Enhancing Targeted Photodynamic Therapy: Star-Shaped Glycopolymeric Photosensitizers for Improved Selectivity and Efficacy.

Targeted photodynamic therapy (PDT) offers advantages over nontargeted approaches, including improved selectivity, efficacy, and reduced side effects. This study developed star-shaped glycopolymeric photosensitizers using porphyrin-based initiators via ATRP. Incorporating a porphyrin core gave the polymers fluorescence and ROS generation, while adding fructose improved solubility and targeting capabilities. The photosensitizers had high light absorption, singlet oxygen production, specificity, low dark toxicity, and biocompatibility. The glycopolymers with longer sugar arms and higher density showed better uptake on MCF-7 and MDA-MB-468 cells compared to HeLa cells, indicating enhanced targeting capabilities. Inhibition of endocytosis confirmed the importance of the GLUT5 receptor. The resulting polymers exhibited good cytocompatibility under dark conditions and satisfactory PDT under light irradiation. Interestingly, the polymers containing fructose have a GLUT5-dependent elimination effect on the MCF-7 and MDA-MB-468 cells. The intracellular ROS production followed a similar pattern, indicating that the fructose polymer exhibits specific targeting toward cells with GLUT5 receptors.

Formation of fluorescent polydopamine dots from hydroxyl radical-induced degradation of polydopamine nanoparticles.

This study describes the synthesis of fluorescent polydopamine dots (PDs) through hydroxyl radical-induced degradation of polydopamine nanoparticles. The decomposition of polydopamine nanoparticles to fluorescent PDs was confirmed using transmission electron microscopy and dark-field microscopy. The analysis of PDs by using laser desorption/ionization time-of-flight mass spectrometry revealed that the PDs consisted of dopamine, 5,6-dihydroxyindole, and trihydroxyindole units. Oligomerization and self-assembly of these units produced a broad adsorption band, resulting in an excitation-wavelength-dependent emission behavior. The maximal fluorescence of PDs appeared at 440 nm with a quantum yield of 1.2%. The coordination between the catechol groups of PDs and ferric ions (Fe(3+)) quenched the fluorescence of PDs; the limit of detection at a signal-to-noise ratio of 3 for Fe(3+) was determined to be 0.3 µM. The presence of pyrophosphate switched on the fluorescence of the PD-Fe(3+) complexes. Compared to the other reported methods for sensing Fe(3+), PDs provided simple, low-cost, and reusable detection of Fe(3+).

Alkaline lignin does not immobilize cadmium in soils but decreases cadmium accumulation in the edible part of lettuce (Lactuca sativa L.).

Heavy metal contamination and low use efficiency of phosphorus (P) fertilizers are worldwide issues. Alkaline lignin is expected to decrease the heavy metal risk and enhance the P availability in heavy-metal-contaminated soils. A 120-day incubation study examined the effects of alkaline lignin on Cd, Pb and P bioavailability and transformation in Cd or Cd/Pb co-contaminated red and cinnamon soils and elucidated the associated mechanisms. A pot experiment further tested Cd accumulation in lettuce (Lactuca sativa L.) grown in the Cd-contaminated red soil. The amendment of alkaline lignin increased the concentrations of bioavailable Cd by 13-20% in the acid red soil and 97-107% in the alkaline cinnamon soil, respectively, due to the increase of dissolved organic C concentrations. Meanwhile, it also increased the concentrations of available P in both soils, Al-P in the red soil and Ca2-P in the cinnamon soil. Consequently, alkaline lignin amendment increased lettuce biomass of shoots by 8-23% and of roots by 56-71%, P uptake by 37-50% in shoots and by 28-62% in roots, and limited Cd transport from root to shoot which decreased Cd concentrations by 26% in lettuce shoot (edible part). The results suggest that alkaline lignin increases plant growth and decreases Cd bioaccumulation in the shoot through restricting Cd translocation from the root to shoot and increasing soil P availability but not Cd immobilization, and hence may have potential to reduce vegetable Cd contamination risk.

Conducting polymer-based sensors for food and drug analysis.

Conducting polymers (CPs) are a category of polymeric materials with conjugated main chains. The characteristic electrical and optical properties of CPs can be fine-tuned through controlling the doping states of CPs. Because of their long-term stability in water, CPs have been demonstrated as electroactive biointerfaces and electrode materials especially in aqueous environments. Serving as multifunctional interfaces and organic electrodes for the integration bioelectronics and devices, CPs have been studied and applied in various biological applications. This paper provides a review of conducting polymer-based electrochemical sensors, particularly those used in biological fields. General conducting polymers and derivatives and their main electrochemical sensing platforms with different design of devices are introduced. Cyclic voltammetry, differential pulse voltammetry, chronoamperometry, electrochemical impedance spectroscopy, and quartz crystal microbalance methods and their features are then explored as detection methods for the analysis of drugs and food. To enhance the sensitivity and lower the detection limit of sensing platforms, various CP-based nanocomposites have been designed and developed. Although the electrodes made of CP-based nanocomposites usually outperform those made of pristine CPs, more systematic studies are required to provide insights into the design of nanocomposite-based electrodes. More applications of CP-based sensors for advanced food and drug analyses are expected.

Facile synthesis of PEI-based crystalline templated mesoporous silica with molecular chirality for improved oral delivery of the poorly water-soluble drug.

The aim of this study was to build up a novel chiral mesoporous silica called PEIs@TA-CMS through a facile biomimetic strategy and to explore its potential to serve as a drug carrier for improving the delivery efficiency of poorly water-soluble drug. PEIs@TA-CMS was synthesized by using a chiral crystalline complex associated of tartaric acid and polyethyleneimine (PEIs) as templates, scaffolds and catalysts. The structural features including morphology, size, pore structure and texture properties were systematacially studied. The results showed that PEIs@TA-CMS was monodispersed spherical nanoparticles in a uniformed diameter of 120-130 nm with well-developed pore structure (SBET: 1009.94 m2/g, pore size <2.21 nm). Then PEIs@TA-CMS was employed as nimodipine (NMP) carrier and compared with the drug carry ability of MCM41. After drug loading, NMP was effectively transformed from the crystalline state to an amorphous state due to the space confinement in mesopores. As expected, PEIs@TA-CMS had superiority in both drug loading and drug release compared to MCM41. It could incorporate NMP with high efficiency, and the dissolution-promoting effect of PEIs@TA-CMS was more obvious because of the unique interconnected curved pore channels. Meanwhile, PEIs@TA-CMS could significantly improve the oral adsorption of NMP to a satisfactory level, which showed approximately 3.26-fold higher in bioavailability, and could effectively prolong the survival time of mice on cerebral anoxia from 10.98 to 17.33 min.

Highly-ordered perpendicularly immobilized FWCNTs on the thionine monolayer-modified electrode for hydrogen peroxide and glucose sensors.

In this paper, we innovatively immobilized few-walled carbon nanotubes (FWCNTs) perpendicularly on Au surface through conductive thionine instead of aminoalkanethiols so as to improve electrochemical properties. Because FWCNTs own smaller aggregates, stronger chemical corrosion resistant, and higher conductivity than single-walled carbon nanotubes (SWCNTs), and thionine is a good electron transfer mediator can provide amino and sulfhydryl groups playing the same function as insulating aminoalkanethiols. The strategy for obtaining perpendicularly aligned FWCNTs (p-FWCNTs) is electrostatically assembled thionine and 11-amino-n-undecanethiol (AUT) on Au surface via Au-S bond to provide amino groups for covalently combining terminus-carboxylated FWCNTs, we confirmed and compared the results by AFM, Raman spectroscopy and electrochemical methods. In order to prove the constructed basement has excellent electrochemical properties can provide a good platform for sensors fabrication, we developed a novel non-enzymatic hydrogen peroxide (H2O2) sensor by electrodepositing Pt nanoparticles (PtNPs) on p-FWCNTs/Thionine/Au electrode surface, and verified the result by TEM, EDX and electrochemical techniques. Furthermore, polyallylamine (PAA) and poly(vinyl sulfate) (PVS) permselective layer, poly(diallyldimethylammonium) (PDDA) and glucose oxidase (GOx) multilayer films were layer-by-layer self-assembled on p-FWCNTs/Thionine/Au surface to fabricate a glucose biosensor. Either the non-enzymatic H2O2 sensor or the enzyme-based glucose biosensor showed good sensitivity, selectivity, reproducibility and stability, both them had been applied for biological sample analysis with satisfactory results. The results show that the p-FWCNTs/Thionine/Au electrode can work as an ideal platform for the development of highly sensitive sensors, coupled with p-FWCNTs are rich in functional groups could be used for fabricating diverse sensors.