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 C60, C70, 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. Interestingly, the profiles of IR-PAS spectra for graphene and CNTs exhibit negative bands using carbon black as the reference; the negative spectral information may provide valuable knowledge about the storage energy, production, structure, defect, or impurity of graphene and CNTs. Thus, this approach may open a new avenue for analyzing carbon materials.

Synthesis of Two-Dimensional (Cu-S)n 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)n MOF 2D nanosheets, significantly increasing production quantity and reducing reaction time compared to traditional autoclave methods. The (Cu-S)n MOF 2D nanosheets with the unique coordination of Cu(I) stabilized in Cu-based MOFs demonstrate impressive activity in mimicking natural peroxidase. The active sites of the peroxidase-like activity of (Cu-S)n MOF 2D nanosheets were predominantly verified as Cu(I) rather than Cu(II) of other Cu-based MOFs. The cost-effective and long-term stability of (Cu-S)n MOF 2D nanosheets make them suitable for practical applications. Furthermore, the inhibition of the peroxidase-like activity of (Cu-S)n MOF nanosheets by glutathione (GSH) could provide a simple strategy for colorimetric detection of GSH against other amino acids. This work remarkably extends the utilization of (Cu-S)n MOF 2D nanosheets in biosensing, revealing the potential for 2D (Cu-S)n MOFs.

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. To adjust the photocatalytic oxidation ability, DAPy and CBPy were designed and synthesized based on the enhancement and diminishment of the intramolecular charge transfer (ICT) process, respectively. Kinetic studies revealed that DAPy and CBPy both exhibited highly efficient photo-activated oxidase-like activity with 3,3',5,5'-tetramethylbenzidine (TMB) as the substrate, which were in good accordance with their molecular engineering to promote either type I or type II reactive oxygen species (ROS) generation. Impressively a colorimetric method based on the visible light induced oxidase-like activity of molecular rotors was developed to determine the environmental temperature for the first time. Both DAPy and CBPy showed distinct sensitivities toward temperature as compared with several molecular rotors based on the typical fluorimetric detection. This work provides a new strategy for the application of molecular rotors to overcome the non-emissive challenge in temperature sensing.

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. Here, we report a new method, called dual-concentration ratio method, for quantifying the binding affinity of fluorescent probes and human serum albumin (HSA). Temperature-dependent fluorescence intensity ratios of a one-to-one complex (L ⋅ HSA) for a turn-on fluorescent probe (L), e. g., ThT (thioflavin T) or DG (dansylglycine), with HSA at two different values of [L]0 /[HSA]0 under the constraint [HSA]0 >[L]0 were collected. The van't Hoff analysis on these association constants further resulted in the thermodynamic properties. Since only two samples at different [L]0 /[HSA]0 are required without the need of [L]0 /[HSA]0 at a wide range, the dual-concentration ratio method is an easy way to greatly reduce the amounts of fluorescent probes and proteins, as well as the acquisition time.

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

A rare in situ-generated mononuclear rhenium complex [Re(bpt)(CO)3(NH3)] (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 Re2(CO)10, 2-cyanopyridine and hydrazine with an in situ formed bpt ligand through cyclization via 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. Interestingly, the emission from 1 could be quenched by the addition of metal ions such as Ni2+ and Cu2+ but the emission efficiently recovered with the introduction of histidine. However, histidine could only be selectively detected when a combination of compound 1 and Ni2+ was used. Therefore, the luminescence response of the Ni2+-modified compound 1 could be utilized as a "turn-on" probe for the selective detection of histidine. This work provides a simple method for developing new sensing platforms of a discrete metal complex based on rare in situ generation.

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. Importantly, both BSA and human serum albumin (HSA) could enhance the peroxidase-like activity of Cu2+, which provided a new sensing platform for distinguishing BSA and HSA from other thiol-containing biomolecules. The PET quenchers could also manipulate the peroxidase-like activity of polyvinylpyrrolidone-stabilized gold nanoparticles (PVP-AuNPs), which exhibited some opposite results between PVP-AuNPs and BSA-AuNCs. The opposite effects on BSA-AuNCs and PVP-AuNPs were speculated to highly depend on their surface properties. Our findings offer an efficient strategy for tuning the peroxidase-like activities of gold-based nanozymes.

Self-Supplying O2 through the Catalase-Like Activity of Gold Nanoclusters for Photodynamic Therapy against Hypoxic Cancer Cells.

Photodynamic therapy (PDT) typically involves oxygen (O2 ) 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-NH2 ) can produce O2 for PDT via their intrinsic catalase-like activity. The AuNCs-NH2 not only show optimum H2 O2 consumption via the catalase-like activity over the physiological pH range (i.e., pH 4.8-7.4), but also extend such activity to acidic conditions. The possible mechanism is deduced from that the enriched tertiary amines of dendrimers are easily protonated in acidic solutions to facilitate the preadsorption of OH on the metal surface, thereby favorably triggering the catalase-like reaction. By taking advantage of the exciting feature on AuNCs-NH2 , the possibility to supply O2 via the catalase-like activity of AuNCs-NH2 for PDT against hypoxia of cancer cells was further studied. This proof-of-concept study provides a simple way to combine current O2 -dependent cancer therapy of PDT to overcome cancer cell hypoxia, thus achieving more effective anticancer treatments.

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. Surprisingly, the methylated form of AuNCs-NH2 (i.e., MAuNCs-N(+) R3 , where R = H or CH3 ) results in a dramatic recovery of the intrinsic peroxidase-like activity while blocking most primary and tertiary amines (1°- and 3°-amines) of dendrimers to form quaternary ammonium ions (4°-amines). However, the hidden peroxidase-like activity is also found in hydroxyl-terminated dendrimer-encapsulated AuNCs (AuNCs-OH, inside backbone with 3°-amines), indicating that 3°-amines are dominant in mediating the peroxidase-like activity. The possible mechanism is further confirmed that the enrichment of polymeric 3°-amines on the surface of dendrimer-encapsulated AuNCs provides sufficient suppression of the critical mediator •OH for the peroxidase-like activity. Finally, it is demonstrated that AuNCs-NH2 with diminished cytotoxicity have great potential for use in primary neuronal protection against oxidative damage.

Interactions of nitroxide radicals with dendrimer-entrapped Au8-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 Au8-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. The quenching mechanism associated with the interactions between Au8-clusters and nitroxide radicals was explored by combined fluorescence and electron paramagnetic resonance (EPR) studies. The controlled quenching of the fluorescent Au8-cluster can be developed as a turn-on fluorescence probe for sensing ascorbic acid (AA) in living cells.

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. When 2-PyT is released via the cleavage of disulfide bonds by biothiols, the PET process from the Au8-cluster to 2-PyT is initiated, resulting in fluorescence quenching. The fluorescence intensity was found to decrease linearly with glutathione (GSH) concentration (0-1500µM) at physiological relevant levels and the limit of detection for GSH was 15.4µM. Compared to most nanoparticle-based fluorescent probes that are limited to detect low molecular weight thiols (LMWTs; i.e., GSH and cysteine), the ultrasmall Au8-cluster-based probe exhibited less steric hindrance and can be directly applied in selectively and sensitively detecting both LMWTs and high molecular weight thiols (HMWTs; i.e., protein thiols). Based on such sensing platform, the surface-functionalized Au8-cluster has significant promise for use as an efficient nanoprobe for intracellular fluorescence imaging of biothiols including protein thiols in living cells whereas other nanoparticle-based fluorescent probes cannot.

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. GA, a porous polysaccharide, can not only provide a confined space in which to produce uniform Au-SNPs (1.6 ± 0.7 nm in diameter), but can also facilitate the formation of Au-SNPs@GA (diameter ≈ 40 nm) after irradiating synchrotron X-rays. Specifically, the Au-SNPs@GA possesses high thermal stability and a strong photothermal effect for killing cancer cells. Importantly, a bioclearance study demonstrated that the Au-SNPs@GA can be gradually excreted by the renal and hepatobiliary system, which might be due to the breakdown and oxidation of GA under irradiating synchrotron X-rays. Thus, the novel gold nanocomposite can be promising photothermal agents for cancer treatment at the therapeutic level, minimizing toxicity concerns regarding long-term accumulation in vivo.

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. The fluorescent hydroxylamine was selectively oxidised by OCl(-) to form a labile oxoammonium cation that underwent further degradation. Without using any troublesomely synthetic steps, the novel sensing platform based on the fragmentation of PAMAM dendrimers, can be applied to detect OCl(-) in macrophage cells. The results suggest that the sensing approach may be useful for the detection of intracellular OCl(-) with minimal interference from biological matrixes.

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. This article reviews recent progress in bringing these nanoparticle-modulated energy transfer schemes to fruition for applications in biosensing, molecular imaging and drug delivery.

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. J. Newby, C. W. Müller, H. D. Lee, T. S. Zwier, J. Phys. Chem. A, 2008, 112, 9454.) to support extensive Duschinsky mixing among its four lowest-frequency out-of-plane normal coordinates Q(45)-Q(48) in the S(1)<-- S(0), i.e. (L(a)) A (1)A'<-- X (1)A', electronic transition. The complexity of this mixing is considerably increased relative to that of its parent styrene due to the longer conjugated side chain. Here we quantitatively analyze this change of the motional character of the four non-totally symmetric vibrations upon electronic excitation. The peak intensities of 182 overtone and combination transitions spread over seven SVLF spectra were fit simultaneously with seven parameters in an automated least-squares fitting procedure in which an unweighted least-squares sum was minimized using a pattern search algorithm. The seven parameters consisted of the six Duschinsky rotation angles and the S(1) frequency of normal mode nu(48). The required four-dimensional Franck-Condon overlap integrals were calculated using previously reported recursion relations between harmonic oscillator wavefunctions. As a consistency check, the intensities of all possible 434 electric dipole allowed overtone and combination bands of normal modes nu(45)-nu(48) up to individual vibrational quantum numbers of v = 4 were simulated. The comparison with the experimental intensities revealed with few exceptions very good agreement. The results of the Duschinsky analysis are discussed in light of the pi-pi* electronic excitation as represented by different ab initio (HF, CIS, CASSCF), density functional (B3LYP and BP86) and time-dependent density functional (TD-B3LYP and TD-BP86) methods. Our Duschinsky mixing analysis reveals a challenging complexity that is not quantitatively reproduced by widely used excited state quantum chemical methods. The sensitivity of Duschinsky mixing coefficients to both excited state equilibrium geometries and force fields thus provides a valuable benchmark for the improvement of excited state quantum chemical methods.

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. Ab initio and density functional theory calculations have been used to show that the most likely source of the nonradiative process is from the interaction of the pi pi* state with a close lying pi sigma* state whose minimum energy structure is bent along the terminal CCH group. Ultraviolet population transfer spectroscopy has been used to probe the extent to which excited-state isomerization is facilitated by the interaction with the pi sigma* state. In ultraviolet population transfer spectroscopy, each isomer was selectively excited to vibronic levels in the S(1) state with energies above and below the threshold for fluorescence quenching. The ultraviolet-excited populations are then recooled to the zero point levels using a reaction tube designed to constrain the supersonic expansion and increase the collision cooling capacity of the expansion. The new isomeric distribution was detected in a downstream position using resonant-2-photon ionization spectroscopy. From these spectra, relative isomerization quantum yields were calculated as a function of excitation energy. While the fluorescence quantum yield drops by a factor of 50-100, the isomerization quantum yields remain essentially constant, implying that the nonradiative process does not directly involve isomerization. On this basis, we postulate that isomerization occurs on the ground-state potential energy surface after internal conversion. In these experiments, the isomerization to naphthalene was not observed, implying a competition between isomerization and cooling on the ground-state potential energy surface.

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. The double-resonance technique of ultraviolet depletion (UVD) spectroscopy was used to show that there are strong absorptions in Z-PVA that are not observed in the LIF spectrum due to the turn of a nonradiative process in this electronic state. The LIF and UVD spectra were compared quantitatively to calculate the relative single vibronic level fluorescence quantum yields. Upon inspection, there are some indications of state specific effects; however, the nature of these effects is unclear. Ab initio and density functional theory calculations of the ground and excited states were used to map the first two excited states of Z-PVA along the C[triple bond]CH bending coordinate, determining them to be pi pi* and pi sigma*, respectively, in character. The crossing of these two states is postulated to be the underlying reason for the observed loss in fluorescence intensity 600 cm(-1) above the pi pi* origin. The spectroscopy of Z-PVA has been compared to the previously characterized E isomer of phenylvinylacetylene [Liu, C. P., Newby, J. J., Muller, C. W., Lee, H. D. and Zwier, T. S. J. Phys. Chem. A 2008, 112 (39), 9454.].

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. The excitation and emission spectra show that the molecule is planar with C(s) symmetry in both the ground and excited states. Torsional potentials were simulated from the observed torsional structure in the excitation and emission spectra. The S(0) potential (V(2) = 1237 cm(-1), V(4) = -256 cm(-1)) is associated with a flat-bottomed potential supporting large inter-ring angular changes with little cost in energy (+/-36 degrees at 200 cm(-1)), with a barrier of 1237 cm(-1) at the perpendicular geometry. The S(1) potential is much stiffer about the planar geometry, with a calculated barrier five times larger than in S(0) (V(2) = 6732 cm(-1), V(4) = -477 cm(-1)). Based on the torsional assignments, weak bands in the same frequency region assigned earlier to the structural isomer phenylcyclopenta-1,4-diene [J. J. Newby, J. A. Stearns, C. P. Liu and T. S. Zwier, J. Phys. Chem. A, 2007, 111, 10914-10927] have been re-assigned as hot bands arising from v'' = 1 in the inter-ring torsion, nu(57).

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)). Much of the vibronic structure is similar to that of styrene and other singly substituted benzene derivatives, with Franck-Condon (FC) activity predominantly in substituent-sensitive benzene modes. Sizeable FC progressions were also found in the inter-ring torsion, reflecting a large displacement in the inter-ring angle upon electronic excitation. No evidence for FC activity in the ring-puckering coordinate is observed. The torsional potentials of the ground and excited states were determined from the experimental transition frequencies by fitting the calculated to the experimental torsional frequency spacings in an automated least-squares fitting procedure. The S(1) torsional potential is a symmetric single-well potential centered around a locally planar equilibrium geometry at a torsional angle of varphi = 0 degrees . The energy levels are reproduced by a cosine term potential function with torsional parameters V(2) = 3765 cm(-1) and V(4) = -183 cm(-1). The S(0) torsional potential possesses a twisted equilibrium geometry that is strongly asymmetric about varphi = 0 degrees due to the non-planarity of the cyclopentene ring. The best-fit potential parameters uses a sin/cos potential function (odd/even), with V = 948 cm(-1), V = -195 cm(-1), V = -162 cm(-1) and V = -268 cm(-1). The shape of the potentials are similar to those predicted by relaxed potential energy scans calculated at the DFT, CIS and TDDFT//CIS levels of theory. The change in the torsional angle varphi upon electronic excitation was determined to be approximately 15 degrees from fits of the displacement delta of the S(0) torsional potential with respect to the S(1) potential. The simulated shift of the S(0) potential with respect to the S(1) potential of approximately 15 degrees is in very good agreement with that obtained from B3LYP calculations.

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. RESULTS: The results showed that the MPI-sC has satisfactory face and content validity, feasibility, acceptable internal consistency reliability (overall Cronbach's alpha of 0.75), and overall support of theoretical assumptions. However, instead of the four-factor structure of the original instrument, we found a three-factor structure (with pain intensity and pain interference merged into one factor) that explained 76.73% of the variance. Close to half the patients (48.1%) had considerable levels of pain interference, and a majority (72.6%) reported not having control in life based on the cut-point of MPI-sC categorization. CONCLUSION: Our results support the brief MPI-sC as a feasible and valid tool for assessing and representing multidimensional pain experiences in terminal cancer patients. The MPI-sC could help clinicians and researchers assess the complex multidimensional pain experiences of terminal cancer patients, including Chinese-speaking cancer populations.