An exceptional water stable terbium-based metal-organic framework for selective detection of pesticides.

A terbium-based metal-organic framework (MOF) with exceptional water stability for highly selective detection of pesticide thiamethoxam (TMX) in aqueous solution is reported. To date, most reported lanthanide metal-organic frameworks (Ln-MOFs) still exhibit poor water stability, which may limit their practical applications in bio-sensing and detecting pollutants in environmental water samples. In this work, a Tb-MOF [Tb(BDC)(DEF)·0.

Analysis of Carbon Materials with Infrared Photoacoustic Spectroscopy.

Measurement of infrared spectroscopy has emerged as a significant challenge for carbon materials due to the sampling problem. To overcome this issue, in this work, we performed measurements of IR spectra for carbon materials including C, C, diamond powders, graphene, and carbon nanotubes (CNTs) using the photoacoustic spectroscopy (PAS) technique; for comparison, the vibrational patterns of these materials were also studied with a conventional transmission method, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, or Raman spectroscopy. We found that the IR photoacoustic spectroscopy (IR-PAS) scheme worked successfully for these carbon materials, offering advantages in sampling.

Synthesis of Two-Dimensional (Cu-S) Metal-Organic Framework Nanosheets Applied as Peroxidase Mimics for Detection of Glutathione.

Facilely synthesized peroxidase-like nanozymes with high catalytic activity and stability may serve as effective biocatalysts. The present study synthesizes peroxidase-like nanozymes with multinuclear active sites using two-dimensional (2D) metal-organic framework (MOF) nanosheets and evaluates them for their practical applications. A simple method involving a one-pot bottom-up reflux reaction is developed for the mass synthesis of (Cu-S) MOF 2D nanosheets, significantly increasing production quantity and reducing reaction time compared to traditional autoclave methods.

Molecular Engineering to Boost the Photo-Oxidase Activity of Molecular Rotors in Colorimetric Sensing of Temperatures.

Some organic dyes and photosensitizers with strong visible absorption can behave as photo-responsive oxidase mimics. However, the relationship between the photo-oxidase activity and molecular structure remains unclear to date. In this work, a new type of photosensitizer with the characteristics of molecular rotors, namely DPPy, served as the molecular scaffold for further investigation.

Noncovalent Association Thermodynamics of Turn-On Fluorescent Probes with Human Serum Albumin: Dual-Concentration Ratio Method.

Efficient quantification of the affinity of a drug and the targeted protein is critical for strategic drug design. Among the various molecules, turn-on fluorescent probes are the most promising signal transducers to reveal the binding strength and site-specificity of designed drugs. However, the conventional method of measuring the binding ability of turn-on fluorescent probes by using the fractional occupancy under the law of mass action is time-consuming and a massive sample is required.

A neutral mononuclear rhenium(I) complex with a rare -generated triazolyl ligand for the luminescence "turn-on" detection of histidine.

A rare -generated mononuclear rhenium complex [Re(bpt)(CO)(NH)] (1, bpt = 3,5-bis(2-pyridyl)-1,2,4-triazolate) can be used as a "turn-on" luminescent probe for selectively sensing L-histidine against other amino acids. Compound 1 was prepared by reacting Re(CO), 2-cyanopyridine and hydrazine with an formed bpt ligand through cyclization C-N and N-N couplings with its single-side chelating mode arrayed with respect to the Re center. Compound 1 was highly stable and showed a green light MLCT emission in DMF solution at 507 nm upon excitation at 360 nm.

Fluorescence Quenchers Manipulate the Peroxidase-like Activity of Gold-Based Nanomaterials.

Although the regulation of the enzyme-like activities of nanozymes has stimulated great interest recently, the exploration of modulators makes it possible to enhance the catalytic performance of nanozymes, though doing so remains a big challenge. Herein, we systemically studied the effects of fluorescence quenchers on the peroxidase-like activity of bovine serum albumin-stabilized gold nanoclusters (BSA-AuNCs) based on photoinduced electron transfer (PET). We found that PET quenchers can not only quench the fluorescence of BSA-AuNCs but also regulate their intrinsic peroxidase-like activity.

Self-Supplying O through the Catalase-Like Activity of Gold Nanoclusters for Photodynamic Therapy against Hypoxic Cancer Cells.

Photodynamic therapy (PDT) typically involves oxygen (O ) consumption and therefore suffers from greatly limited anticancer therapeutic efficacy in tumor hypoxia. Here, it is reported for the first time that amine-terminated, PAMAM dendrimer-encapsulated gold nanoclusters (AuNCs-NH ) can produce O for PDT via their intrinsic catalase-like activity. The AuNCs-NH not only show optimum H O consumption via the catalase-like activity over the physiological pH range (i.

Tailoring Enzyme-Like Activities of Gold Nanoclusters by Polymeric Tertiary Amines for Protecting Neurons Against Oxidative Stress.

The cytotoxicity of nanozymes has drawn much attention recently because their peroxidase-like activity can decompose hydrogen peroxide (H2 O2 ) to produce highly toxic hydroxyl radicals (•OH) under acidic conditions. Although catalytic activities of nanozymes are highly associated with their surface properties, little is known about the mechanism underlying the surface coating-mediated enzyme-like activities. Herein, it is reported for the first time that amine-terminated PAMAM dendrimer-entrapped gold nanoclusters (AuNCs-NH2 ) unexpectedly lose their peroxidase-like activity while still retaining their catalase-like activity in physiological conditions.

Interactions of nitroxide radicals with dendrimer-entrapped Au-clusters: a fluorescent nanosensor for intracellular imaging of ascorbic acid.

When gold nanoparticles (AuNPs) become extremely small (<2 nm in diameter) as gold nanoclusters (AuNCs), an intriguing issue is whether the interactions of free radicals with AuNCs would be essentially different at sufficiently small size. Herein, we report for the first time that the fluorescence of a polyamidoamine (PAMAM) dendrimer-entrapped Au-cluster is quenched by the paramagnetic nitroxide radical. Based on an upward curving Stern-Volmer plot, the system shows complex fluorescence quenching with a combination of static and dynamic quenching processes.

Live-cell imaging of biothiols via thiol/disulfide exchange to trigger the photoinduced electron transfer of gold-nanodot sensor.

Biothiols have been reported to involve in intracellular redox-homeostasis against oxidative stress. In this study, a highly selective and sensitive fluorescent probe for sensing biothiols is explored by using an ultrasmall gold nanodot (AuND), the dendrimer-entrapped Au8-cluster. This strategy relies upon a thiol/disulfide exchange to trigger the fluorescence change through a photoinduced electron transfer (PET) process between the Au8-cluster (as an electron donor) and 2-pyridinethiol (2-PyT) (as an electron acceptor) for sensing biothiols.

In-situ formation and assembly of gold nanoparticles by gum arabic as efficient photothermal agent for killing cancer cells.

Gold nanoparticles (AuNPs) have been established to sufficiently eradicate tumors by means of heat production for photothermal therapy. However, the translation of the AuNPs from bench to the clinic still remains to be solved until realizing high bioclearance after treatment. Herein, we developed a simple strategy for simultaneous formation and assembly of small-size gold nanoparticles (Au-SNPs) to form a novel nanocomposite in the presence of gum arabic (GA) by synchrotron X-ray irradiation in an aqueous solution within 5 min.

Fluorescent hydroxylamine derived from the fragmentation of PAMAM dendrimers for intracellular hypochlorite recognition.

Herein, a promising sensing approach based on the structure fragmentation of poly(amidoamine) (PAMAM) dendrimers for the selective detection of intracellular hypochlorite (OCl(-)) is reported. PAMAM dendrimers were easily disrupted by a cascade of oxidations in the tertiary amines of the dendritic core to produce an unsaturated hydroxylamine with blue fluorescence. Specially, the novel fluorophore was only sensitive to OCl(-), one of reactive oxygen species (ROS), resulting in an irreversible fluorescence turn-off.

Recent advances in nanoparticle-based Förster resonance energy transfer for biosensing, molecular imaging and drug release profiling.

Förster resonance energy transfer (FRET) may be regarded as a "smart" technology in the design of fluorescence probes for biological sensing and imaging. Recently, a variety of nanoparticles that include quantum dots, gold nanoparticles, polymer, mesoporous silica nanoparticles and upconversion nanoparticles have been employed to modulate FRET. Researchers have developed a number of "visible" and "activatable" FRET probes sensitive to specific changes in the biological environment that are especially attractive from the biomedical point of view.

Duschinsky mixing between four non-totally symmetric normal coordinates in the S(1)-S(0) vibronic structure of (E)-phenylvinylacetylene: a quantitative analysis.

(E)-Phenylvinylacetylene was shown previously (C.-P. Liu, J.

Probing E/Z isomerization on the C10H8 potential energy surface with ultraviolet population transfer spectroscopy.

The excited-state dynamics of phenylvinylacetylene (1-phenyl-1-buten-3-yne, PVA) have been studied using laser-induced fluorescence spectroscopy, ultraviolet depletion spectroscopy, and the newly developed method of ultraviolet population transfer spectroscopy. Both isomers of PVA (E and Z) show a substantial loss in fluorescence intensity as a function of excitation energy. This loss in fluorescence was shown to be due to the turn-on of a nonradiative process by comparison of the laser-induced fluorescence spectrum to the ultraviolet depletion spectrum of each isomer, with a threshold 600 cm(-1) above the electronic origin in Z-PVA and 1000 cm(-1) above the electronic origin in E-PVA.

Spectroscopy and photophysics of structural isomers of naphthalene: Z-phenylvinylacetylene.

The fluorescence spectroscopy of Z-phenylvinylacetylene (Z-PVA) has been studied under jet-cooled conditions. The laser-induced fluorescence (LIF) spectrum shows vibronic activity up to 600 cm(-1) above the pi pi* electronic origin at 33 838 cm(-1). In contrast, the single vibronic level fluorescence spectrum of the electronic origin shows strong intensity in transitions ending in ground state levels at least 1200 cm(-1) above the ground state zero-point level.

Jet-cooled vibronic spectroscopy and asymmetric torsional potentials of phenylcyclopentene.

The ultraviolet spectroscopy of the S(1) <-- S(0) transition of 1-phenylcyclopentene (PCP) was studied by resonant-two-photon ionization (R2PI), laser-induced fluorescence (LIF) and single vibronic level fluorescence (SVLF). UV-UV hole-burning (UVHB) spectroscopy was used to determine that there is only one spectroscopically distinct conformer in the supersonic expansion. The excitation spectrum shows extensive vibronic structure extending to over 1000 cm(-1) above the electronic origin (34,646 cm(-1)).

Jet-cooled vibronic spectroscopy of potential intermediates along the pathway to PAH: phenylcyclopenta-1,3-diene.

The vibronic excitation spectrum of phenylcyclopenta-1,3-diene (PCP3D) has been recorded in a supersonic expansion using resonant-two-photon ionization (R2PI) and laser-induced fluorescence (LIF) techniques. The spectrum is dominated by the S(0)-S(1) origin transition (31,739 cm(-1)), with several low-frequency vibronic bands in the first 400 cm(-1), followed by a sharp cut-off in intensity due to turn-on of a non-radiative process. Single vibronic level fluorescence (SVLF) spectra were recorded for the S(1) origin and several vibronic bands of PCP3D.

Multidimensional Pain Inventory-Screening Chinese version (MPI-sC): psychometric testing in terminal cancer patients in Taiwan.

Introduction: Cancer pain is identified as a multidimensional experience, but relatively few brief instruments are available for assessing the complex pain-related experiences of terminal cancer patients in Taiwan. The purposes of this study were to (1) translate and examine the feasibility and psychometric characteristics of the eight-item Multidimensional Pain Inventory-Screening Chinese (MPI-sC) when used with patients having terminal cancer and (2) apply the MPI-sC to examine multidimensional pain-related experiences of terminal cancer patients in Taiwan.

Materials And Methods: The MPI-sC was tested in 106 terminal cancer inpatients at a hospice setting in Taipei.

Direct observation of single molecule conformational change of tight-turn paperclip DNA triplex in solution.

DNA triplex modulates gene expression by forming stable conformation in physiological condition. However, it is not feasible to observe this unique molecular structure of large molecule with 54 oligodeoxynucleotides directly by conventional nuclear magnetic approach. In this study, we observed directly single molecular images of paperclip DNA triplexes formation in a buffer solution of pH 6.

Spectroscopic characterization of structural isomers of naphthalene: (E)- and (Z)-phenylvinylacetylene.

Near-pure samples of (E)-phenylvinylacetylene ((E)-PVA) and (Z)-phenylvinylacetylene ((Z)-PVA) were synthesized, and their ultraviolet spectroscopy was studied under jet-cooled conditions. The fluorescence excitation and UV-UV holeburning (UVHB) spectra of both isomers were recorded. The S0-S1 origin of (E)-PVA occurs at 33,578 cm(-1), whereas that for (Z)-PVA occurs at 33,838 cm(-1), 260 cm(-1) above that for (E)-PVA.

Application of quality audit tools to evaluate care quality received by terminal cancer patients admitted to a palliative care unit.

Goals: We aimed to evaluate the palliative care quality for terminal cancer patients as a reference for prospective service improvements.

Patients And Methods: A prospective study was conducted to analyze the quality audit data collected from 1,476 samples in one medical center's palliative care unit. Lai's modified version of the support team assessment schedule was utilized for 2-year data collection, applying 17 categories of audit criteria rated on a scale of 0 to 4 (0-no symptoms, 4-significant symptoms).

Photochemical and discharge-driven pathways to aromatic products from 1,3-butadiene.

A detailed study of the photochemical and discharge-driven pathways taken by gas-phase 1,3-butadiene has been carried out. Photolysis or discharge excitation was initiated inside a short reaction tube attached to the outlet of a pulsed valve. Bath gas temperatures near 100 K were achieved in the reaction tube by the constrained expansion of the gas mixture into the tube, simulating temperatures of relevance in Titan's atmosphere.