Synthesis of NaYF(4):Yb/Er/Gd up-conversion luminescent nanoparticles and luminescence resonance energy transfer-based protein detection

High-quality NaYF₄:Yb/Er/Gd up-conversion nanoparticles (UCNPs) were first synthesized by a solvothermal method using rare earth stearate, sodium fluoride, ethanol, water, and oleic acid as precursors. Doped Gd³⁺ ions can promote the transition of NaYF₄ from cubic to hexagonal phase, shorten the reaction time, and reduce the reaction temperature without reducing the luminescence intensity of NaYF₄:Yb/Er UCNPs. X-ray diffraction, infrared spectroscopy, transmission electron microscopy, and luminescence spectroscopy were applied to characterize the UCNPs. The nanoparticles exhibited small size and excellent green up-conversion photoluminescence, making them suitable for biological applications. After the surfaces of NaYF₄:Yb/Er/Gd UCNPs were modified with amino groups through the Stöber method, they could be brought close enough to the analytically important protein called R-phycoerythrin (R-PE) bearing multiple carboxyl groups so that energy transfer could occur. A luminescence resonance energy transfer (LRET) system was developed using NaYF₄:Yb/Er/Gd UCNPs as an energy donor and R-PE as an energy acceptor. As a result, a detection limit of R-PE of 0.5 μg/ml was achieved by the LRET system with a relative standard deviation of 2.0%. Although this approach was first used successfully to detect R-PE, it can also be extended to the detection of other biological molecules.     

Redox luminescence switch based on Mn2+‐doped NaYF4:Yb,Er upconversion nanorods

An redox luminescence switch was developed for the sensing of glutathione (GSH), l ‐cysteine (Cys) or l ‐ascorbic acid (AA) based on redox reaction. The Mn²⁺‐doped NaYF₄:Yb,Er upconversion nanorods (UCNRs) with an emission peak located in the red region were synthesized. The luminescence intensity of the UCNRs could be quenched due to the Mn²⁺ could be oxidized to MnO₂ by KMnO₄. Subsequently, when the AA, GSH or Cys was added into the MnO₂ modified upconversion nanosystem, which could reduced MnO₂ to Mn²⁺ and the luminescence intensity was recovered. The concentration ranges of the nanosystem are 0.500–3.375 mM (R² = 0.99) for AA, 0.6250–11.88 mM (R² = 0.99) for GSH and 0.6250–9.375 mM (R² = 0.99) for Cys, respectively.     

Synthesis and properties of (6,7-dimethoxy-4-coumaryl)alanine: a fluorescent peptide label.

The synthesis of racemic and l-(6,7-dimethoxy-4-coumaryl)alanine (Dmca) is described and some spectral and physicochemical properties are reported. The utility of Dmca as a highly sensitive and specific label for the quantitative detection of synthetic peptides in HPLC and in minimal essential media (MEM) is also described.     

Growth, thermal and spectral properties of Er3+-Doped and Er3+/Yb3+-Codoped Li3Ba2La3(WO4)8 crystals

This paper reports the growth and spectral properties of Er(3+)-doped and Er(3+)/Yb(3+)-codoped Li(3)Ba(2)La(3)(WO(4))(8) crystals. The Er(3+): Li(3)Ba(2)La(3)(WO(4))(8) crystal with dimensions of 56 mm × 28 mm × 9 mm and Er(3+)/Yb(3+): Li(3)Ba(2)La(3)(WO(4))(8) crystal with dimensions of 52 mm × 24 mm × 8 mm were obtained by the top-seeded solution growth (TSSG) method. Thermal expansion coefficients and thermal conductivity of both crystals were measured. The spectroscopic characterizations of both crystals were investigated. The spectroscopic analysis reveals that the Er(3+)/Yb(3+): Li(3)Ba(2)La(3)(WO(4))(8) crystal has much better optical properties than the Er(3+): Li(3)Ba(2)La(3)(WO(4))(8) crystal, thus it may become a potential candidate for solid-state laser gain medium material.     

Synthesis and characterization of a stable dispersion of multifunctional Gd2O3:Er,Yb in polyvinyl alcohol

A stable dispersion of multifunctional Gd₂O₃:Er,Yb phosphor in polyvinyl alcohol (PVA) was synthesized by varying the concentration of Yb³⁺ ions. It had a strong ultraviolet–visible‐near infrared (UV–vis) upconversion emission and applications in temperature and magnetic field sensors (e.g., nano‐heaters), as well as potential use in bioleveling and bioimaging. Stability of the dispersion was found to strongly depend on the mixing process of the powder in the polymer solution. Spherical shaped nanoparticles in cubic phase of ~ 43 nm diameter were synthesized and characterized by X‐ray diffraction; results were confirmed by scanning electron microscopy (SEM). Fourier transform infrared sspectroscopy (FT‐IR) and thermal analysis supported the presence of PVA. NIR pumping produced strong UC emission bands in the red and green regions extending up to very high UV (240 nm). This method provides an alternative for synthesizing a highly UC‐efficient non‐agglomerated pure transparent dispersion from various efficient phosphors for biological applications. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and study of optical properties of a Gd3+-doped NaYF4 phosphor for phototherapy lamp application

In recent trends, radiation falls under the narrowband ultraviolet-B region (305–315 nm) widely used in phototherapy lamp applications in the treatment of skin diseases. In this paper, we report a Gd³⁺-doped NaYF₄ luminescent material synthesized for the first time using the low-temperature co-precipitation method. It crystallized into a face-centred cubic structure, as confirmed by X-ray diffraction characterization techniques and Rietveld refinement. The photoluminescence property of the as-prepared sample shows a highly intense, sharp emission band obtained at 311 nm, which belongs to the narrowband ultraviolet-B region and corresponds to the transition of the ⁶P_7/2→⁸S_7/2 level of the Gd³⁺ ions under 272 nm excitation (⁸S_7/2 to ⁶I_J). The transitions of the Gd³⁺ ions are detected entirely with different concentrations of Gd³⁺ ions. Scanning electron microscopy analysis indicated that the average particle was 288 nm. The critical distance for energy transfer was calculated to be equal to 11.5017 Å. Dipole–dipole interaction is responsible for energy transfer, as analyzed by Dexter theory. These excellent optical characteristics, together with their highly efficient and low-cost synthesis approach, indicate that synthesized NaYF₄:Gd³⁺ phosphors have excessive potential for phototherapeutic lamp applications.     

Synthesis and evaluation of N-(4-benzylphenyl)piperazines as VGF inducers

A series of compounds was discovered that induce the production of VGF mRNA in SH-SY5Y cells and exhibit cytoprotection under tunicamycin induced endoplasmic reticulum (ER) stress. The aminophenol ring and linker chain of the template SUN N8075 (1) was modified to yield compounds with higher efficacy and lower propensity for adverse effects.     

Gas adsorption on the Zn-, Pd- and Os-doped armchair (5,5) single-walled carbon nanotubes

The adsorption of NO₂, NH₃, H₂O, CO₂ and H₂ gases on the undoped, Zn–, Pd– and Os–doped armchair (5,5) single–walled carbon nanotubes (SWCNTs) were studied using density functional method. The adsorptions of these five gases on the Zn–, Pd– and Os–doped SWCNTs are obviously stronger than on the undoped SWCNT and their adsorption abilities are in the same order: NO₂ > NH₃ > H₂O > CO₂ > H₂. Adsorption energies for all the studied gases on the undoped, Zn–, Pd– and Os–doped SWCNTs computed at the B3LYP/LanL2DZ level are reported.     

2-(4-Fluorophenyl)-quinazolin-4(3H)-one as a novel tyrosinase inhibitor: Synthesis,inhibitory activity,and mechanism

2-(4-Fluorophenyl)-quinazolin-4(3H)-one (FQ) was synthesized, and its structure was identified with ¹H nuclear magnetic resonance (¹H NMR), ¹³C nuclear magnetic resonance (¹³C NMR), fourier transform infrared spectroscopy (FTIR), and high resolution mass spectrometry (HRMS). From the enzyme analysis, the results showed that it could inhibit the diphenolase activity of tyrosinase (IC₅₀ = 120 ± 2 μM). Furthermore, the results of kinetic studies showed that the compound was a reversible mixed-type inhibitor, and that the inhibition constants were determined to be 703.2 (K_I) and 222.1 μM (K_IS). The results of fluorescence quenching experiment showed that the compound could interact with tyrosinase and the substrates (tyrosine and l-DOPA). Molecular docking analysis revealed that the mass transfer rate was affected by FQ blocking the enzyme catalytic center. In brief, current study identified a novel tyrosinase inhibitor which deserved further study for hyperpigmentation drugs.     

Synthesis of an amphiphilic poly(gamma-glutamic acid)-cholesterol conjugate and its application as an artificial chaperone

A poly(gamma-glutamic acid) (gammaPGA)-cholesterol conjugate was synthesized and the properties of an aqueous solution were evaluated. The conjugate showed amphiphilic nature derived from the hydrophilic gammaPGA backbone and the hydrophobic cholesterol side chain. The conjugate spontaneously formed nanoparticles in the aqueous solution of the low concentration, and the high concentration resulted in the formation of the physical gel. By utilizing the self-aggregating properties of the conjugate in water, an artificial chaperone was developed. The complex of protein with the nanoparticles of the conjugate was formed and the protein was released upon the dissociation of the nanoparticles by the addition of beta-cyclodextrin. For denatured carbonic anhydrase, the activity was recovered in the artificial chaperone of the nanoparticle conjugate.     

Synthesis and characterizations of amphiphilic poly(L-lactide)-grafted chondroitin sulfate copolymer and its application as drug carrier

In this investigation, new biodegradable brush-like amphiphilic copolymers were synthesized by ring opening polymerization. Poly(L-lactide) (PLLA) was grafted onto chondroitin sulfate (CS), which is one of the physiologically significant specific glycosaminoglycans (GAGs), using a tin octanoate [Sn(Oct)2] catalyst in DMSO. The hydroxyl groups of the chondroitin sulfate were used as initiating groups. These functional groups enable specific mucoadhesion or receptor recognition. The degree of substitution (DS), the degree of polymerization (DP) and the chondroitin sulfate content (from 1.1 to 15.4%) were analyzed by 1H NMR. The characteristics of these grafted copolymers, including the structure, the thermal properties and biodegradability, etc., were examined with respect to CS content. Meanwhile, the amphiphilic core (PLLA)-corona (CS) nanoparticles, with size smaller than 200 nm, was examined by dynamic light scattering (DLS). Zeta potential analysis exhibited the value in the range -18.3 to -49.4 mV. The morphologies of the nanoparticles were observed by field-emission scanning electron microscopy (FE-SEM). The nanoparticles with lower cytotoxicity were examined by MTT assay. Furthermore, the in vitro BSA release kinetics of those CSn-PLLA nanoparticles was also determined in this study.     

Noncovalent and covalent functionalization of a (5, 0) single-walled carbon nanotube with alanine and alanine radicals

We have systematically investigated the noncovalent and covalent adsorption of alanine and alanine radicals, respectively, onto a (5, 0) single-walled carbon nanotube using first-principles calculation. It was found that XH···π (X = N, O, C) interactions play a crucial role in the non-ovalent adsorption and that the functional group close to the carbon nanotube exhibits a significant influence on the binding strength. Noncovalent functionalization of the carbon nanotube with alanine enhances the conductivity of the metallic (5, 0) nanotube. In the covalent adsorption of each alanine radical onto a carbon nanotube, the binding energy depends on the adsorption site on CNT and the electronegative atom that binds with the CNT. The strongest complex is formed when the alanine radical interacts with a (5, 0) carbon nanotube through the amine group. In some cases, the covalent interaction of the alanine radical introduces a half-filled band at the Fermi level due to the local sp ³ hybridization, which modifies the conductivity of the tube.     

Abnormal expression and processing of keratins in pupoid fetus (pf/pf) and repeated epilation (Er/Er) mutant mice

The pupoid fetus (pf) and repeated epilation (Er) mutations of mice result in a failure of epidermal differentiation in homozygotes. Expression of the epidermal keratins has been followed in pf/pf and Er/Er mice by two-dimensional gel electrophoresis, and by immunohistochemistry and Western blotting using polyclonal antibodies that are monospecific for individual keratin polypeptides. Our results show that expression of the differentiation-specific keratins (K1 and K10) is delayed in both the pf/pf and Er/Er mutants and that, when these keratins do appear later in development, they are localized in the deeper layers of the thickened mutant epidermis. Conversely, K6 and K16, two keratins found in low abundance in normal epidermis, are abundant in mutant epidermis. In newborn mutant epidermis, K6 and K16 are found to be most abundant in the outermost epidermal cells, a distribution opposite to that of K1 and K10. These findings suggest that the expression of these hyperplastic keratins in mutant mice may occur to the exclusion of the differentiation-specific keratins both during development and in newborn animals. Differentiation, and an apparently normal pattern of keratin expression, occur when whole pf/pf or Er/Er skin is grafted to normal mice. These results suggest that the pf and Er genes may be expressed systemically and that transfer of the mutant skin to a "normal" environment results in the recovery of a normal phenotype.     

Symmetrical bis-(NHC) palladium(II) complexes: Synthesis, structure, and application in catalysis

The synthesis and characterization of symmetrically substituted bis-N-heterocyclic carbene palladium(II) complexes with a functional group attached to the bridging moiety is described, as well as the immobilization of one of them on polystyrene Wang resin. The resulting complexes were tested both in homogeneous and heterogeneous Suzuki-Miyaura cross-coupling reactions.     

Synthesis of graft copolymer (CgOH-g-AGA): Physicochemical properties, characterization and application

A graft copolymer of κ-carrageenan and 2-acrylamidoglycolic acid (CgOH-g-AGA) was synthesized via free radical polymerization initiated by potassium peroxymonosulphate/malonic acid redox pair. For affording maximum percentage of grafting, optimum conditions were determined by varying the concentrations of κ-carrageenan, 2-acrylamidoglycolic acid, potassium peroxymonosulphate, malonic acid, hydrogen ion, time and temperature. The swelling, metal ion uptake and flocculation studies were investigated with water, three metals (Ni(2+), Pb(2+) and Zn(2+)) solutions, coal (coking and non-coking) suspensions, respectively. Both, polymer backbone and its corresponding graft copolymer samples were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis.     

On the elastic properties of single-walled carbon nanotubes/poly(ethylene oxide) nanocomposites using molecular dynamics simulations

Molecular dynamics simulations are used to study the physical and mechanical properties of single-walled carbon nanotubes/poly(ethylene oxide) nanocomposites. The effects of nanotube atomic structure, diameter, and volume fraction on the polymer density distribution, polymer atom distribution, stress–strain curves of nanocomposites and Young’s, and shear moduli of single-walled carbon nanotubes/poly(ethylene oxide) nanocomposites are explored. It is shown that the density of polymer, surrounding the nanotube surface, has a peak near the nanotube surface. However, increasing distance leads to dropping it to the value near the density of pure polymer. It is seen that for armchair nanotubes, the average polymer atoms distances from the single-walled carbon nanotubes are larger than the polymer atom distance from zigzag nanotubes. It further is shown that zigzag nanotubes are better candidates to reinforce poly (ethylene oxide) than their armchair counterparts.     

Sulfonamide-based 4-anilinoquinoline derivatives as novel dual Aurora kinase (AURKA/B) inhibitors: Synthesis,biological evaluation and in silico insights

Aurora kinases (AURKs) were identified as promising druggable targets for targeted cancer therapy. Aiming at the development of novel chemotype of dual AURKA/B inhibitors, herein we report the design and synthesis of three series of 4-anilinoquinoline derivatives bearing a sulfonamide moiety (5a-d, 9a-d and 11a-d). The % inhibition of AURKA/B was determined for all target quinolines, then compounds showed more than 50% inhibition on either of the enzymes, were evaluated further for their IC₅₀ on the corresponding enzyme. In particular, compound 9d displayed potent AURKA/B inhibitory activities with IC₅₀ of 0.93 and 0.09 µM, respectively. Also, 9d emerged as the most efficient anti-proliferative analogue in the US-NCI anticancer assay toward the NCI 60 cell lines panel, with broad spectrum activity against different cell lines from diverse cancer subpanels. Docking studies, confirmed that, the sulfonamide SO₂ oxygen was involved in a hydrogen bond with Lys162 and Lys122 in AURKA and AURKB, respectively, whereas, the sulfonamide NH could catch hydrogen bond interaction with the surrounding amino acid residues Lys141, Glu260, and Asn261 in AURKA and Lys101, Glu177, and Asp234 in AURKB. Furthermore, N1 nitrogen of the quinoline scaffold formed an essential hydrogen bond with the hinge region key amino acids Ala213 and Ala173 in AURKA and AURKB, respectively.     

Synthesis and evaluation of 4-(substituted styryl/alkenyl)-3,5-bis(4-hydroxyphenyl)-isoxazoles as ligands for the estrogen receptor

A series of 3,5-bis (4-hydroxyphenyl) isoxazoles bearing a styryl/alkyl vinyl group at the 4-position were prepared and evaluated as ligands for the estrogen receptor-alpha (ERα). The target compounds were prepared using the Suzuki reaction to couple an iodo-isoxazole intermediate with a series of styryl/alkenyl boronic acids, followed by O-demethylation. The products were evaluated for their estrogen receptor-α ligand binding domain (ERα-LBD) binding affinity using a competitive binding assay. The 4-(4-hydroxystyryl) derivative 4h displays binding properties similar to those of the previously described pyrazole class of ER ligands, indicating that the ERα-LBD tolerates the presence of the added vinyl group at the 4-position of the isoxazole ring.