The structural origin of the efficient photochromism in natural minerals.

SignificanceNatural photochromic minerals have been reported by geologists for decades. However, the understanding of the photochromism mechanism has a key question still unanswered: What in their structure gives rise to the photochromism's reversibility? By combining experimental and computational methods specifically developed to investigate this photochromism, this work provides the answer to this fundamental question. The specific crystal structure of these minerals allows an unusual motion of the sodium atoms stabilizing the electronic states associated to the colored forms. With a complete understanding of the photochromism mechanism in hand, it is now possible to design new families of stable and tunable photochromic inorganic materials-based devices.

Single-Peptide TR-FRET Detection Platform for Cysteine-Specific Post-Translational Modifications.

Post-translational modifications (PTMs) are one of the most important regulatory mechanisms in cells, and they play key roles in cell signaling both in health and disease. PTM catalyzing enzymes have become significant drug targets, and therefore, tremendous interest has been focused on the development of broad-scale assays to monitor several different PTMs with a single detection platform. Most of the current methodologies suffer from low throughput or rely on antibody recognition, increasing the assay costs, and decreasing the multifunctionality of the assay. Thus, we have developed a sensitive time-resolved Förster resonance energy transfer (TR-FRET) detection method for PTMs of cysteine residues using a single-peptide approach performed in a 384-well format. In the developed assay, the enzyme-specific biotinylated substrate peptide is post-translationally modified at the cysteine residue, preventing the subsequent thiol coupling with a reactive AlexaFluor 680 acceptor dye. In the absence of enzymatic activity, increase in the TR-FRET signal between the biotin-bound Eu(III)-labeled streptavidin donor and the cysteine-coupled AlexaFluor 680 acceptor dye is observed. We demonstrate the detection concept with cysteine modifying S-nitrosylation and ADP-ribosylation reactions using a chemical nitric oxide donor S-nitrosoglutathione and enzymatic ADP-ribosyltransferase PtxS1-subunit of pertussis toxin, respectively. As a proof of concept, three peptide substrates derived from the small GTPase K-Ras and the inhibitory α-subunit of the heterotrimeric G-protein Gαi showed expected functionality in both chemical and enzymatic assays. Measurements yielded signal-to-background ratios of 28.7, 33.0, and 8.7 between the modified and the nonmodified substrates for the three peptides in the S-nitrosylation assay, 5.8 in the NAD+ hydrolysis assay, and 6.8 in the enzymatic ADP-ribosyltransferase inhibitor dose-response assay. The developed antibody-free assay for cysteine-modifying enzymes provides a detection platform with low nanomolar peptide substrate consumption, and the assay is potentially applicable to investigate various cysteine-modifying enzymes in a high throughput compatible format.

Series of Near-IR-Absorbing Transition Metal Complexes with Redox Active Ligands.

New soluble and intensely near-IR-absorbing transition metal (Ti, Zr, V, Ni) complexes were synthesized using a redox non-innocent N,N'-bis(3,5-di-tertbutyl-2-hydroxy-phenyl) -1,2-phenylenediamine (H4L) as a ligand precursor. In all the complexes, ([Ti(Lox)2, [Zr(Lox)2], [V(Lsq1)(HLox)] and [Ni(HLox)2], two organic molecules coordinate to the metal center as tri- or tetradentate ligands. The solid-state structures of the complexes were determined using single crystal XRD, and the compounds were further characterized with Electrospray Ionisation Mass Spectrometry (ESI-MS). Thermoanalytical measurements indicated the thermal stabilities of the complexes. All compounds absorb strongly in the near-IR region and show very interesting magnetic and electrochemical properties. Moreover, it was shown that the V and Ni complexes can also convert absorbed near-IR photons to (un)paired electrons, which indicates great promise in photovoltaic applications.

Red- and green-emitting nano-clay materials doped with Eu3+ and/or Tb3.

Trivalent europium (Eu3+ ) and terbium (Tb3+ ) ions are important activator centers used in different host lattices to produce red and green emitting materials. The current work shows the design of new clay minerals to act as host lattices for rare earth (RE) ions. Based on the hectorite structure, nano-chlorohectorites and nano-fluorohectorites were developed by replacing the OH- present in the hectorite structure with Cl- or F- , thus avoiding the luminescence quenching expected due to the OH- groups. The produced matrices were characterized through X-ray powder diffraction (XPD), transmission electron microscopy (TEM), FT-IR, 29 Si MAS (magic angle spinning) NMR, nitrogen sorption, thermogravimetry-differential scanning calorimetry (TGA-DSC) and luminescence measurements, indicating all good features expected from a host lattice for RE ions. The nano-clay materials were successfully doped with Eu3+ and/or Tb3+ to yield materials preserving the hectorite crystal structure and showing the related luminescence emissions. Thus, the present work shows that efficient RE3+ luminescence can be obtained from clays without the use of organic 'antenna' molecules.

Effective Shielding of NaYF4:Yb3+,Er3+ Upconverting Nanoparticles in Aqueous Environments Using Layer-by-Layer Assembly.

Aqueous solutions are the basis for most biomedical assays, but they quench the upconversion luminescence significantly. Surface modifications of upconverting nanoparticles are vital for shielding the obtained luminescence. Modifications also provide new possibilities for further use by introducing attaching sites for biomolecule conjugation. We demonstrate the use of a layer-by-layer surface modification method combining varying lengths of negatively charged polyelectrolytes with positive neodymium ions in coating the upconverting NaYF4:Yb3+,Er3+ nanoparticles. We confirmed the formation of the bilayers and investigated the surface properties with Fourier transform infrared and reflectance spectroscopy, thermal analysis, and ζ-potential measurements. The effect of the coating on the upconversion luminescence properties was characterized, and the bilayers with the highest improvement in emission intensity were identified. In addition, studies for the nanoparticle and surface stability were carried out in aqueous environments. It was observed that the bilayers were able to shield the materials' luminescence from quenching also in the presence of phosphate buffer that is currently considered the most disruptive environment for the nanoparticles.

Persistent Luminescence of Tenebrescent Na8Al6Si6O24(Cl,S)2: Multifunctional Optical Markers.

Na8Al6Si6O24(Cl,S)2 materials were prepared with a solid state reaction. The products were studied using X-ray powder diffraction, reflectance measurements as well as X-ray fluorescence, conventional and persistent luminescence, nuclear magnetic resonance, and electron paramagnetic resonance spectroscopies. All materials containing sulfur showed purple tenebrescence, which persisted 2 days in a lit room at room temperature. Considerable blue persistent luminescence peaking at 460 nm and lasting for 1 h was obtained, as well. Persistent luminescence was obtained with irradiation at 365 nm, while tenebrescence required 254 nm. The materials show great promise as low-cost multifunctional optical markers.

Optically stimulated persistent luminescence of europium-doped LaAlO3 nanocrystals.

Optically stimulated persistent luminescence was investigated for europium-doped LaAlO3 nanocrystals. This system shows conventional luminescence of both the Eu(3+) line emission and the weak broad-band emission of Eu(2+) upon UV excitation. The persistent luminescence is predominantly associated with the Eu(3+) emission, and can be amplified significantly through irradiation with IR at 975 nm. The conventional luminescence from Eu(3+) is strongly enhanced when the material is excited simultaneously with both UV and IR radiation. The enhancement of persistent luminescence is accompanied by increased persistent photoconductivity. The charge transfer band of the LaAlO3:Eu(3+) nanocrystals in the UV excitation spectra significantly weakens with increasing IR excitation power, also correlating well with the enhancement of persistent luminescence. Finally, a mechanism is presented for the optically stimulated and persistent luminescence in this Eu(2+)- and Eu(3+)-doped LaAlO3 material.

Crystalline nanoxylan from hot water extracted wood xylan at multi-length scale: Molecular assembly from nanocluster hydrocolloids to submicron spheroids.

As a contribution to expand accessibility in the territory of bio-based nanomaterials, we demonstrate a novel material strategy to convert amorphous xylan preserved in wood biomass to hierarchical assemblies of crystalline nanoxylan on a multi-length scale. By reducing the end group in pressurized hot water extracted (PHWE) xylan to primary alcohol as a xylitol form with borohydride reduction, the endwise-peeling depolymerization is effectively impeded in the alkali-catalyzed hydrolytic cleavage of side substitutions in xylan. Nanoprecipitation by a gradual pH decrease resulted in a stable hydrocolloid dispersion in the form of worm-like nanoclusters assembled with primary crystallites, owing to the self-assembly of debranched xylan driven by strong intra- and inter-chain H-bonds. With evaporation-induced self-assembly, we can further construct the hydrocolloids as dry submicron spheroids of crystalline nanoxylan (CNX) with a high average elastic modulus of 47-83 GPa. Taking the advantage that the chain length and homogeneity of PHWE-xylan can be tailored, a structure-performance correlation was established between the structural order in CNX and the phosphorescent emission of this crystalline biopolymer. Rigid clusterization and high crystallinity that are constructed by strong intra- and inter-molecule interactions within the nanoxylan effectively restrict the molecular motion, thereby promoting the emission of ultralong organic phosphorescence.

Excitation Wavelength Engineering through Organic Linker Choice in Luminescent Atomic/Molecular Layer Deposited Lanthanide-Organic Thin Films.

We demonstrate multiple roles for the organic linker in luminescent lanthanide-organic thin films grown with the strongly emerging atomic/molecular layer deposition technique. Besides rendering the hybrid thin film mechanically flexible and keeping the lanthanide nodes at a distance adequate to avoid concentration quenching, the organic moieties can act as efficient sensitizers for the lanthanide luminescence. We investigate six different aromatic organic precursors in combination with Eu3+ ions to reveal that by introducing different nitrogen species within the aromatic ring, it is possible to extend the excitation wavelength area from the UV range to the visible range. This opens new horizons for the application space of these efficiently photoluminescent thin-film materials.

Quantitative multianalyte microarray immunoassay utilizing upconverting phosphor technology.

A quantitative multianalyte immunoassay utilizing luminescent upconverting single-crystal nanoparticles as reporters on an antibody array-in-well platform was demonstrated. Upconverting nanoparticles are inorganic rare earth doped materials that have the unique feature of converting low energy infrared radiation into higher energy visible light. Autofluorescence, commonly limiting the sensitivity of fluorescence-based assays, can be completely eliminated with photon upconversion technology because the phenomenon does not occur in biological materials. Biotinylated antibodies for three analytes (prostate specific antigen, thyroid stimulating hormone, and luteinizing hormone) were printed in an array format onto the bottom of streptavidin-coated microtiter wells. Analyte dilutions were added to the wells, and the analytes were detected with antibody-coated upconverting nanoparticles. Binding of the upconverting nanoparticles was imaged with an anti-Stokes photoluminescence microwell imager, and the standard curves for each analyte were quantified from the selected spot areas of the images. Single analyte and reference assays were also carried out to compare with the results of the multianalyte assay. Multiplexing did not have an effect on the assay performance. This study demonstrates the feasibility of upconverting single-crystal nanoparticles for imaging-based detection of quantitative multianalyte assays.

Reusable radiochromic hackmanite with gamma exposure memory.

Radiochromic films are used as position-sensitive dose meters in e.g. medical physics and radiation processing. The currently available films like those based on lithium-10,12-pentacosdiynoate or leucomalachite green are either toxic or non-reusable, or both. There is thus a great need for a sustainable solution for radiochromic detection. In the present work, we present a suitable candidate: hackmanite with the general formula Na8Al6Si6O24(Cl,S)2. This material is known as a natural intelligent material capable of changing color when exposed to ultraviolet radiation or X-rays. Here, we show for the first time that hackmanites are also radiochromic when exposed to alpha particles, beta particles (positrons) or gamma radiation. Combining experimental and computational data we elucidate the mechanism of gamma-induced radiochromism in hackmanites. We show that hackmanites can be used for gamma dose mapping in high dose applications as well as a memory material that has the one-of-a-kind ability to remember earlier gamma exposure. In addition to satisfying the requirements of sustainability, hackmanites are non-toxic and the films made of hackmanite are reusable thus showing great potential to replace the currently available radiochromic films.

Up-conversion luminescence of the NaRF4-NaR'F4 (R: Y, Yb, Er) core-shell nanomaterials.

Up-converting NaRF(4)-NaR'F(4) (R: Y, Yb, Er) nanomaterials with different core-shell combinations were prepared with the co-precipitation method. The X-ray powder diffraction (XPD) measurements revealed the presence of both the cubic and hexagonal NaRF(4) phases. The crystallite sizes calculated with the Scherrer formula were 100 and 150 nm for the cubic and hexagonal phases, respectively. The FT-IR spectra showed water impurities. The up-conversion luminescence and luminescence decays were studied with NIR laser excitation at 970 nm. The up-conversion luminescence spectra showed strong red (640-685 nm) ((4)F(9/2) → (4)I(15/2)) and moderate green (515-560 nm) ((2)H(11/2,) (4)S(3/2) → (4)I(15/2)) Er(3+) luminescence. The strongest up-conversion luminescence and longest red luminescence decay was obtained from the Na(Y,Yb)F(4)-NaErF(4) core-shell combination.

A diamagnetic iron complex and its twisted sister - structural evidence on partial spin state change in a crystalline iron complex.

We report here the syntheses of a diamagnetic Fe complex [Fe(HL)2] (1), prepared by reacting a redox non-innocent ligand precursor N,N'-bis(3,5-di-tert-butyl-2-hydroxy-phenyl)-1,2-phenylenediamine (H4L) with FeCl3, and its phenoxazine derivative [Fe(L')2] (2), which was obtained via intra-ligand cyclisation of the parent complex. Magnetic measurements, accompanied by spectroscopic, structural and computational analyses show that 1 can be viewed as a rather unusual Fe(III) complex with a diamagnetic ground state in the studied temperature range due to a strong antiferromagnetic coupling between the low-spin Fe(III) ion and a radical ligand. For a paramagnetic high-spin Fe(II) complex 2 it was found that, when crystalline, it undergoes a thermally induced process where 25% of the molecules in the material change to a diamagnetic low-spin ground state below 100 K. Single crystal X-ray studies conducted at 95 K afforded detailed structural evidence for this partial change of spin state of 2 showing the existence of crystallographically distinct molecules in a 3 : 1 ratio which exist in high- and low-spin states, respectively. Also, the magnetic behaviour of 2 was found to be related with the crystallinity of the material as demonstrated by near-IR radiation to unpaired electrons conversion ability of amorphous sample of 2.

Abnormal co-doping effect on the red persistent luminescence SrS:Eu2+,RE3+ materials.

Persistent luminescence materials are a reality in several applications. However, there is still a lack of efficient red-emitting materials. SrS:Eu2+ phosphor is a potential candidate since its strong nephelauxetic effect shifts Eu2+4f65d1 → 4f7 to red, and its weak bond between strontium and sulphide, due to the soft base-hard acid character, generates a high number of intrinsic defects. SrS:Eu2+,RE3+ materials were efficiently prepared by two rounds of 22 min microwave-assisted solid-state synthesis. The highly crystalline purity and the material organization at the micro-scale were observed with X-ray powder diffraction and scanning electron microscopy, respectively. X-ray absorption spectroscopy revealed a low amount of Eu2+ compared to Eu3+ due to the efficient Eu2+ photo-oxidation by X-ray irradiation in the high storage capability SrS host matrix. Electron paramagnetic resonance spectra confirmed that at least 50% of Eu2+ ions in the material are photo-oxidized during excitation, reinforcing the previously established mechanisms. The RE2+ energy level positioned very close to or into the conduction band led to an abnormal co-doping effect, with similar effects independent of the co-dopant. The high concentration of intrinsic defects in SrS indicates that the soft-hard pair host is an excellent approach to develop efficient persistent luminescence materials.

Restraining fluoride loss from NaYF4:Yb3+,Er3+ upconverting nanoparticles in aqueous environments using crosslinked poly(acrylic acid)/poly(allylamine hydrochloride) multilayers.

The use of upconverting nanoparticles in various applications in aqueous media relies on their surface modifications as most synthesis routes yield hydrophobic particles. However, introducing upconverting nanoparticles in aqueous solutions commonly results in the quenching of their luminescence intensity and in the worst case, disintegration of the nanoparticles. We demonstrate the use of poly(acrylic acid) and poly(allylamine hydrochloride) as a protecting layer-by-layer coating for the upconverting NaYF4:Yb3+,Er3+ nanoparticles. The formation and crosslinking of the bilayer coating was confirmed with Fourier transform infrared spectroscopy, thermal analysis and zeta potential. The release of internal fluoride ions from the nanoparticle structure and subsequent particle disintegration was decelerated especially by crosslinking the bilayer coating on the surface. In addition, we studied the effect of the coating on the upconversion luminescence properties and learned that with additional fluoride ions present during the layer-by-layer assembly the most intense enhancement in the luminescent intensity is obtained. This is due both to not allowing the disintegration of the particles during the surface modification process as well as preventing the water molecules accessing the surface by crosslinking the bilayer coating.

Layered Double Hydroxide-Cellulose Hybrid Beads: A Novel Catalyst for Topochemical Grafting of Pulp Fibers.

Cellulose-based materials are very attractive for emerging bioeconomy as they are renewable, inexpensive, and environmentally friendly. Cellulose beads are spherical and porous and can be highly engineered to be used as catalyst support material. This type of inorganic catalysts is cost-effective and suitable for multiple re-usage and has been rarely explored in cellulose reaction research. In this work, NiFe-layered double hydroxide (LDH) was tailor-made in situ on anionic cellulose beads to form a hybrid, supported photocatalyst for the first time. The hybrid beads were prepared in a size larger than the pulp fibers in order to make the catalysis reaction heterogeneous in nature. Hydrophilic pulp fibers were converted into hydrophobic pulp by photocatalytic topochemical grafting of ethyl acrylate using the LDH-cellulose bead catalyst. The approach identified for the modification of the pulp fibers is the "hydrogen abstraction-UV photografting" because the low-energy, UV radiation-induced grafting offers advantages, such as a reduced degradation of the backbone polymer and a control over the grafting reaction. After grafting, the pulp fibers showed increased water repellency and unaltered thermal stability, indicating the hydrophobic, plasticizing nature of the pulp, which in turn accounts for its thermoformable behavior. These acrylated pulp fibers can be further designed/customized for waterproof or oil absorption applications.

Amorphous-to-crystalline transition and photoluminescence switching in guest-absorbing metal-organic network thin films.

An amorphous metal-organic framework (aMOF) is an oxymoron as the porosity derived from the ordered network of the metal and organic moieties is the main characteristic of conventional crystalline MOFs. However, amorphous metal-organic materials can be synthesized from gaseous precursors through atomic/molecular layer deposition (ALD/MLD). We demonstrate an exciting interplay between luminescence properties and amorphous-to-crystalline transition realized upon water absorption in ALD/MLD aMOF films.

Preparation and characterization of nanocrystalline ZrO2:Yb3+,Er3+ up-conversion phosphors.

Nanocrystalline up-converting phosphors with zirconium oxide (ZrO(2)) as the host lattice were prepared with combustion and sol-gel methods. Impurities were analyzed with Fourier transform infrared (FT-IR) spectroscopy. Yb(3+) absorption was studied in the wave number region 10,000-11,500 cm(-1) at room temperature and at 10 K. The whole-blood absorption was measured in the region 9100-41,600 cm(-1) at room temperature. Up-conversion luminescence was excited at room temperature with an IR-laser at 977 nm. The up-conversion luminescence spectra showed red (650-685 nm) and green emission (520-560 nm) due to the (4)F(9/2) --> (4)I(15/2) and ((2)H(11/2), (4)S(3/2)) --> (4)I(15/2) transitions of Er(3+), respectively. The materials prepared with combustion synthesis were found to yield the most efficient up-conversion intensity and the longest luminescence decay.

Three- and Two-Photon NIR-to-Vis (Yb,Er) Upconversion from ALD/MLD-Fabricated Molecular Hybrid Thin Films.

We report blue, green, and red upconversion emissions with strongly angular-dependent intensities for a new type of hybrid (Y,Yb,Er)-pyrazine thin films realized using the atomic/molecular layer deposition thin-film fabrication technology. The luminescence emissions in our amorphous (Y,Yb,Er)-pyrazine thin films of a controllable nanothickness originate from three- and two-photon NIR-to-vis excitation processes. In addition to shielding the lanthanide ions from nonradiative de-excitation, the network of interconnected organic molecules serves as an excellent matrix for the Yb3+-to-Er3+ excitation energy transfer. This suggests a new approach to achieve efficient upconverting molecular materials with the potential to be used for next-generation medical diagnostics, waveguides, and surface-sensitive detectors.

Fast, low-cost preparation of hackmanite minerals with reversible photochromic behavior using a microwave-assisted structure-conversion method.

A microwave-assisted structure-conversion (MASC) method was used to obtain photochromic hackmanites (M,Na)8Al6Si6O24(Cl,S)2 (M: Li, Na, and K) in a fast (12 to 20 min) one-step process. Structural conversion from Zeolite A to hackmanite minerals has been proven to be very effective through an aluminosilicate crystalline intermediate. Photochromism is observed with both UV and X-ray (CuKα) excitation.