Thermally Induced Reversible Fluorescence Switching of Lead Chloride Hybrids for Anticounterfeiting and Encryption.

Metal halide hybrids with thermally induced fluorescence transition have the potential to be utilized as the next generation of smart materials in optoelectronic devices. However, the fabrication of thermochromic materials with simultaneously reversible and lower transition temperatures is still a challenge. Herein, we present a novel one-dimensional (1D) organic-inorganic lead chloride hybrid (TPA)PbCl3-Green (TPA = tetrapropylammonium) single crystal that exhibits green emission and up to 30% photoluminescence quantum yield (PLQY). It is worth noting that the (TPA)PbCl3-Green crystal changes emission from green to blue light when heated at 323 K. The emission spectra indicate that the blue light is attributed to the combination of two emission peaks located at 438 and 520 nm, respectively. Furthermore, the green luminescence is restored after natural cooling to room temperature. The dynamic transition process is demonstrated via steady-state photoluminescence, single-crystal X-ray diffraction (SCXRD), and powder X-ray diffraction (XRD). (TPA)PbCl3-Green crystals and (TPA)PbCl3-Green@PVP complexes have also been explored as fluorescent security inks for dynamic anticounterfeiting and message encryption as well as optical logic gate applications due to the excellent cycling stability and low transition temperature. This material offers a completely new option for thermochromic materials used for security information.

Controlled Morphology, Improved Photoluminescent Properties, and Application of an Efficient Non-rare Earth Deep Red-Emitting Phosphor.

Transition-metal tetravalent manganese ions (Mn4+) as luminescence center of red phosphors have drawn much attention owing to their broad-band absorption extended from UV to blue regions and narrow red-emissive band. In the present work, a series of Mn4+-doped BaGeF6 red phosphors were obtained via hydrothermal method. X-ray powder diffraction, energy-dispersive X-ray spectrometer, scanning electron microscope, and photoluminescence spectra were employed to determine the crystal structure, composition, morphology, and photoluminescence properties of all samples. The prepared BaGeF6:Mn4+ samples demonstrate two dominant broadband absorption at near-UV (∼366 nm) and blue regions (∼470 nm) and intense red emissions (∼635 nm) under 470 nm excitation. In addition, the morphology and the emission intensities were successfully controlled by adjusting doping concentrations, reaction times, reaction temperatures, barium sources, and surfactants. Concentration quenching and thermal quenching mechanisms were studied in detail. When the BaGeF6:Mn4+ red phosphor was introduced into the light-emitting diode, warm white light-emitting diodes (w-LEDs) were successfully fabricated, which have high color rendering index (Ra = 86.3) and low correlated color temperature (4766 K), indicating that the BaGeF6:Mn4+ red phosphor provides a good opportunity for application in w-LEDs.

Significantly Enhanced Mechanical, Thermal, and Ablative Properties of the Lightweight Carbon Fabric/Phenol-Formaldehyde Resin/Siloxane Aerogels Ternary Interpenetrating Network.

Lightweight ablative thermal protection materials (TPMs), which can resist long-term ablation in an oxidizing atmosphere, are urgently required for aerospace vehicles. Herein, carbon fabric/phenol-formaldehyde resin/siloxane aerogels (CF/PFA/SiA) nanocomposite with interpenetrating network multiscale structure was developed via simple and efficient sol-gel followed by atmospheric pressure drying. The ternary networks structurally interpenetrating in macro-, micron-, and the nanoscales, chemically cross-linking at the molecular scale, and silica layer generated by in situ heating synergistically bring about low density (∼0.3 g cm-3), enhanced mechanical properties, thermal stability, and oxidation resistance, and a low thermal conductivity of 81 mW m-1 K-1. More intriguingly, good thermal protection with near-zero surface recession at 1300 °C for 300 s and remarkable thermal insulation with a back-side temperature below 60 °C at 20 mm thickness. The interpenetrating network strategy can be extended to other porous components with excellent high-temperature properties, such as ZrO2 and SiC, which will facilitate the improvement of lightweight ablative TPMs. Moreover, it may open a new avenue for fabricating multifunctional binary, ternary, and even multiple interpenetrating network materials.

One-Dimensional Copper-Doped Rb2AgI3 with Efficient Sky-Blue Emission as a High-Performance X-ray Scintillator.

Scintillators have garnered heightened attention for their diverse applications in medical imaging and security inspection. Nonetheless, commercial scintillators encounter challenges with costly rare-earth metals and toxic elements like thallium (Tl), driving the need for sustainable, cost-effective, and eco-friendly alternatives to meet contemporary X-ray detection demands. This study focuses on exploring the potential of Cu+-doped Rb2AgI3 as an effective metal halide (MH) scintillator. One-dimensional (1D) Rb2AgI3 and Cu+-doped Rb2AgI3 single crystals (SCs) were synthesized by using the conventional temperature-lowering crystallization method. When excited by UV light, Cu+-doped SCs emitted a broad sky-blue light at 490 nm with a high photoluminescence (PL) quantum yield (PLQY) of 76.48%. Remarkably, under X-ray excitation, these Cu+-doped SCs demonstrated an outstanding light yield of 36,293 photons MeV-1, a relatively low detection threshold of 1.022 µGyair s-1, and a rapid scintillation decay time of 465 ns. The prepared translucent scintillation film has good uniformity and flexibility, with a high spatial resolution of 10.2 lp mm-1. These results position Cu+-doped Rb2AgI3 as a leading candidate among promising X-ray scintillators, offering superior scintillation light yield, excellent stability, and nontoxicity.

Novel green/red oxyfluoride phosphors with excellent optical properties for near-UV excited white light emitting diode.

Novel eye-sensitive Ba3Nb2O2F12(H2O)2:Tb3+ green and Ba3Nb2O2F12(H2O)2:Mn4+ red oxyfluoride phosphors with extremely strong absorption in the UV region were designed and synthesized by simple co-precipitation strategy. Particularly, Tb3+ ions were doped in this matrix for the first time, which greatly improves their absorption efficiency in the near ultraviolet region (367 nm) and emits sharp green light (544 nm). In addition, the Ba3Nb2O2F12(H2O)2:Mn4+ red phosphors have strong zero phonon line (ZPL) emission at 625 nm, which is conducive to improving the sensitivity of human eye and color purity. Meanwhile, the optical properties of the red phosphor are significantly enhanced via doping K+ cations as charge compensators. Crystal field environment and nephelauxetic effect of the as-prepared phosphors before and after K+ cation doping were systematically analyzed. Moreover, these synthesized red/green phosphors have good thermal stability and moisture resistance. Remarkably, the as-prepared Ba3Nb2O2F12(H2O)2:5%Mn4+ or K0.9Ba2.1Nb2O2F12(H2O)2:5%Mn4+ red phosphors can be directly mixed with the as-synthesized Ba3Nb2O2F12(H2O)2:13%Tb3+ green phosphor coating on 365 nm near-ultraviolet LED chip to package WLED devices with excellent electroluminescence performance. These findings are conducive to opening an avenue for screening the unique structure of optical materials.

Sn(II)-doped one-dimensional hybrid metal halide [C5H14NO]CdCl3 single crystals with broadband greenish-yellow light emission.

Low-dimensional organic-inorganic hybrid halides, as an important branch of metal halide materials, have attracted much attention due to their excellent photoelectric properties. Herein, we designed one new hybrid cadmium chloride [C5H14NO]CdCl3 based on combinations of the d10 metal cation (Cd2+) and choline chloride molecules. [C5H14NO]CdCl3 single crystals belong to the orthorhombic Pna21 space group and show a one-dimensional (1D) structure with distorted [CdCl5O]5- octahedra. The second harmonic generation (SHG) response of [C5H14NO]CdCl3 exhibits an intensity of approximately 0.4 × KDP. Moreover, the photoluminescence properties of the [C5H14NO]CdCl3 crystal are activated by doping with Sn2+ ions having stereochemically active lone pair 5s2 electrons. Under UV excitation conditions, bright greenish-yellow light emission can be observed, and the quantum efficiency (PLQY) is as high as 91.27%. The luminescence mechanism is revealed by combining the results of temperature dependent luminescence and density functional theory (DFT) calculation. This work can serve as a guide for the design and synthesis of emerging optical materials.

Optical enhancement of highly efficient organic-inorganic oxyfluoride red phosphors via the cation co-doping strategy.

Herein, a new organic cationic matrix [N(CH3)4]3MoO3F3 suitable for Mn4+ doping was constructed. Due to the large steric hindrance of N[CH3]4+ (TMA), charge compensation defects can be effectively prevented in the heterovalent Mn4+-doping process, and a high IQE (91.05%) was obtained. Through the cation co-doping strategy, Mg2+/Zn2+/Li+ cations were introduced into the Mo6+ cationic site, which improved the crystallinity of the matrix and reduced energy losses, so as to improve luminescence intensity, QE, thermal stability, water stability and other spectral properties. Meanwhile, [N(CH3)4]2TiF6:Mn4+ phosphors with the same TMA organic cation and equivalent Mn4+ doping were synthesized for comparison, and the effects of the Mg2+ cation co-doping strategy on the spectral properties of phosphors with different matrix types (fluoride/oxyfluoride) and substitution types (equivalent/non-equivalent) were analyzed. These findings provide the basis for the preparation of new luminescent materials. Furthermore, according to the optical properties exhibited by these phosphors, they are packaged into WLED devices with excellent photoelectric properties, which are suitable for indoor lighting and display fields.

Location of glycine mutations within a bacterial collagen protein affects degree of disruption of triple-helix folding and conformation.

The hereditary bone disorder osteogenesis imperfecta is often caused by missense mutations in type I collagen that change one Gly residue to a larger residue and that break the typical (Gly-Xaa-Yaa)(n) sequence pattern. Site-directed mutagenesis in a recombinant bacterial collagen system was used to explore the effects of the Gly mutation position and of the identity of the residue replacing Gly in a homogeneous collagen molecular population. Homotrimeric bacterial collagen proteins with a Gly-to-Arg or Gly-to-Ser replacement formed stable triple-helix molecules with a reproducible 2 °C decrease in stability. All Gly replacements led to a significant delay in triple-helix folding, but a more dramatic delay was observed when the mutation was located near the N terminus of the triple-helix domain. This highly disruptive mutation, close to the globular N-terminal trimerization domain where folding is initiated, is likely to interfere with triple-helix nucleation. A positional effect of mutations was also suggested by trypsin sensitivity for a Gly-to-Arg replacement close to the triple-helix N terminus but not for the same replacement near the center of the molecule. The significant impact of the location of a mutation on triple-helix folding and conformation could relate to the severe consequences of mutations located near the C terminus of type I and type III collagens, where trimerization occurs and triple-helix folding is initiated.

Preparation of immobilized pepsin for extraction of collagen from bovine hide.

In the extraction of collagens from mammalian tissues, the free pepsin used in the acid-pepsin extraction system is hard to recycle, and there is a risk of enzyme protein contamination in the extracted collagen products, which limits their applications. To solve this problem, an immobilized pepsin was successfully prepared via the covalent crosslinking of glutaraldehyde using a 3-aminopropyltriethoxysilane (APTES) surface modified silica clay as the support. The immobilized pepsin was applied for the extraction of collagen from bovine hide. The optimal immobilization process involves incubating pepsin with an initial concentration of 35 mg mL-1 and glutaraldehyde with 5% activated APTES modified silica clay at 25 °C for 60 min, by which the loading amount of pepsin was 220 mg g-1 and the activity of the immobilized pepsin was 4.2 U mg-1. The collagen extracted using acetic acid and the immobilized pepsin method retained its complete triple helix structure. This research thus details an effective separation method using pepsin for extraction of collagen via an acetic acid-enzyme method, where the extracted collagen may be a candidate for use in biomaterial applications.

Osteogenesis imperfecta missense mutations in collagen: structural consequences of a glycine to alanine replacement at a highly charged site.

Glycine is required as every third residue in the collagen triple helix, and a missense mutation leading to the replacement of even one Gly in the repeating (Gly-Xaa-Yaa)(n) sequence with a larger residue leads to a pathological condition. Gly to Ala missense mutations are highly underrepresented in osteogenesis imperfecta (OI) and other collagen diseases, suggesting that the smallest replacement residue, Ala, might cause the least structural perturbation and mildest clinical consequences. The relatively small number of Gly to Ala mutation sites that do lead to OI must have some unusual features, such as greater structural disruption because of local sequence environment or location at a biologically important site. Here, peptides are used to model a severe OI case in which a Gly to Ala mutation is found within a highly stabilizing Lys-Gly-Asp sequence environment. Nuclear magnetic resonance, circular dichroism, and differential scanning calorimetry studies indicate this Gly to Ala replacement leads to a substantial loss of triple-helix stability and nonequivalence of the Ala residues in the three chains such that only one of the three Ala residues is capable of forming a good backbone hydrogen bond. Examination of reported OI Gly to Ala mutations suggests their preferential location at known collagen binding sites, and we propose that structural defects caused by Ala replacements may lead to pathology when they interfere with interactions.

Preparation of dynamic covalently crosslinking keratin hydrogels based on thiol/disulfide bonds exchange strategy.

Dynamic covalently crosslinking (DCC) hydrogels can mimic extracellular matrix and have the functions such as self-healing, self-adapting, and shape memory. The DCC keratin hydrogels based on thiol group-disulfide bonds exchange strategy have no reports so far as we know. Herein, inspired by the rich content of the intramolecular disulfide bonds and free thiol groups in the keratins extracted by reducing agents, we report a simple thiol-disulfide bonds exchange strategy for preparing the DCC keratin hydrogels. While the pH value of the keratin solution extracted by reducing agents was adjusted to 9.5-10.0, the keratin hydrogels showed the characteristic with injectability, self-healing, self-adapting, biocompatibility, and redox-responsive capacity. The extracted type II neutral/alkali keratin plays a critical role in imparting the keratin hydrogels with the reversibility behaviors due to that the keratins could build dynamic covalent bonds through thiol oxidation and disulfide exchange reactions in alkali conditions. This strategy provides an inspiration for forming DCC keratin hydrogel by avoiding the extra introduction of chemical crosslinking agents.

Ion-imprinted modified molecular sieves show the efficient selective adsorption of chromium(vi) from aqueous solutions.

Molecular sieve 5A was modified with (3-aminopropyl) triethoxysilane (APTES) as the support matrix, on which 4-VP was used as the ionic imprinting group. The as-prepared IIZMS-APTES was applied as the adsorbent for the recovery of chromium(vi) from aqueous solutions. The adsorbent was characterized via Fourier transform infrared spectroscopy (FT-IR), scanning electronic microscopy (SEM), and X-ray diffraction (XRD). The influences of adsorption time, concentration of the ions, initial pH, and temperature on the adsorption performance to Cr(vi) were investigated. The selectivity and reusability of IIZMS-APTES are also evaluated. The results showed that the maximum adsorption capacity reached 56.46 mg g-1 when the initial concentration of metal ions was at 100 mg L-1 at pH 2 and 30 °C. The adsorption process followed the pseudo-second-order kinetic model and Langmuir adsorption isotherm model. The IIZMS-APTES exhibits an efficient selective adsorption of Cr(vi) from aqueous solutions.

The interaction of sodium dodecyl sulfate with trypsin: Multi-spectroscopic analysis, molecular docking, and molecular dynamics simulation.

The bioactivity of enzymes is sensitive to certain factors in their application environment, such as the pH, temperature, ionic strength, and additives, which can alter the native conformation of enzymes. To determine the mechanism by which the interaction of SDS influences the structure and activity of trypsin, molecular docking, molecular dynamics simulations, DSC, and multi-spectroscopic measures including UV absorption, fluorescence, and circular dichroism were used. The results show that the hydrolytic activity towards casein could be dramatically restrained by SDS. UV absorption, CD, and fluorescence spectra demonstrated the formation of a trypsin-SDS complex. Thermodynamic parameters and molecular docking data revealed that the binding process was spontaneous, and that the main binding forces between SDS and trypsin were hydrogen bonds and van der Waals forces. In addition, molecular docking predicted that the binding site of SDS on trypsin was located at the active center. Molecular dynamic simulations showed that treatment with SDS resulted in the structure of trypsin becoming unstable and unfolded near its active center. This work provides insights into the interaction of SDS with trypsin on the molecular level and is beneficial to understanding of how SDS affects the conformation and activity of trypsin in application processes.

Preparation of ZnO nanoparticle loaded amidoximated wool fibers as a promising antibiofouling adsorbent for uranium(vi) recovery.

In this study, nano-ZnO loaded amidoxime-functionalized wool fibers (wool-AO@ZnO) were synthesized by radiation-induced copolymerization and in situ co-precipitation as a novel adsorbent with good antibiofouling properties for uranium recovery. The prepared adsorbent was characterized by SEM-EDS and FT-IR spectroscopy. Batch adsorption experiments showed that the prepared wool-AO@ZnO have a good uranium adsorption property at pH 6.0-9.0. Meanwhile, wool-AO@ZnO displayed a good inhibition of aerobic bacteria such as S. aureus and E. coli; of anaerobic bacteria; of sulfate reducing bacteria; of fungus C. albicans and of mildew Aspergillus niger. After four cyclic cultivations with microorganisms, the inhibition rate of wool-AO@ZnO to E. coli and S. aureus still remains at 77.8% and 84.9%, respectively; and a good adsorption capacity for uranium(vi) was maintained. The prepared wool-AO@ZnO could be a promising antibiofouling adsorbent for the recovery of uranium(vi) from seawater.

The preparation of organophosphorus ligand-modified SBA-15 for effective adsorption of Congo red and Reactive red 2.

P,P-bis (2-oxooxazolidin-3-yl)-N-(3-(triethoxysilyl)propyl)phosphinic amide (APTES-BOP)-modified SBA-15 (SBA-15-BOP) was prepared by a post-synthesis grafting method for the removal of anionic azo dyes from aqueous solutions. The properties of the prepared adsorbent were characterized by PXRD, FT-IR, SEM, TEM, nitrogen sorption, and elemental analysis. Adsorption equilibrium and adsorption kinetic studies demonstrated that the experimental data fitted well with the Langmuir isotherm model and pseudo-second-order model. According to Langmuir fitting, SBA-15-BOP showed high adsorption capacity for CR and RR2 dyes, with the maximum adsorption capacities of 518.1 mg g-1 and 253.8 mg g-1, respectively. The thermodynamic study indicated that the adsorption processes of CR and RR2 dyes on SBA-15-BOP were spontaneous and exothermal. The prepared SBA-15-BOP can be a promising adsorbent for the removal of anionic dyes from aqueous solutions.

Novel polygonal structure Mn4+ activated In3+-based Elpasolite-type hexafluorides red phosphor for warm white light-emitting diodes (WLEDs).

A novel type polygonal structure red emission Elpasolite-type hexafluorides (NH4)2NaInF6:Mn4+ phosphor is successfully synthesized by hydrothermal and coprecipitation methods. The samples exhibit two typical absorption bands located at the ultraviolet-visible (369 nm) and the blue light area (470 nm) and emit bright red light centered at 633 nm with high color purity. Powder X-ray diffraction (XRD) has been used to demonstrate the phase purity and crystal structure of the samples synthesized. The corresponding surface morphology and composition have been confirmed via scanning electron microscope (SEM) with an attached energy-dispersive X-ray spectrometer (EDS), respectively. All luminescence properties have been deeply investigated by excitation spectra, emission spectra, luminescence decay curves and temperature-dependent luminescent spectra. The morphology of the as-prepared phosphor is successfully controlled by adjusting reaction solvents and adding different surfactants. In addition, the optical behaviours of the red phosphors are evidently relied on the experimental procedure, the concentrations of the K2MnF6, different surfactants and reaction solvents. Concentration and thermal quenching mechanisms are discussed according to detailed experimental results. A warm white light-emitting diode (WLED) with the as-obtained red phosphor (NH4)2NaInF6:Mn4+ has been successfully produced, which has low CCT (3960 K), high CIR (Ra = 85.5) and LE of 129 lm W-1. Above results reveal the extraordinary application value of (NH4)2NaInF6:Mn4+ red phosphor for highly efficient warm WLEDs.

Super flame-retardant lightweight rime-like carbon-phenolic nanofoam.

The desire for lightweight nanoporous materials with high-performance thermal insulation and efficient anti-ablation resistance for energy conservation and thermal protection/insulation has greatly motivated research and development recently. The main challenge to synthesize such lightweight materials is how to balance the relationship of low thermal conductivity and flame retardancy. Herein, we propose a new concept of lightweight "rime-like" structured carbon-phenolic nanocomposites to solve this problem, where the 3D chopped network-structured carbon fiber (NCF) monoliths are incorporated with nanoporous phenolic aerogel to retain structural and functional integrity. The nanometer-scaled porous phenolic (NP) was synthesized through polymerization-induced phase separation and ambient pressure drying using phenolic resin (PR) solution as reaction source, ethylene glycol (EG) as solvent and hexamethylenetetramine (HMTA) as catalyst. We demonstrate that the as-prepared NCF-NP nanocomposite exhibits with a low density of 0.25-0.35 g/cm(3), low thermal conductivity of 0.125 Wm(-1)K(-1) and outstanding flame retardancy exceeding 2000 °C under arc-jet wind tunnel simulation environment. Our results show that the synthesis strategy is a promising approach for producing nanocomposites with excellent high-temperature heat blocking property.

Sequence environment of mutation affects stability and folding in collagen model peptides of osteogenesis imperfecta.

Osteogenesis imperfecta (OI), a disorder characterized by fragile bones, is often a consequence of missense mutations in type I collagen, which change one Gly in the repeating (Gly-Xaa-Yaa)(n) sequence to a larger amino acid. The impact of local environment and the identity of the residue replacing Gly were investigated using two sets of triple-helical peptides. Gly mutations in the highly stable (Pro-Hyp-Gly)(10) system are compared with mutations in T1-865 peptides where the mutation is located within a less stable natural collagen sequence. Replacement of a Gly residue by Ala, Ser, or Arg leads to significant triple-helical destabilization in both peptide systems. The loss of stability (ΔT(m) ) due to a Gly to Ala or Gly to Ser change was greater in the more rigid (Pro-Hyp-Gly)(10) peptides than in the T1-865 set, as expected. But the final T(m) values, which may be the more biologically meaningful parameters, were higher for the (Pro-Hyp-Gly)(10) mutation peptides than for the corresponding T1-865 mutation peptides. In both peptide environments, a Gly to Arg replacement prevented the formation of a fully folded triple-helix. Monitoring of folding by differential scanning calorimetry showed a lower stability species as well as the fully folded triple-helical molecules for T1-865 peptides with Gly to Ala or Ser replacements, and this lower stability species disappears as a function of time. The difficulty in propagation through a mutation site in T1-865 peptides may relate to the delayed folding seen in OI collagens and indicates a dependence of folding mechanism on the local sequence environment.

[Quantity of released nickel ion from Ni-Cr alloy of compound galvano-ceramic bridge].

OBJECTIVE: To evaluate the biological safety of compound galvano-ceramic bridge by measuring the consistency of released nickel ion of the galvano-form slices cohered with Ni-Cr alloy slice specimens which were immersed in artificial saliva. METHODS: Specimens were divided into five groups with four tests and one control. Test specimens were made into the structure like rectangle sandwich that one side of Ni-Cr alloy was cohered to the center surface of galvano golden base of 0.2 mm and another side was fused porcelain with the thickness of 0.3 mm (group A), 0.5 mm (group B), 1.0 mm (group C), and 0.3 mm (group D). And the Ni-Cr alloys were totally embedded in galvano golden base and firing porcelain. Naked Ni-Cr alloy was taken as control. Group D was immersed into acid artificial saliva (AS) with high fluoride, while others were in acid AS at 37 degrees C for 120 h. Then the consistency of released nickel ion in the solution was measured with inductively coupled plasma-atomic emission spectrometry (ICP-AES). RESULTS: Nickel ions detected in the artificial saliva for the groups A, B, C, and D in acid AS with or without high fluoride were all under 0.005 mg/L Significant differences were found between each test group and the control [(0.65 +/- 0.45) mg/L]. CONCLUSIONS: Galvano-ceramic bridge, Ni-Cr alloy bridge with fused porcelain and golden base, shows biological safety responsible for the consistency of released nickel ion.