Luminescent Ultralong Microfibers Prepared through Supramolecular Self-Assembly of Lanthanide Ions and Thymidine in Water.

Luminescent materials are of great interest in many fields, such as fluorescent sensing and medical imaging. Here, the construction of lanthanide-based luminescent ultralong microfibers through supramolecular self-assembly (SSA) is reported. Nucleosides (thymidine in particular), the building blocks of nucleic acids, were used as new ligands to mediate the formation of luminescent microfibers in water. The length of microfibers from thymidine-lanthanide ion (Eu and Tb) SSA was on the centimeter scale. Notably, the microfibers exhibited strong luminescence because the lanthanide ions had been chelated, sensitized and effectively protected by thymidine molecules in water. Only when the stoichiometric ratio of lanthanide ion to thymidine was 1:3 and the pH of the solution was 7, are luminescent microfibers formed. Other nucleosides, such as adenosine, cytidine, and guanosine, could not form microfibers with the lanthanide ions. This work opens a new avenue for constructing nucleoside-lanthanide SSA architectures, which hold great potential in biological and optical related applications.

Effects of compound chemical activators on the hydration of low-carbon ferrochrome slag-based composite cement.

Low-carbon ferrochrome slag (LCFS), a by-product of the ferrochrome alloy industry, has potential for use as a cementitious material due to its pozzolanic characteristic. The objective of the present study was to determine the optimum compound chemical activators for LCFS-based composite cement using an orthogonal test, in which 7 d and 28 d compressive strengths were used as the evaluating indices. The influences of compound chemical activators on the hydration of a composite cement mix were investigated using X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS) and thermogravimetry-differential scanning calorimetry (TG-DSC). The optimum activator to activate the composite cement was a compound of NaCl (NC) at a dosage of 0.6%, Na2SO4 (NS) at a dosage of 1.2%, NaF (NF) at a dosage of 0.6% and Al2(SO4)3 (AS) at a dosage of 0.9% or 0.7%. The compressive strengths of the optimum composite cement mix at ages of 3, 28 and 180 d increased by 50.1%, 22.4% and 16.5%, respectively. More hydration products including ettringite and calcium silicate hydrate were formed at an early age of hydration. The compound chemical activators effectively activated the ferrochrome slag (FS), blast-furnace slag (BFS) and fly ash (FA) in the composite cement.

Assay of fluoride by a novel organic-inorganic mesoporous nano-sized sensor.

In this report, we prepared a novel mesoporous silica nanostructure for selective detection of fluoride through ultraviolet absorption and emission changes. In the sensing system, a silica coupling reagent (3-(triethoxysilyl)propyl isocyanate) linked 1-naphthylamine has been covalently grafted onto the mesopores of inorganic network. These specially designed nanospheres can recognize fluoride from other anions based on hydrogen bond interactions. This approach may provide new opportunities for designing related sensing systems with enhanced physical or chemical properties. Copyright © 2016 John Wiley & Sons, Ltd.

Chloride Permeability of Alkali-Activated Slag Concretes after Exposure to High Temperatures.

The number of fires in buildings and on bridges has increased worldwide in recent years. As a structural material, the strength of alkali-activated slag (AAS) concrete after exposure to high temperatures has been given much attention. However, research of its durability is still lacking, which limits the application of this type of concrete on a larger scale. In this context, as one of the most important aspects of durability, the chloride permeability of AAS concretes after exposure to high temperatures was examined in this study. The influence of the alkali concentration (Na2O%) and the modulus (Ms) of the activator, as well as the influence of heating regimes, including the heating rate, duration of exposure to the target temperature, and cooling method, was also discussed. The results show that the chloride permeability of the AAS concretes increased with temperature elevation. Due to the interference of pore solution conductivity, the influence of the Na2O% and the Ms of the activator on the chloride permeability of the AAS concretes was not made clear by using the ASTM C 1202 charge passed method; however, after exposure to high temperatures, AAS with a lower Na2O% and lower Ms has lower porosity and may have lower chloride permeability, which needs further investigation. Faster heating for a longer duration at the target temperature and water cooling reduced the resistance of the AAS concretes to chloride permeability as a result of their increased porosity.

Effect of Coffee Grounds/Coffee Ground Biochar on Cement Hydration and Adsorption Properties.

Taking advantage of the strong adsorption characteristics of coffee grounds (CGs) and coffee ground biochar (CGB), this research employed equal amounts of 2%, 4%, 6%, and 8% CGs and CGB to replace cement. This study thereby examined the impacts of CGs and CGB on cement compressive strength, as well as their abilities to adsorb chloride ions and formaldehyde. X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG-DTG), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) were employed to investigate the hydration mechanism and characterize the microscopic structure. The results show the following: (1) The presence of a substantial quantity of organic compounds in CGs is found to have an adverse effect on both the compressive strength and hydration degree of the sample. The use of CGB after high-temperature pyrolysis of phosphoric acid can effectively improve the negative impact of organic compounds on the sample. (2) The addition of CGs reduces the adsorption of chloride ions by cement, primarily due to the presence of fewer hydration products. However, when CGB was incorporated into cement, it enhanced the ability to adsorb chloride ions. (3) Cement containing 8% CGB content can slightly enhance the adsorption of formaldehyde. However, the cement sample with 8% CGB content exhibited the most significant ability to adsorb formaldehyde.

Thermal-Related Stress-Strain Behavior of Alkali Activated Slag Concretes under Compression.

In this paper, the thermal-related stress-strain behavior of alkali-activated slag (AAS) concretes, with different alkali concentrations and moduli, was studied under compression. After exposure to high temperatures (200 °C, 400 °C, 600 °C, 800 °C, and 1000 °C), a compression test was carried out on the specimens. The stress-strain relationship, axial compressive strength, and elastic modulus were expressed using both a displacement extensometer and the digital image correlation (DIC) technique. It was mainly determined that: (1) With the increase in temperature, the stress-strain curves of the AAS concretes tended to be flattened, indicating reductions in both axial compressive strength and elastic modulus. After 1000 °C, only 2.5-3.7% axial compressive strength and 1.4-3.9% elastic modulus remained, respectively. (2) The DIC technique was used for thermal strain measurements of the AAS concrete. Compared to the traditional extensometer, DIC yielded a small error of 4.5% and 7.2% for axial compressive strength and elastic modulus measurements, respectively. The strain cloud chart obtained from DIC was helpful for monitoring the damage process of the specimens. The findings of this paper refined scientific systems of AAS concrete under thermal action, and also provided a newly non-contact approach for thermal strain measurements of AAS concrete under compression.

Study of Piezoresistive Behavior of Smart Cement Filled with Graphene Oxide.

A cement-based piezoelectric composite, modified by graphene oxide (GO), was prepared to study piezoresistive capacity. The testing confirms that GO is more effective than other carbon nanomaterials at improving piezoresistive sensitivity of cement-based composites, because the content of GO in cement paste was much lower than other carbon nanomaterials used in previously published research. Further investigation indicates that the addition of GO significantly improved the stability and repeatability for piezoresistive capacity of cement paste under cycle loads. Based on experiment results, the piezoresistive sensitivity of this composite depended on GO content, water-to-cement weight ratio (w/c) and water-loss rate, since the highest piezoresistive gauge factor value (GF = 35) was obtained when GO content was 0.05 wt.%, w/c was 0.35 and water-loss rate was 3%. Finally, microstructure analysis confirmed that conductivity and piezoresistivity were achieved through a tunneling effect and by contacting conduction that caused deformation of GO networks in the cement matrix.

A Reversibly Responsive Fluorochromic Hydrogel Based on Lanthanide-Mannose Complex.

Fluorochromic materials that are dynamic in response to external stimuli are of great interest for the development of advanced sensors and luminescent materials. Herein, a design based on a lanthanide-containing polymeric hydrogel possessing characteristic emission of lanthanides (Eu and Tb) and showing response to stimuli of metal ions is reported. The fluorochromic hydrogel is prepared using a lanthanide-mannose complex in gelation matrix. The lanthanide-mannose complex shows tunable fluorescent emission in response to Fe2+, due to the inhibition of the "antenna effect" between metal ions and ligands upon stimulation. The fluorescent hydrogel shows reversible "On/Off" fluorochromic response to Fe2+/ethylenediaminetetraacetic acid (EDTA). Remarkably, the fluorescent hydrogel is proven nontoxic and biocompatible; and a proof-of-application as in situ 3D cell culture extracellular matrix with reversible fluorochromic "On/Off" switch upon Fe2+/EDTA is demonstrated. This reversibly responsive fluorochromic hydrogel demonstrates a way to fabricate smart optical materials, particularly for biological-related applications where reversible response is required.

Multiresponsive Supramolecular Luminescent Hydrogels Based on a Nucleoside/Lanthanide Complex.

Supramolecular luminescent hydrogels based on natural molecules have shown high potential for a variety of applications because of unique optical properties and biocompatibility, particularly serving as advanced biomaterials for bioimaging, biosensing, cell engineering, and so forth. A lanthanide complex-based system provides a promising way to prepare supramolecular luminescent hydrogels. Herein, we realize the creation of a luminescent hydrogel assembled from lanthanides and nucleosides. Nucleosides, the essential components of nucleic acids, functioning as the ligands, successfully chelate with lanthanides and form complexes in water. The complexes subsequently serve as building-blocks to form supramolecular hydrogels, which exhibit characteristic luminescent emission of lanthanides. The coordination modes and forming mechanism are studied by electrospray ionization time-of-flight mass spectrometry, matrix-assisted laser desorption/ionization time of flight mass spectrometry, 1H NMR spectroscopy, and Fourier transform infrared spectroscopy; the corresponding molecular simulations are presented, and macro-/micro-morphologies, mechanical properties, and luminescent performances of hydrogels are systemically studied. Remarkably, these luminescent hydrogels show fluorochromic properties in response to external stimuli, including pH, temperature, anions, and cations, which are thus adopted to design smart luminescent switches and detect specific species such as Cu2+. Our work provides a feasible strategy to prepare stimuli-responsive luminescent hydrogels, reveals the diverse potential of nucleoside-based hydrogels, and exhibits a novel pathway for the preparation of smart optical materials.

Lanthanide induced formation of novel luminescent alginate hydrogels and detection features.

Responsive photo-luminescent soft matters have led to the design of optical sensors and switches. In this research, two new organic-inorganic type hybrid hydrogels have been fabricated by the self-assembly of sodium alginate and lanthanide elements. The incorporation of europium ions (Eu(3+)) (or terbium ions (Tb(3+))) was required for the gelation of the dissolved alginate and thermally stable gels were formed. It has been found that red/green emissions derived from lanthanide ions were clearly identified in pure aqueous media through the metal coordination interactions with assembled alginate. These supramolecular structures could partially prevent the Eu(3+) (or Tb(3+)) from being attacked by high frequency vibrations. More importantly, the lanthanide luminescence could be switched "off-on" in the presence of the anthrax biomarker sodium dipicolinate (NaDPA). The detection limits (for NaDPA) were determined to be 8.3×10(-8)M and 9.0×10(-8)M based on Eu(III) and Tb(III) gel, respectively.