Bioresponsive Nanoarchitectonics-Integrated Microneedles for Amplified Chemo-Photodynamic Therapy against Acne Vulgaris.

The excessive colonization of Propionibacterium acnes (P. acnes) is responsible for the genesis of acne vulgaris, a common inflammatory disease of skin. However, the conventional anti-acne therapies are always limited by various side effects, drug resistance, and poor skin permeability. Microneedles (MNs) are emerging topical drug delivery systems capable of noninvasively breaking through the skin stratum corneum barrier to efficiently enhance the transdermal drug penetration. Herein, MNs loaded with intelligent pH-sensitive nanoplatforms were constructed for amplified chemo-photodynamic therapy against acne vulgaris, jointly exerting antimicrobial and anti-inflammatory effects. The photosensitizer indocyanine green (ICG) was loaded into the zeolitic imidazolate framework-8 (ZIF-8) to improve its photostability, which would be triggered by 808 nm laser irradiation to generate cytotoxic reactive oxygen species (ROS) to result in oxidative damage and disturbed metabolic activities of P. acnes. In addition to the efficient drug delivery, the ZIF-8 carrier could selectively degrade in response to the acidic microenvironment of acne lesions, and the released Zn2+ also exhibited a potent antimicrobial activity. The fabricated ZIF-8-ICG@MNs presented an outstanding synergistic anti-acne efficiency both in vitro and in vivo. This bioresponsive microneedle patch is expected to be readily adapted as a generalized, modular strategy for noninvasive therapeutics delivery against superficial skin diseases.

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.

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.

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.

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.

Switching protein metalloporphyrin binding specificity by design from iron to fluorogenic zinc.

Metalloporphyrins play important roles in areas ranging from biology to nanoscience. Using computational design, we converted metalloporphyrin specificity of cytochrome b562 from iron to fluorogenic zinc. The new variant had a near total preference for zinc representing a switch in specificity, which greatly enhanced the negligible aqueous fluorescence of free ZnPP in vitro and in vivo.

Photocatalytic degradation of gemifloxacin antibiotic using Zn-Co-LDH@biochar nanocomposite.

The aim of the present study was to investigate the photocatalytic performance of biochar (BC)-incorporated Zn-Co-layered double hydroxide (LDH) nanostructures in gemifloxacin (GMF) degradation as a model pharmaceutical pollutant. The as-prepared Zn-Co-LDH@BC showed high photocatalytic efficiency due to the enhanced separation of photo-generated charge carriers using cobalt hydroxide as well as inhibiting the agglomeration of LDH nanostructures by incorporation of BC. According to the results, 92.7% of GMF was degraded through photocatalysis in the presence of Zn-Co-LDH catalyst. The photocatalytic performance of BC-incorporated Zn-Co-LDH was highly dependent on the solute concentration and photocatalyst dosage. The addition of ethanol caused more inhibiting effect than that of benzoquinone (BQ), indicating the major role of •OH in decomposition of GMF compared to the negligible role of O2•-. A greater enhancement in the photocatalytic degradation of GMF was obtained when the photoreactor containing Zn-Co-LDH@BC nanostructures was oxygenated. Less than 10% drop in the removal efficiency of GMF was observed within five successive operational runs. The results of chemical oxygen demand (COD) analysis indicated the COD removal efficiency of about 80% within 200 min, indicating the acceptable mineralization of GMF. The reaction pathways were also proposed for the photocatalytic conversion of GMF under UV light irradiation.

Direct Z-scheme 1D/2D WO2.72/ZnIn2S4 hybrid photocatalysts with highly-efficient visible-light-driven photodegradation towards tetracycline hydrochloride removal.

There are increasing environmental concerns of serious pollution from emission of antibiotic wastewater. Herein, a series of direct Z-scheme WO2.72/ZnIn2S4 (WOZIS) hybrid photocatalysts composed of one-dimensional (1D) WO2.72 (WO) nanorods and two-dimensional (2D) ZnIn2S4 (ZIS) nanosheets have been designed and constructed for tetracycline hydrochloride (TCH) degradation without presence of solid-state electron mediators. The crystalline phase, chemical composition, morphology, optical properties and photocatalytic activity of the as-prepared samples were characterized by the XRD, XPS, SEM, HRTEM, BET, UV-vis DRS, and PL. Obviously, all the WOZIS hybrid photocatalysts exhibited significantly enhanced photocatalytic activity towards TCH degradation. Meanwhile, WOZIS-1 sample with WO/ZIS molar ratio of 1:1 showed the highest photocatalytic activity. The significantly enhanced photoactivity of WOZIS hybrid photocatalyst was due to Z-scheme charge separation mechanism based on the build of tight interfacial contacts between WO nanorods and ZIS nanosheets, thereby driving efficient charge separation. Moreover, the high photocatalytic stability of as-prepared WOZIS-1 hybrid sample was revealed through seven successive cycling reactions.

A Parts Per Billion (ppb) Sensor for NO2 with Microwatt (µW) Power Requirements Based on Micro Light Plates.

A film of gas sensitive ZnO nanoparticles has been coupled with a low-power micro light plate (µLP) to achieve a NO2-parts-per-billion conductometric gas sensor operating at room temperature. In this µLP configuration, an InGaN-based LED (emitting at 455 nm) is integrated at a few hundred nanometers distance from the sensor material, leading to sensor photoactivation with well controlled, uniform, and high irradiance conditions, and very low electrical power needs. The response curves to different NO2 concentrations as a function of the irradiance displayed a bell-like shape. Responses of 20% to 25 ppb of NO2 were already observed at irradiances of 5 mWatts·cm-2 (applying an electrical power as low as 30 µW). In the optimum illumination conditions (around 60 mWatts·cm-2, or 200 µW of electric power), responses of 94% to 25 ppb were achieved, corresponding to a lower detection limit of 1 ppb of NO2. Higher irradiance values worsened the sensor response in the parts-per-billion range of NO2 concentrations. The responses to other gases such as NH3, CO, and CH4 were much smaller, showing a certain selectivity toward NO2. The effects of humidity on the sensor response are also discussed.

MONITORING OF HIGH-ENERGY PHOTON FLUENCE IN CLINAC USING Zn AND Cr PHOTOACTIVATION.

Monitoring of high-energy photon dose in radiation therapy is crucial for radiation protection, as well as to estimate the radiation effects in the operating microelectronic devices. The aim of this work was to investigate the possibility of using the photoactivation technique to monitor the high-energy photon fluence in the Varian 21EX 23MV CLINAC. The 52Cr(γ,n)51Cr and 66Zn(γ,n)65Zn reactions were used. It was found that 51Cr and 65Zn can be used successfully to monitor the fluence for short term (80 days) and long term (110 days), respectively.

Spectrum reconstruction method based on the detector response model calibrated by x-ray fluorescence.

Accurate estimation of distortion-free spectra is important but difficult in various applications, especially for spectral computed tomography. Two key problems must be solved to reconstruct the incident spectrum. One is the acquisition of the detector energy response. It can be calculated by Monte Carlo simulation, which requires detailed modeling of the detector system and a high computational power. It can also be acquired by establishing a parametric response model and be calibrated using monochromatic x-ray sources, such as synchrotron sources or radioactive isotopes. However, these monochromatic sources are difficult to obtain. Inspired by x-ray fluorescence (XRF) spectrum modeling, we propose a feasible method to obtain the detector energy response based on an optimized parametric model for CdZnTe or CdTe detectors. The other key problem is the reconstruction of the incident spectrum with the detector response. Directly obtaining an accurate solution from noisy data is difficult because the reconstruction problem is severely ill-posed. Different from the existing spectrum stripping method, a maximum likelihood-expectation maximization iterative algorithm is developed based on the Poisson noise model of the system. Simulation and experiment results show that our method is effective for spectrum reconstruction and markedly increases the accuracy of XRF spectra compared with the spectrum stripping method. The applicability of the proposed method is discussed, and promising results are presented.

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.

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.

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.

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.

The water soluble peripherally tetra-substituted zinc(ii), manganese(iii) and copper(ii) phthalocyanines as new potential anticancer agents.

In this study, [2-(2-morpholin-4-ylethoxy)ethoxy] group substituted zinc(ii), manganese(iii) and copper(ii) phthalocyanines 2-4 and their water soluble derivatives 2a, 3a and 4a were synthesized and the interactions of compounds 2a, 3a and 4a with CT-DNA and supercoiled pBR322 plasmid DNA were investigated. The results of binding experiments showed that these compounds were able to interact with CT-DNA via intercalative mode with a strong binding affinity in the order 3a > 2a > 4a. DNA-photocleavage activities of compounds 2a, 3a and 4a were determined. These compounds cleaved supercoiled pBR322 plasmid DNA efficiently under irradiation at 650 nm for 2a and 4a, and at 750 nm for 3a. These compounds displayed remarkable inhibitory activities against topoisomerase I enzyme in a dose-dependent manner. All of these results suggest that these phthalocyanines might be suitable anticancer agents due to their strong binding affinities, significant cleavage activities and effective topoisomerase I inhibition.

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.

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.

Clinical significance of right ventricular activity on treadmill thallium-201 myocardial single-photon emission computerized tomography using cadmium-zinc-telluride cameras.

OBJECTIVE: Identification of right ventricular (RV) abnormalities is important in patients with suspected coronary artery disease (CAD). RV activity can be better visualized on myocardial single-photon emission computerized tomography (SPECT) using a higher sensitivity cadmium-zinc-telluride (CZT) detector. The aim of this study was to investigate the clinical significance of RV/left ventricular (LV) uptake ratios during exercise thallium-201 SPECT using CZT detectors. PATIENTS AND METHODS: A total of 102 patients underwent treadmill ECG-gated SPECT, coronary angiography, and echocardiography. SPECT myocardial perfusion was interpreted using a 17-segment model and a 0-4-point scale. RV/LV uptake ratios were calculated on the basis of maximum counts per pixel within the entire RV and LV walls. The relationships between RV/LV uptake ratio and gated SPECT, presence of CAD (≥50% stenosis in the left main or ≥70% in the main branches), demographics, and echocardiographic parameters were analyzed. RESULTS: Stress RV/LV ratios correlated positively with the presence of left main or multivessel disease, and tricuspid regurgitation maximum pressure gradient. After multivariate regression, stress/rest RV/LV ratios correlated positively with mitral flow deceleration time, age, female sex, and use of ß-blockers. CONCLUSION: RV/LV uptake ratios on the basis of exercise myocardial perfusion SPECT imaging using CZT cameras are useful for the detection of severe CAD and could serve as an indicator of pulmonary hypertension and LV diastolic dysfunction.

Application of a CZT detector to in situ environmental radioactivity measurement in the Fukushima area.

Instead of conventional Ge semiconductor detectors and NaI(Tl) scintillation spectrometers, an application of a CdZnTe semiconductor (CZT) whose crystal has the dimension of 1 cm cubic to the in situ environmental radioactivity measurement was attempted in deeply affected areas in Fukushima region. Results of deposition density on soil for (134)Cs/(137)Cs obtained seemed consistent, comparing obtained results with those measured by the Japanese government.