and 18.58%, respectively, after a 7-day hydration process compared with a blank sample. The improved hydration degree, highly polymerized C-S-H gel, and refined pore structure provided enhanced mechanical properties.

Occurrence Mechanism of the Abnormal Gelation Phenomenon of High Temperature Cementing Slurry Induced by a Polycarboxylic Retarder.

The class G oil well cement is a type of special cement that can be subjected to a high temperature formation environment. It was found that the class G cement tail slurry with a low polycarboxylic retarder dosage (usually ≤1% by weight of cement) was more prone to cause the abnormal gelation phenomenon (AGP) than the lead slurry with a high retarder dosage at a high temperature (usually when T ≥ 120 °C). This study aimed at the occurrence mechanism of this unfavorable phenomenon that seriously endangers the cementing security. Results showed that the abnormal gelatinous region underwent premature hydration; namely, the calcium hydroxide and calcium silicate hydrate (C-S-H) content were all higher than the nongelatinous region, while the copolymer content was the opposite. Correspondingly, the theory of "premature hydration and crystal nucleation" was proposed to explain the abnormal gelation mechanism of a cementing tail slurry with an insufficient retarder dosage. Furthermore, a novel functionalized copolymer retarder "PAIANS" was synthesized to alleviate the AGP.

Design of Janus Nanoparticles for Mobility Control in Heterogeneous Reservoirs.

Unfavorable mobility ratios in heterogeneous reservoirs have resulted in progressively poor waterflood sweep efficiency and diminishing production. In order to address this issue, our study has developed amphiphilic-structured nanoparticles aimed at enhancing the microscopic displacement capability and oil displacement efficiency. First, the transport process of Janus nanoparticles in porous media was investigated. During the water flooding, Janus nanoparticle injection, and subsequent water flooding stages, the injection pressure increased in a "stepped" pattern, reaching 0.023, 0.029, and 0.038 MPa, respectively. Second, emulsification effects and emulsion viscosity experiments demonstrated that the amphiphilic structure improved the interaction at the oil-water interface, reducing the seepage resistance of the oil phase through emulsification. In porous media, Janus nanoparticles transported with water exhibit 'self-seeking oil' behavior and interact with the oil phase, reducing the viscosity of the oil phase from 19 to 5 mPa·s at 80 °C. Finally, the core model displacement experiment verified the characteristics of Janus nanoparticles in improving the oil-water mobility ratio. Compared with the water flooding stage, the recovery percent increased by 20.8%, of which 13.7% was attributed to the subsequent water flooding stage. Utilizing the asymmetry of the Janus particle structure can provide an effective path to enhanced oil recovery in inhomogeneous reservoirs.

A potential nonthrombogenic small-diameter vascular scaffold with polyurethane/poly(ethylene glycol) hybrid materials by electrospinning technique.

A small-diameter vascular graft (inner diameter 4 mm) was fabricated from polyurethane (PU) and poly(ethylene glycol) (PEG) solutions by electrospinning technology. The fiber diameter decreased from 1023 +/-185 nm to 394 +/- 106 nm with increasing weight ratio of PEG in electrospinning solutions. The PU/PEG scaffolds showed randomly nanofibrous morphology and well-interconnected porous structure. The hydrophilicity of these scaffolds was improved significantly with increasing weight ratio of PEG. The mechanical properties of electrospun PU/PEG scaffolds were obviously different from that of pure PU scaffold, which was caused by plasticizing or hardening effect imparted by PEG composition. Under hydrated state, the PU/PEG scaffolds demonstrated low mechanical performance due to the hydrophilic property of materials. Compared with dry PU/PEG scaffolds with the same weight ratio of PEG, the tensile strength and elastic modulus of hydrated PU/PEG scaffolds decreased significantly, while the elongation at break increased. The results demonstrated that the electrospun PU/PEG hybrid tubular scaffolds are potential candidates for artificial blood vessels.

Grafting of poly(ethylene glycol) monoacrylates on polycarbonateurethane by UV initiated polymerization for improving hemocompatibility.

Poly(ethylene glycol) monoacrylates (PEGMAs) with a molecular weight between 400 and 1,000 g mol(-1) were grafted by ultraviolet initiated photopolymerization on the surface of polycarbonateurethane (PCU) for increasing its hydrophilicity and improving its hemocompatibility. The surface-grafted PCU films were characterized by Fourier transformation infrared spectroscopy, X-ray photoelectron spectroscopy, water contact angle, scanning electron microscopy (SEM) and atomic force microscopy measurements. The surface properties of the modified films were studied in dry and wetted state. Blood compatibility of the surfaces was evaluated by platelet adhesion tests and adhered platelets were determined by SEM. The results showed that the hydrophilicity of the films had been increased significantly by grafting PEGMAs, and platelets adhesion onto the film surface was obviously suppressed. Furthermore, the molecular weight of PEGMAs had a great effect on the hydrophilicity and hemocompatibility of the PCU films after surface modification and increased with increasing molecular weight of PEGMAs.

Mechanical Properties of Calcium Aluminate Cement Reinforced with Plasma-Treated Basalt Fibers for In Situ Combustion.

Brittleness and poor tensile/flexural properties restrict the application of calcium aluminate cement (CAC) in oil and gas wells. Reinforcing CAC with fibers is an effective method for improving its strength and toughness and overcoming the shortcomings of its mechanical properties. In this article, as an auxiliary cementing material, slag does not affect the thickening time of CAC. After adding slag, the cement slurry meets the thickening time during cementing construction, and basalt fiber is selected as the toughening material. The enhancement effect of basalt fiber on the mechanical properties of CAC slag composites is studied, including the evaluation of the macroscopic mechanical properties and microstructure at a high temperature (500 °C). The optimum composition of basalt and fiber-reinforced CAC was determined. Basalt fibers were added to CAC at different contents of 0, 0.1, 0.2, 0.3, 0.4, and 0.5% based on the weight of the cement. All the results showed that the introduction of basalt fibers could significantly enhance the strength of the cement at high temperatures. Compared with the control samples, an additional increase in the compressive and tensile strengths of the samples of 35.1 and 85.2%, respectively, was achieved at high temperature with approximately 0.4% fiber content. Plasma treatment further improved the reinforcing effect of the basalt fibers, where the high-temperature compressive and tensile strengths of the samples increased from 28.88 and 1.52 to 35.23 and 1.87 MPa, respectively, an increase of 21.98 and 20.6%, respectively, compared with the untreated basalt fibers. When the cement paste is cured by simulated curing for 28 d, the high-temperature compressive strength and tensile strength with plasma modification increased from 28.26 and 1.5 to 29.1 and 2.15 MPa, respectively, an increase of 3.0 and 43.3%, respectively. The structure of the formed hydrates was studied using scanning electron microscopy. Furthermore, toughening of the basalt fiber-reinforced CAC-based composites resulted mainly from crack bridging and fiber pull-out.

Effects of Hybrid Graphene Oxide-Nanosilica on Calcium Silicate Hydrate in the Simulation Environment and Cement.

This research aims to investigate the synergistic reinforcing mechanisms of chemically combined graphene oxide and nanosilica (GO-NS) in the structure of calcium silicate hydrate (C-S-H) gels compared with physically combined GO/NS. The results confirmed that the NS chemically deposited on the GO surface formed a coating to keep GO from aggregation, while the connection between GO and NS in GO/NS was too weak to prevent GO from clumping, making GO-NS better dispersed than GO/NS in pore solution. When applied to cement composites, the incorporation of GO-NS enhanced the compressive strength by 27.3% after 1-day hydration compared to that of the plain sample. This is because that GO-NS generated multiple nucleation sites at early hydration, reduced the orientation index of calcium hydroxide (CH), and increased the polymerization degree of C-S-H gels. GO-NS acted as the platforms for the growing process of C-S-H, enhancing its interface bonding strength with C-S-H and increasing the connection degree of the silica chain. Furthermore, the well-dispersed GO-NS was prone to insert in C-S-H and induced deeper cross-linking, thereby refining the microstructure of C-S-H. All these effects on hydration products resulted in the mechanical improvement of cement.

Water-Adaptive Microcapsules with a Brittle-Ductile-Brittle Transition Based on an O/W/O Emulsion for the Self-Healing of Cementitious Materials.

Cementitious materials inevitably develop cracks, posing a serious threat to the long-term security of infrastructure, especially in the complex underground environment of cementing engineering. Microcapsules are facing the problem of encapsulated structure damage during the mixing and breaking difficultly during self-healing when applied in cementitious materials, resulting in the decline of self-healing efficiency. Herein, the calcium alginate water-adaptive microcapsules (CaAlg-NS/E-51) were prepared via an O/W/O emulsion, and the water adaptability of the shell was applied to achieve a rapid brittle-ductile transition by absorbing water. The water adaptability of the microcapsule is conducive to resisting shear stress during stirring due to the decreased elastic modulus and the increased ductility of the shell when it absorbs water. Meanwhile, the water-bearing shell loses water and becomes brittle during dry curing, making it prone to fracture when self-healing. In the self-healing measurement, the self-healing efficiency of cementitious specimens with microcapsules absorbing water for 10 min improved by 234.9 and 60.0% at 1 and 7 days, respectively, compared with those containing dry microcapsules, owing to the water adaptability of the shell.

Synthesis and characterization of a phosphotungstic acid composite carrier and its application in solid chlorine dioxide disinfectant.

Chlorine dioxide (ClO2) is an antimicrobial compound used in water. The short release time of existing solid chlorine dioxide disinfectants significantly inhibits their bactericidal efficiency. We propose a novel approach in which attapulgite was introduced into phosphotungstic acid and SBA-15 to achieve the slow-release of chlorine dioxide disinfectant tablets. The emphasis of the study lies in slow release of chlorine dioxide and reducing the escape of chlorine dioxide gas to increase the reaction time and improve disinfection efficiency. When dissolved in water the decrease rate of chlorine dioxide within 15 days after mixing SBA-15/HPW with sodium chlorite is 78.6%. Moreover, the sterilization efficiency of Escherichia coli reaches 100% within 5 minutes, and the killing rate of Staphylococcus aureus exceeds 99.999% within 10 minutes. The research solved the storage and transportation problems of ClO2 and resulted in a solution for the disinfection of water requiring long-term disinfection.

Synthesis of a hydrophobic associating polymer and its application in plugging spacer fluid.

The high temperature of formation and multiple stages of leakage zone seriously affect the efficiency and safety of drilling and cementing operations. To improve leakage plugging quality before the cementing process, the hydrophobic associating polymer PHAAO was synthesized from acrylamide (AM), 2-acrylamide-2-methyl propane sulfonic acid (AMPS), and the long side-chain hydrophobic monomer octadecyl dimethyl allyl ammonium chloride (ODAAC) in this study. The structure and molecular weight of the polymer were characterized, and it was proved that the polymer has strong association properties and excellent heat resistance. Utilizing the bridge plugging principle, the polymer PHAAO was used with 36-mesh walnut shells and lignin fiber to form a compound plugging agent. This agent was added to spacer fluid to become a plugging spacer. API water loss tests and loading capacity tests under high temperatures show that the filter cake formed by the spacer fluid is dense. The sealing pressure of the spacer fluid on a 1 mm crack can reach 6.5 MPa at 160 °C, and it has good compatibility with cement slurry. A scanning electron microscopy (SEM) test was conducted to explore the membrane formation mechanism of the polymer. An ultra-low permeability membrane is formed on the surface of the filter cake from the spacer fluid due to the hydrophobic association and hydrogen bonding between the polymer and lignin fiber, thereby greatly reducing the loss of spacer fluid.