Photoinduced charge transfer in Zn(II) and Au(III)-ligated symmetric and asymmetric bacteriochlorin dyads: A computational study.

The excited-state properties and photoinduced charge-transfer (CT) kinetics in a series of symmetrical and asymmetrical Zn- and Au-ligated meso-meso-connected bacteriochlorin (BChl) complexes are studied computationally. BChl derivatives, which are excellent near-IR absorbing chromophores, are found to play a central role in bacterial photosynthetic reaction centers but are rarely used in artificial solar energy harvesting systems. The optical properties of chemically linked BChl complexes can be tuned by varying the linking group and involving different ligated metal ions. We investigate charge transfer in BChl dyads that are either directly linked or through a phenylene ring (1,4-phenylene) and which are ligating Zn or Au ions. The directly linked dyads with a nearly perpendicular arrangement of the BChl units bear markedly different properties than phenylene linked dyads. In addition, we find that the dielectric dependence of the intramolecular CT rate is very strong in neutral Zn-ligated dyads, whereas cationic Au-ligated dyads show negligible dielectric dependence of the CT rate. Rate constants of the photo induced CT process are calculated at the semiclassical Marcus level and are compared to fully quantum mechanical Fermi's golden rule based values. The rates are calculated using a screened range separated hybrid functional that offers a consistent framework for addressing environment polarization. We study solvated systems in two solvents of a low and a high scalar dielectric constant.

The value of local normal limits in quantitative Thallium-201 CZT MPI SPECT.

BACKGROUND: Considering the distinctive characteristics of CZT detectors, automatic quantification of ischemia using normal limits included with software package may deliver suboptimal results for CAD detection. The present study aims to evaluate the benefits of creating normal limits specific to a local population and laboratory protocol. METHODS AND RESULTS: Two groups were selected from patients who had undergone a CZT MPI. Normal limits were generated with the QPS application based on the population with low likelihood of CAD. Using the vendor-supplied and the population-specific normal limits i-TPD and vessel-specific SDS results obtained for patients who had subsequently undergone coronary angiography were compared with coronary angiography data. A weak correlation was observed for low i-TPD (stress TPD minus rest TPD) and SDS values. Both databases gave similar values for the area under the ROC curve concerning i-TPD (0.75 to 0.74) and SDS results (0.72 to 0.75 for the LAD, 0.62 to 0.64 for the LCx, and 0.63 to 0.67 for the RCA). Sensitivity (60%), specificity (78%), and predictive positive (84%) and negative (52%) values were also similar with a diagnostic and prognostic threshold value. CONCLUSION: The use of a population-specific created database did not influence the diagnostic value of thallium-201 MPI QPS results using a CZT camera.

Comparison of the prognostic value of myocardial perfusion imaging using a CZT-SPECT camera with a conventional anger camera.

BACKGROUND: Recent studies have shown that myocardial perfusion imaging (MPI) in cadmium-zinc-telluride (CZT) cameras allow faster exams with less radiation dose but there are little data comparing its prognosis information with that of dedicated cardiac Na-I SPECT cameras OBJECTIVE: The objective of this study is to compare the prognostic value of MPI using an ultrafast protocol with low radiation dose in a CZT-SPECT and a traditional one. METHODS: Group 1 was submitted to a two-day MIBI protocol in a conventional camera, and group 2 was submitted to a 1-day MIBI protocol in CZT camera. MPI were classified as normal or abnormal, and perfusion scores were calculated. Propensity score matching methods were performed RESULTS: 3554 patients were followed during 33±8 months. Groups 1 and 2 had similar distribution of age, gender, body mass index, risk factors, previous revascularization, and use of pharmacological stress. Group 1 had more abnormal scans, higher scores than group 2. Annualized hard events rate was higher in group 1 with normal scans but frequency of revascularization was similar to normal group 2. Patients with abnormal scans had similar event rates in both groups CONCLUSION: New protocol of MPI in CZT-SPECT showed similar prognostic results to those obtained in dedicated cardiac Na-I SPECT camera, with lower prevalence of hard events in patients with normal scan.

Value of attenuation correction in stress-only myocardial perfusion imaging using CZT-SPECT.

BACKGROUND: Attenuation correction (AC) improves the diagnostic outcome of stress-only myocardial perfusion imaging (MPI) using conventional SPECT. Our aim was to determine the value of AC using a cadmium zinc telluride-based (CZT)-SPECT camera. METHODS AND RESULTS: We retrospectively included 107 consecutive patients who underwent stress-optional rest MPI CZT-SPECT/CT. Next, we created three types of images for each patient; (1) only displaying reconstructed data without the CT-based AC (NC), (2) only displaying AC, and (3) with both NC and AC (NC + AC). Next, two experienced physicians visually interpreted these 321 randomized images as normal, equivocal, or abnormal. Image outcome was compared with all hard events over a mean follow-up time of 47.7 ± 9.8 months. The percentage of images interpreted as normal increased from 45% using the NC images to 72% using AC and to 67% using NC + AC images (P < .001). Hard event hazard ratios for images interpreted as normal were not different between using NC and AC (1.01, P = .99), or NC and NC + AC images (0.97, P = .97). CONCLUSIONS: AC lowers the need for additional rest imaging in stress-first MPI using CZT-SPECT, while long-term patient outcome remained identical. Use of AC reduces the need for additional rest imaging, decreasing the mean effective dose by up to 1.2 mSv.

Performance of cardiac cadmium-zinc-telluride gamma camera imaging in coronary artery disease: a review from the cardiovascular committee of the European Association of Nuclear Medicine (EANM).

The trade-off between resolution and count sensitivity dominates the performance of standard gamma cameras and dictates the need for relatively high doses of radioactivity of the used radiopharmaceuticals in order to limit image acquisition duration. The introduction of cadmium-zinc-telluride (CZT)-based cameras may overcome some of the limitations against conventional gamma cameras. CZT cameras used for the evaluation of myocardial perfusion have been shown to have a higher count sensitivity compared to conventional single photon emission computed tomography (SPECT) techniques. CZT image quality is further improved by the development of a dedicated three-dimensional iterative reconstruction algorithm, based on maximum likelihood expectation maximization (MLEM), which corrects for the loss in spatial resolution due to line response function of the collimator. All these innovations significantly reduce imaging time and result in a lower patient's radiation exposure compared with standard SPECT. To guide current and possible future users of the CZT technique for myocardial perfusion imaging, the Cardiovascular Committee of the European Association of Nuclear Medicine, starting from the experience of its members, has decided to examine the current literature regarding procedures and clinical data on CZT cameras. The committee hereby aims 1) to identify the main acquisitions protocols; 2) to evaluate the diagnostic and prognostic value of CZT derived myocardial perfusion, and finally 3) to determine the impact of CZT on radiation exposure.

Synthesis of asymmetric zinc(II) phthalocyanines with two different functional groups & spectroscopic properties and photodynamic activity for photodynamic therapy.

Zinc(II) phthalocyanine containing [2-(tert-butoxycarbonyl)amino]ethoxy and iodine groups (A and B), as well as their deprotected mono-amino and tri-iodine zinc(II) phthalocyanine (2) were obtained. This structure surrounds by substituents with functional groups. From this perspective it can be used a starting material for many reactions and applications, such as sonogashira coupling, carbodiimide coupling. An example of a first diversification reaction of this compound was obtained with conjugation of a biotin. Asymmetrically biotin conjugated and heavy atom bearing zinc(II) phthalocyanine (3) were synthesized characterized for the first time and photophysical, photochemical and photobiological properties of these phthalocyanines were compared in this study.

An Electrostatically Self-Assembled Thin Film Made of Zn-Substituted Tungstoborate and Rhodamine B with Photoelectrochemical Properties.

An electrostatically self-assembled multilayer thin film consisting of alternating layers of Keggin polyoxometalate of Zn-substituted tungstoborate (BW11Zn) and Rhodamine B (RhB) has successfully been prepared on a quartz and indium-tin oxide (ITO) glass substrate. The ultraviolet-visible (UV-vis) absorption spectra demonstrated that the electrostatically self-assembled film of (BW11Zn/RhB)n was uniformly deposited layer by layer, and the RhB molecules in the film formed the J-aggregation. The photoelectrochemical investigations showed that the films generated stable cathodic photocurrents that originated from RhB, and the maximal cathodic photocurrent density generated by an eight-layer film was 4.9 µA/cm2 while the film was irradiated with 100 mW/cm2 polychromatic light of 730 nm > λ > 325 nm at an applied potential of 0 V versus a saturated calomel electrode.

Development and validation of a patient-tailored dose regime in myocardial perfusion imaging using CZT-SPECT.

BACKGROUND: Guidelines for SPECT myocardial perfusion imaging (MPI) traditionally recommend a fixed tracer dose. Yet, clinical practice shows degraded image quality in heavier patients. The aim was to optimize and validate the tracer dose and scan time to obtain a constant image quality less dependent on patients' physical characteristics. METHODS: 125 patients underwent Cadmium Zinc Telluride (CZT)-SPECT stress MPI using a fixed Tc-99m-tetrofosmin tracer dose. Image quality was scored by three physicians on a 4-point grading scale and related to the number of photon counts normalized to tracer dose and scan time. Counts were correlated with various patient-specific parameters dealing with patient size and weight to find the best predicting parameter. From these data, a formula to provide constant image quality was derived, and subsequently tested in 92 new patients. RESULTS: Degradation in image quality and photon counts was observed for heavier patients for all patients' specific parameters (P < .01). We found body weight to be the best-predicting parameter for image quality and derived a new dose formula. After applying this new body weight-depended tracer dose and scan time in a new group, image quality was found to be constant (P > .19) in all patients. CONCLUSIONS: Also in CZT SPECT image quality decreases with weight. The use of a tracer dose and scan time that depends linearly on patient's body weight corrected for the varying image quality in CZT-SPECT MPI. This leads to better radiation exposure justification.

3D iteratively reconstructed spatial resolution map and sensitivity characterization of a dedicated cardiac SPECT camera.

BACKGROUND: A solid-state cadmium zinc telluride (CZT) SPECT device provides ultrafast myocardial perfusion imaging (MPI) with a spherical field-of-view (FOV). This study aims at determining the spatial resolution and sensitivity throughout this FOV as a guide for patient positioning. METHODS AND RESULTS: For this CZT camera (Discovery 570c, GE Healthcare), the iteratively reconstructed spatial resolution along 3 Cartesian axes was compared (average resolution 6.9 ± 1.0 mm full-width at half-maximum) using a 2 dimensional array of point sources in air which was aligned with a transverse plane shifted throughout the FOV. Sensitivity was plotted in the central transverse slice and axially in locations comparable to the placement of the heart in 266 rest/stress cardiac studies (M 78, age 63 ± 13 years). The average sensitivity was 0.46 ± 0.19 kc/s/MBq with a transverse gradient of 0.039 ± 0.001 kc/s/MBq/cm (8.9% of the sensitivity per cm). Reconstructed relative activity was uniform (uniformity <9%) and count rate was linear (R = 0.999) over 3 orders of magnitude. CONCLUSIONS: The CZT SPECT camera offers good resolution, sensitivity, and uniformity, and provides linearity in count rate. A gradient of >8%/cm in sensitivity justifies the crucial role of patient positioning with the heart closest to the detector.

Gated tomographic radionuclide angiography using cadmium-zinc-telluride detector gamma camera; comparison to traditional gamma cameras.

PURPOSE: Estimation of left ventricular ejection fraction (LVEF) with equilibrium 99MTc-HSA equilibrium radionuclide angiography (MUGA) is frequently used for assessing cardiac function. The purpose of this study was to compare intra- and interobserver variation between three different gamma cameras. MATERIALS AND METHODS: Eighty-two patients, scanned in the same sequential order on the three cameras. Each acquisition was analyzed twice by two technologists. Inter- and intraobserver variations were calculated as the coefficient of variation and the 95% confidence interval for limits of agreement between each sequence of analyses for each of the three cameras. RESULTS: The lowest intraobserver variations in LVEF for the two NaI-detector cameras were 3.1% (-4.0% to 3.5%) for the planar and 3.4% (-4.2% to 4.5%) for SPECT (P ≤ 0.001-0.019), the highest result for the CZT SPECT camera was 2.6% (-2.9% to 3.1%). Similarly, interobserver variation was 4.8% (-4.8% to 6.4%) and 4.9% (-5.4% to 7.5%), respectively, for each of the NaI-detector cameras and 3.3% (-3.4% to 4.3%) for the CZT SPECT camera (P ≤ 0.001-0.008). DISCUSSION: The CZT detector camera was superior to both NaI detector cameras regarding intra- and interobserver variation. The CZT SPECT camera may identify changes in LVEF with greater certainty than its NaI detector-equipped counterparts.

Recent advances in nanosized Mn-Zn ferrite magnetic fluid hyperthermia for cancer treatment.

This paper reviews the recent research and development of nanosized manganese zinc (Mn-Zn) ferrite magnetic fluid hyperthermia (MFH) for cancer treatment. Mn-Zn ferrite MFH, which has a targeted positioning function that only the temperature of tumor tissue with magnetic nanoparticles can rise, while normal tissue without magnetic nanoparticles is not subject to thermal damage, is a promising therapy for cancer. We introduce briefly the composition and properties of magnetic fluid, the concept of MFH, and features of Mn-Zn ferrite magnetic nanoparticles for MFH such as thermal bystander effect, universality, high specific absorption rate, the targeting effect of small size, uniformity of hyperthermia temperature, and automatic temperature control and constant temperature effect. Next, preparation methods of Mn-Zn ferrite magnetic fluid are discussed, and biocompatibility and biosecurity of Mn-Zn ferrite magnetic fluid are analyzed. Then the applications of nanosized Mn-Zn ferrite MFH in cancer are highlighted, including nanosized Mn-Zn ferrite MFH alone, nanosized Mn-Zn ferrite MFH combined with As2O3 chemotherapy, and nanosized Mn-Zn ferrite MFH combined with radiotherapy. Finally, the combination application of nanosized Mn-Zn ferrite MFH and gene-therapy is conceived, and the challenges and perspectives for the future of nanosized Mn-Zn ferrite MFH for oncotherapy are discussed.

Saturation of the free carrier absorption in ZnTe crystals.

This study systematically investigates the influence of free carriers on the generation of THz in ZnTe crystals, over a wide range of pumping fluences. As the pumping fluence is increased (< 6.36 mJ/cm(2)), the concentration of free carriers gradually increases and the THz output power is saturated, as clearly demonstrated by the time delay in the THz temporal waveforms, the changes in the THz spectral weight and the red-shift in the PL spectra. For high pumping fluences (> 6.36 mJ/cm(2)), spectacularly, there is a significant quadratic increase in the THz output power when the pumping fluence is increased, as well as at low pumping fluences of < 0.58 mJ/cm(2), because of the saturation of free carriers.

Fabrication of high-quality ZnTe nanowires toward high-performance rigid/flexible visible-light photodetectors.

ZnTe is an important p-type semiconductor with great applications as field-effect transistors and photodetectors. In this paper, individual ZnTe nanowires based field-effect transistors was fabricated, showing evident p-type conductivity with an effect mobility of 11.3 cm(2)/Vs. Single ZnTe nanowire based photodetectors on rigid silicon substrate exhibited high sensitivity and excellent stability to visible incident light with responstivity and quantum efficiency as high as 1.87 × 10(5) A/W and 4.36 × 10(7)% respectively and are stable in a wide temperature range (25-250 °C). The polarization-sensitivity of the ZnTe nanowires was studied for the first time. The results revealed a periodic oscillation with the continuous variation of polarization angles. Besides, flexible photodetectors were also fabricated with the features of excellent flexibility, stability and sensitivity to visible incident light. Our work would enable application opportunities in using ZnTe nanowires for ultrahigh-performance photodetectors in scientific, commercial and industrial applications.

Synthesis and photocatalytic properties of ZnWO4 nanocrystals via a fast microwave-assisted method.

High crystallinity of ZnWO4 nanoparticles has been successfully synthesized via a highly effective and environmentally friendly microwave route by controlling the reaction time and temperature. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and Fourier infrared spectrum (FT-IR). The crystallinity was enhanced with the increase of the reaction temperature and time. The photocatalytic activities of ZnWO4 nanocrystals were evaluated by testing the photodegradation of rhodamine B (RhB) dye under ultraviolet (UV) light irradiation. The results indicated that as-prepared ZnWO4 was highly effective for the degradation of RhB. The degradation rate of RhB reached 98.01% after 6 h of UV illumination.

Effects of pH value of the electrolyte and glycine additive on formation and properties of electrodeposited Zn-Fe coatings.

Environmentally friendly and cyanide-free sulfate bath under continuous current and the corrosion behavior of electrodeposits of zinc-iron alloys were studied by means of electrochemical tests in a solution of 3.5% NaCl in presence and absence of glycine. The effects of pH on the quality of Zn-Fe coatings were investigated in order to improve uniformity and corrosion protection performance of the coating films. The deposit morphology was analyzed using scanning electron microscopy (SEM), and X-ray diffraction (XRD) was used to determine the preferred crystallographic orientations of the deposits. It was found that the uniformity and corrosion resistance of Zn-Fe coating films were strongly associated with pH of the coating electrolyte. To obtain the effect of pH on the film quality and corrosion performances of the films, the corrosion test was performed with potentiodynamic anodic polarization method. It was also observed that uniformity and corrosion resistivity of the coating films were decreased towards pH = 5 and then improved with increasing pH value of the electrolyte. The presence of glycine in the plating bath decreases the corrosion resistance of Zn-Fe coatings.

Zinc coproporphyrin I derived from meconium has an antitumor effect associated with singlet oxygen generation.

INTRODUCTION: Zinc coproporphyrin I (ZnCP-I) is a photosensitive molecule and a major component of meconium. Here, we examined the effects of ZnCP-I as a potential photosensitizer in photodynamic therapy for tumors. MATERIALS AND METHODS: (1) Aqueous ZnCP-I was irradiated with a pulsed YAG-SHG laser (wavelength: 532 nm)/YAG-SHG dye laser (wavelength: 566 nm). (2) HeLa cells were incubated in 200 mM ZnCP-I, and accumulation of ZnCP-I in HeLa cells was evaluated with ZnCP-I-specific fluorescence over 500 nm. (3) Aqueous ZnCP-I was administered intravenously to HeLa tumor-bearing mice at a dose of 10.2 mg/kg body weight. The tumors were irradiated with a filtered halogen lamp (wavelength: 580 nm) at 100 J/cm(2) 20 min after administration. RESULTS: (1) An intense near-infrared emission spectrum was observed at around 1,270 nm after irradiation. The emission intensity was proportional to the laser power between 10 and 80 mW and was completely inhibited by addition of NaN3, a singlet oxygen scavenger. (2) ZnCP-I-specific fluorescence was detected in the HeLa cell cytoplasm. (3) Irradiated tumors treated with ZnCP-I were mostly necrotized. CONCLUSION: ZnCP-I accumulated in tumor cells, produced singlet oxygen upon irradiation, and necrotized the tumor cells. These results suggest that ZnCP-I may be an effective photosensitizer.

Thermal stability of embedded metal nanoparticles elongated by swift heavy ion irradiation: Zn nanoparticles in a molten state but preserving elongated shapes.

Solid Zn and V nanoparticles (NPs) embedded in silica were elongated by swift heavy ion (SHI) irradiation with 200 MeV Xe(14+) ions to a fluence of 5.0 × 10(13) ions cm(-2). Isochronal annealing was carried out in a vacuum from 200 to 1000 °C in steps of 100 °C for 10 min each. The degree of shape elongation was evaluated at room temperature (RT) by two different optical methods: linear dichroism spectroscopy and birefringence spectroscopy. In the as-irradiated state, the samples showed an absorption band at 5 eV due to radiation-induced defects in the silica in addition to the anisotropic absorption due to the elongated metal NPs. After annealing at 400 °C the defect band had completely disappeared, while the degree of shape elongation was almost unchanged or rather slightly increased in both the Zn and V NPs. The elongation of the Zn NPs slightly decreased but maintained a certain value after annealing at 500 °C, which is much higher than the melting point (MP) of Zn NPs (~420 °C). This observation indicates that shape elongation is mostly maintained even if the Zn NPs are in the molten state to some extent during annealing. The elongation of the Zn NPs was almost eliminated after annealing at 600 °C. In the case of the V NPs, elongation was maintained up to 800 °C but mostly eliminated at 900 °C. Since the recovery temperature of 900 °C from the elongated to the spherical shape is much lower than the MP of bulk V (1890 °C), we consider that the elongation is eliminated without melting of V NPs, i.e. via solid state mass transportation. The melting of NPs is not the key factor for the recovery to the spherical shape.

Effect of ultrasonic frequency and power on the sonodynamic therapy activity of cationic Zn(II) phthalocyanines.

We report on the sonodynamic activity of cationic phthalocyanines (Pcs) and the effect of the variation of two parameters: ultrasound frequency and power (Par I (1 MHz, 1 W cm-2), Par II (1 MHz, 2 W cm-2), Par III (3 MHz, 1 W cm-2) and Par IV (3 MHz, 2 W cm-2)) on the efficiency of their reactive oxygen species generation and cancer eradication in vitro thereof. Where Par stands for the various combinations of these parameters. Four Pcs were investigated with substituents bearing diethylamine, ortho- and para-pyridine and morpholine groups. Overall, the para-pyridine and morpholine Pcs showed substantial sono-activity in the various ultrasound parameters with Par I and IV generally showing better singlet oxygen and hydroxyl radicals generation confirmed by electron paramagnetic resonance spectroscopy. In some cases, very high hydroxyl radicals' generation was observed at Par II. Furthermore, the fragmentation of the Pcs after Par II treatments was confirmed using UV-vis and magnetic circular dichroism spectroscopy. The reactive species generation efficacy decreased at Par III for all samples. Ultrasound assisted cytotoxicity of the Pcs was confirmed in vitro using the human (Michigan Cancer Foundation-7) breast cancer cell line.

Zn and N Codoped TiO2 Thin Films: Photocatalytic and Bactericidal Activity.

We explore a series of Zn and N codoped TiO2 thin films grown using chemical vapor deposition. Films were prepared with various concentrations of Zn (0.4-2.9 at. % Zn vs Ti), and their impact on superoxide formation, photocatalytic activity, and bactericidal properties were determined. Superoxide (O2•-) formation was assessed using a 2,3-bis(2-methoxy-4-nitro-5-sulfophenyl)-5-[(phenylamino)carbonyl]-2H-tetrazolium sodium salt (XTT) as an indicator, photocatalytic activity was determined from the degradation of stearic acid under UVA light, and bactericidal activity was assessed using a Gram-negative bacterium E. coli under both UVA and fluorescent light (similar to what is found in a clinical environment). The 0.4% Zn,N:TiO2 thin film demonstrated the highest formal quantum efficiency in degrading stearic acid (3.3 × 10-5 molecules·photon-1), while the 1.0% Zn,N:TiO2 film showed the highest bactericidal activity under both UVA and fluorescent light conditions (>3 log kill). The enhanced efficiency of the films was correlated with increased charge carrier lifetime, supported by transient absorption spectroscopy (TAS) measurements.

Emissive oxidase-like nanozyme based on an organic molecular cage.

In this study, we introduced four "claw-like" units of dipicolylamine (DPA) to a tetraphenylethylene (TPE)-based organic molecular cage (DPA-TPE-Cage). Coordinated with Zn2+ ions, the obtained ZnDPA-TPE-Cage exhibited aggregation induced emission (AIE) effects and oxidase-like properties, which endowed it with the ability to selectively image and kill Gram-positive bacteria S. aureus efficiently.