9-Cyanopyronin probe palette for super-multiplexed vibrational imaging.

Multiplexed optical imaging provides holistic visualization on a vast number of molecular targets, which has become increasingly essential for understanding complex biological processes and interactions. Vibrational microscopy has great potential owing to the sharp linewidth of vibrational spectra. In 2017, we demonstrated the coupling between electronic pre-resonant stimulated Raman scattering (epr-SRS) microscopy with a proposed library of 9-cyanopyronin-based dyes, named Manhattan Raman Scattering (MARS). Herein, we develop robust synthetic methodology to build MARS probes with different core atoms, expansion ring numbers, and stable isotope substitutions. We discover a predictive model to correlate their vibrational frequencies with structures, which guides rational design of MARS dyes with desirable Raman shifts. An expanded library of MARS probes with diverse functionalities is constructed. When coupled with epr-SRS microscopy, these MARS probes allow us to demonstrate not only many versatile labeling modalities but also increased multiplexing capacity. Hence, this work opens up next-generation vibrational imaging with greater utilities.

On the production of ancient Egyptian blue: Multi-modal characterization and micron-scale luminescence mapping.

The ancient pigment Egyptian blue has long been studied for its historical significance; however, recent work has shown that its unique visible induced luminescent property can be used both to identify the pigment and to inspire new materials with this characteristic. In this study, a multi-modal characterization approach is used to explore variations in ancient production of Egyptian blue from shabti statuettes found in the village of Deir el-Medina in Egypt (Luxor, West Bank) dating back to the New Kingdom (18th-20th Dynasties; about 1550-1077 BCE). Using quantitative SEM-EDS analysis, we identify two possible production groups of the Egyptian blue and demonstrate the presence of multiple phases within samples using cluster analysis and ternary diagram representations. Using both macro-scale non-invasive (X-rays fluorescence and multi-spectral imaging) and micro-sampling (SEM-EDS and Raman confocal microspectroscopy) techniques, we correlate photoluminescence and chemical composition of the ancient samples. We introduce Raman spectroscopic imaging as a means to capture simultaneously visible-induced luminesce and crystal structure and utilize it to identify two classes of luminescing and non-luminescing silicate phases in the pigment that may be connected to production technologies. The results presented here provide a new framework through which Egyptian blue can be studied and inform the design of new materials based on its luminescent property.

Post-synthesis strategy to integrate porphyrinic metal-organic frameworks with CuS NPs for synergistic enhanced photo-therapy.

Multifunctional nanotheranostic systems with both therapeutic and imaging functions are highly desired for the development of more effective and less toxic anti-tumor drugs. Herein, a simple but effective method is reported to fabricate a novel PCN-CuS-FA-ICG-based nanoplatform for dual-modal imaging-guided synergistic photothermal/photodynamic therapy. Porphyrinic metal-organic frameworks with CuS NPs are obtained in aqueous solution via a simple post-synthesis strategy. Furthermore, to obtain a more effective therapy, indocyanine green (ICG) was incorporated into the multifunctional theranostic platform to promote the photothermal therapeutic effect. The as-prepared PCN-CuS-FA-ICG not only exhibits an excellent 1O2 generation efficiency under 650 nm irradiation to achieve remarkable photodynamic cell killing, but also presents outstanding photothermal conversion under 808 nm irradiation to destroy tumor tissues by hyperthermia. In particular, the nanotherapeutic agent realized fluorescence and thermal imaging dual-modal imaging-guided cancer treatment. Meanwhile, in vivo experiments confirmed the evident accumulation of nanoparticles (NPs) at local tumors, and tumor growth was inhibited obviously via synergistic photothermal/photodynamic therapy with negligible side effects.

Biogenic approach to synthesize rod shaped Gd2 O3 nanoparticles and its optimization using response surface methodology-Box-Behnken design model.

The rare earth metal oxide nanoparticles such as gadolinium oxide nanoparticles (Gd2 O3 NPs) have been synthesized by green synthesis process using methanolic extract of Moringa oleifera (M oleifera) peel. In this process, the Gd2 O3 NPs formation was observed at 280-300 nm in UV-Vis spectroscopy. The XRD pattern of the synthesized Gd2 O3 NPs was exactly matched with JCPDS No 3-065-3181which confirms the crystalline nature of Gd2 O3 NPs. In addition, Energy-dispersive X-ray spectroscopy (EDX) analysis was stated that Gd and O elements were present as 70.31 and 29.69%, respectively in Gd2 O3 NPs. The SEM and TEM analysis were said Gd2 O3 NPs are in rod shape and 26 ± 2 nm in size. Further the synthesized Gd2 O3 NPs were confirmed by X-ray photoemission spectroscopy (XPS). The synthesized Gd2 O3 NPs were further examined for anti-fungal activity against Alternaria saloni (A saloni) and Sclerrotium rolfsii (S rolfsii) and it showed moderate activity. Also, Gd2 O3 NPs evaluated as good antibacterial agent against different Gram +ve and Gram -ve bacteria. Moreover, the toxicity of the Gd2 O3 NPs on red blood cells (RBCs) of the human blood was determined using hemolytic assay, the obtained results were stated the synthesized Gd2 O3 NPs are nontoxic to the human erythrocytes. The photocatalytic activity against malachite green (MG) dye was tested and confirmed as 92% of dye was degraded within 2 hr by Gd2 O3 NPs. The results were stated the green synthesized Gd2 O3 NPs are good anti-fungal agents, nontoxic and we can use as a photocatalyst. Copyright © 2019 John Wiley & Sons, Ltd.

Application of quadrupole-Orbitrap high-resolution mass spectrometry in rapid screening and identification of synthetic dyes in herbal medicines.

In this work, a method combining ultra-high performance liquid chromatography and hybrid quadrupole-Orbitrap high-resolution mass spectrometry (HR-MS) was developed and validated for use in the simultaneous screening, identification, and quantification of 21 synthetic dyes in herbal medicines. To optimize the chromatographic conditions, we used a combined Full mass scan and data-dependent MS/MS (Full MS/dd-MS2) approach in positive and negative ion mode. Under this mode, selected ions with given fragmentation energy were subjected to a dd-MS2 scan following a Full MS scan. The selectivity of this method was effectively improved using 70,000 full width at half maximum mass resolution and narrow mass window (typically 5 ppm), and a single injection was sufficient for simultaneous identification and quantification of 21 synthetic dyes within 10 min. The combined method was fully validated and complies with all criteria for selectivity, sensitivity, calibration curve linearity, accuracy, precision, recovery, matrix effect, and stability. All analytes showed excellent linear relationships as all the coefficients of determination (r2) are greater than 0.9978 over wide ranges of concentrations (e.g. 1.0-500 ng/mL for sunset yellow). The validated method was employed to detect synthetic dyes in herbal medicines and was demonstrated to provide a reliable technical basis for drug regulation and public health protection.

Biofunctionalized prussian blue nanoparticles for multimodal molecular imaging applications.

Multimodal, molecular imaging allows the visualization of biological processes at cellular, subcellular, and molecular-level resolutions using multiple, complementary imaging techniques. These imaging agents facilitate the real-time assessment of pathways and mechanisms in vivo, which enhance both diagnostic and therapeutic efficacy. This article presents the protocol for the synthesis of biofunctionalized Prussian blue nanoparticles (PB NPs)--a novel class of agents for use in multimodal, molecular imaging applications. The imaging modalities incorporated in the nanoparticles, fluorescence imaging and magnetic resonance imaging (MRI), have complementary features. The PB NPs possess a core-shell design where gadolinium and manganese ions incorporated within the interstitial spaces of the PB lattice generate MRI contrast, both in T1 and T2-weighted sequences. The PB NPs are coated with fluorescent avidin using electrostatic self-assembly, which enables fluorescence imaging. The avidin-coated nanoparticles are modified with biotinylated ligands that confer molecular targeting capabilities to the nanoparticles. The stability and toxicity of the nanoparticles are measured, as well as their MRI relaxivities. The multimodal, molecular imaging capabilities of these biofunctionalized PB NPs are then demonstrated by using them for fluorescence imaging and molecular MRI in vitro.

Synthesis, thermal and spectral characterization of nanosized Ni(x)Mg(1-x)Al2O4 powders as new ceramic pigments via combustion route using 3-methylpyrozole-5-one as fuel.

New Ni(x)Mg(1-x)Al(2)O(4) nanosized in different composition (0.1≤x≤0.8) powders have been synthesized successively for first time by using low temperature combustion reaction (LTCR) of corresponding metal chlorides, carbonates and nitrates as salts with 3-methylpyrozole-5-one (3MP5O) as fuel at 300°C in open air furnace. Magnesium aluminate spinel (MgAl(2)O(4)) was used as crystalline host network for the synthesis of nickel-based nano ceramic pigments. The structure of prepared samples was characterized by using different techniques such as thermal analysis (TG-DTG/DTA), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM). UV/Visible and Diffuse reflectance spectroscopy (DRS) using CIE-L*a*b* parameters methods have been used for color measurements. The obtained results reveal that Ni(x)Mg(1-x)Al(2)O(4) powder of samples is formed in the single crystalline and pure phase with average particle size of 6.35-33.11 nm in the temperature range 500-1200°C. The density, particle size, shape and color are determined for all prepared samples with different calcination time and temperature.

Synthesis and spectral properties of near-infrared aminophenyl-, hydroxyphenyl-, and phenyl-substituted heptamethine cyanines.

Diverse meso-aminophenyl-, hydroxyphenyl-, and phenyl-substituted heptamethine cyanine dyes were prepared by a modified Suzuki--Miyaura method in good yields. In addition, direct Suzuki coupling of Vilsmeier--Haack reagent extends the procedure to the synthesis of otherwise difficult cyanine dyes containing multiple heteroatoms in the indolium ring. The new compounds possess excellent spectral properties and can be used to label bioactive molecules and nanoparticles. The one-pot synthesis procedure eliminates the cumbersome steps of protecting/deprotecting amino or hydroxy groups.

Extrato de Passiflora edulis na cicatrização de anastomose colônica em ratos: estudo morfológico e tensiométrico / Extract of Passiflora edulis in the healing of colonic anastomosis in rats: a tensiometric and morphologic study

INTRODUÇÃO: Pesquisas de novas substâncias com finalidades terapêuticas têm sido realizadas procurando isolar, extrair ou purificar novos compostos de origem vegetal. A Passiflora edulis (maracujá), espécie pertencente à família Passifloracea, originária das regiões tropicais e subtropicais do continente americano, é popularmente usada como sedativo, analgésico e antinflamatório e no tratamento de lesões cutâneas, feridas e erisipelas. OBJETIVO: Avaliar a cicatrização de anastomoses colônicas em ratos, que receberam extrato hidroalcoólico de Passiflora edulis no trans-operatório. MÉTODOS: Foram utilizados 40 ratos Wistar, distribuídos em dois grupos de 20 animais cada, denominados: grupo Passiflora (GP) e grupo controle (GC). Os ratos de cada grupo foram separados em dois subgrupos de 10 animais cada, avaliados no 3º e 7º dia do pós-operatório. O procedimento cirúrgico constou de secção da alça colônica esquerda, 5cm acima da reflexão peritoneal com preservação da arcada vascular e anastomose término-terminal em plano único. O grupo Passiflora recebeu dose única intraperitoneal do extrato hidroalcoólico de Passiflora edulis na dose de 250 mg/Kg. O grupo controle recebeu dose única de solução salina intraperitoneal em volume igual ao GP. Os parâmetros avaliados foram: aspectos macroscópicos da parede e cavidade abdominal, aderências perianastomóticas, pressão de ruptura à insuflação de ar, reação inflamatória tecidual da anastomose que constou de polimorfonucleares, monomorfonucleares e proliferação fibroblástica. RESULTADOS: Os aspectos macroscópicos não apresentaram diferenças significantes entre os grupos. Não ocorreu nenhuma deiscência de anastomose nos grupos estudados. Com relação à pressão de ruptura à insuflação de ar, observou-se que a média foi significantemente maior no subgrupo que recebeu o extrato de Passiflora no 3º dia (P3), cuja pressão foi 42,6 ± 17,8 mmHg em comparação ao subgrupo controle (C3), cuja pressão foi 25,4 ± 14,1 mmHg, p=0,028. O mesmo não ocorreu no 7º dia, onde o subgrupo C7 apresentou pressão de ruptura de 187,3 ± 39,5 mmHg, enquanto o subgrupo P7, apresentou pressão de ruptura de 203,0 ± 50,0 mmHg, p=0,447. Na análise histológica, os polimorfonucleares foram mais freqüentes no subgrupo C3, em comparação ao subgrupo P3, com diferença significante (p=0,034). Os monomorfonucleares (MMN) e proliferação fibroblástica foram mais freqüentes no subgrupo P3, com diferença significante, onde p=0,02 para MMN, e p=0,001 para proliferação fibroblástica. No 7º dia, houve diferença significante em todas as variáveis histológicas coradas pela hematoxilina-eosina e Tricômico de Masson (p<0,05) no subgrupo que recebeu o extrato de Passiflora. CONCLUSÃO: A administração peroperatória do extrato hidroalcoólico de Passiflora edulis influencia de forma significante na cicatrização das anastomoses colônicas em ratos.

INTRODUCTION: Investigation of new substances with therapeutic effects have been done trying to isolate, extract or purify new compounds of vegetable origin. The Passiflora edulis (maracujá) species from the Plassifloracia family, originated from the tropical and subtropical regions of the american continent, is found all over Brazil. It is commonly used as a sedative, painkiller and anti-inflammatory drug and also for the treatment of skin wounds, lesions and Erisipelae. PURPOSE: To evaluate the wound healing in colonic anastomosis in rats that received an hydro-alcoholic extract of Passiflora edulis peri-operatively. METHOD: 40 wistar rats were used distributed into two groups of 20 rats each, named: Passiflora edulis group (GP) and control group (GC). The rats of each group were separated into two subgroups of 10 animals each and were evaluated on the 3rd and 7th postoperative days. The surgical procedure consisted of a section of the left colon, 5 cm above the peritoneal reflexion with preservation of the vascular elements. Intestinal continuity was restored by an end-to-end single layer anastomosis. The Passiflora edulis group received an intraperitoneal application of the hydro-alcoholic extract in the dosage of 250 mg/kg. The control-group received one intraperitoneal dose of a saline with the same volume of the GP. The parameters evaluated were: macroscopic aspects of the wall and abdominal cavity, perianastomotic (adherences), bursting pressure, inflammatory tissue reaction on the anastomotic wound. RESULTS: The macroscopic aspects did not differ between the groups. No rupture in the anastomotic wound was seen in any rat. Regarding the bursting pressure, it was noticed that the average pressure was significantly higher in the subgroup that received the Passiflora edulis extract on the 3rd day (P3) (42,6 ± 17,8 mmHg vs. 25,4 ± 14,1 mmHg, p=0,028), as compared to the control sub-group (C3). However, on the 7th day, bursting pressure was similar in both groups (p=0.447). Rats from the C7 sub-group had a mean bursting pressure of 203,0 ± 50,0 mmHg vs. 187,3 ± 39,5 mmHg in the C7 sub-group. In the histologic analysis the polimorphic nuclear cells were more frequent in the C3 group, with significant differences (p=0,034). The monomorphic nuclear cells (MMN) and the fibrobastic proliferation were more frequent in the P3 sub-group with a significant difference, p=0,02 to MMN, and p=0,001 to the fibroblastic proliferation. On the 7th day there was a significant difference in all histologic criteria stained by hematoxin-eosin and Masson Trichomic (p<0,05) in the sub-group that received the Passiflora edulis extracts. CONCLUSION: The peri-operative administration of the hydro-alcoholic extract of Passiflora edulis has a positive influence on the healing of colonic anastomosis in rats.

Comparison of the dark and light-induced toxicity of thio and seleno analogues of the thiopyrylium dye AA1.

2,6-Bis(4-anilino)-4-(4-N,N-dimethylanilino)thiopyrylium chloride (AA1) and -selenopyrylium chloride (AA1-Se) and 2,6-bis(4-anilino)-4-(4-N-morpholinophenyl)thiopyrylium chloride (1) and -selenopyrylium chloride (2) were prepared via the addition of 4-N,N-dimethylanilino magnesium bromide and 4-N-morpholinophenyl magnesium bromide to chalcogenopyranones 3 followed by treatment with HCl gas then water. Cellular uptake of these dyes varied from 12+/-3fmol/cell for AA1 to 150+/-40 fmol/cell for AA1-Se. upon exposure to 5 x 10(-5) M solutions of the dyes for 3 h. Exposure of cell cultures to 1.8 J/cm2) of 360-750-nm light following incubation with 1 x 10(-6) M of either AA1, 1, or 2 for 24h resulted in no significant additional phototoxicity while AA1-Se showed a significant (p < 0.05) reduction in cell viability from 81% to 46%. Thiopyrylium dyes AA1 and 1 showed significant dark toxicity relative to selenopyrylium dyes AA1-Se and 2, respectively. AA1 was the only one of the four dyes to show inhibition of whole-cell mitochondrial cytochrome c oxidase activity in the dark. Irradiation of whole cells or mitochondrial suspensions treated with AA1, AA1-Se, or 2 gave inhibition of mitochondrial cytochrome c oxidase activity. Studies of JC-1-efflux indicated that all four cationic dyes accelerated the loss of JC-1 from the mitochondria, which suggests that all four dyes target the mitochondria.

Screening of natural and synthetic drugs against Trypanosoma cruzi. 1. Establishing a structure/activity relationship.

The activity of 45 compounds against bloodstream forms of Trypanosoma cruzi was investigated. The aim was to consider new agents which might subsequently be assayed for chemoprophylaxis in donated blood. In a preliminary screening the drugs were assayed (50 to 1,000 microM at 29 degrees C) and those active against bloodstream forms at concentrations below 600 microM were selected for further assays under blood-bank conditions (4 degrees C/24 h). Three compounds isolated from natural sources and six synthetic agents were selected. The active compounds of plant origin included purpurin, a member of the trihydroxylated anthraquinone group, which is known to exhibit trypanocidal activity. Among the active synthetic compounds, five displayed a common structural feature in that they were potentially one-electron acceptors, via reductive functional groups. All five compounds form tricentered C or N intermediates, joined in a hypothetical 'Y' radical pattern. It is possible that the trypanocidal mechanisms initiated by these compounds are similar to those found with crystal violet, since this dye, which is already used in endemic areas for the treatment of banked blood, also conforms to this general Y structural pattern.