Lighting the Path: Light Delivery Strategies to Activate Photoresponsive Biomaterials In Vivo

Photoresponsive biomaterials are experiencing a transition from in vitro models to in vivo demonstrations that point toward clinical translation. Dynamic hydrogels for cell encapsulation, light-responsive carriers for controlled drug delivery, and nanomaterials containing photosensitizers for photodynamic therapy are relevant examples. Nonetheless, the step to the clinic largely depends on their combination with technologies to bring light into the body. This review highlights the challenge of photoactivation in vivo, and presents strategies for light management that can be adopted for this purpose. The authors’ focus is on technologies that are materials-driven, particularly upconversion nanoparticles that assist in “direct path” light delivery through tissue, and optical waveguides that “clear the path” between external light source and in vivo target. The authors’ intention is to assist the photoresponsive biomaterials community transition toward medical technologies by presenting light delivery concepts that can be integrated with the photoresponsive targets. The authors also aim to stimulate further innovation in materials-based light delivery platforms by highlighting needs and opportunities for in vivo photoactivation of biomaterials.     

Tailored-Made Polydopamine Nanoparticles to Induce Ferroptosis in Breast Cancer Cells in Combination with Chemotherapy

Ferroptosis is gaining followers as mechanism of selective killing cancer cells in a non-apoptotic manner, and novel nanosystems capable of inducing this iron-dependent death are being increasingly developed. Among them, polydopamine nanoparticles (PDA NPs) are arousing interest, since they have great capability of chelating iron. In this work, PDA NPs were loaded with Fe³⁺ at different pH values to assess the importance that the pH may have in determining their therapeutic activity and selectivity. In addition, doxorubicin was also loaded to the nanoparticles to achieve a synergist effect. The in vitro assays that were performed with the BT474 and HS5 cell lines showed that, when Fe³⁺ was adsorbed in PDA NPs at pH values close to which Fe(OH)₃ begins to be formed, these nanoparticles had greater antitumor activity and selectivity despite having chelated a smaller amount of Fe³⁺. Otherwise, it was demonstrated that Fe³⁺ could be released in the late endo/lysosomes thanks to their acidic pH and their Ca²⁺ content, and that when Fe³⁺ was co-transported with doxorubicin, the therapeutic activity of PDA NPs was enhanced. Thus, reported PDA NPs loaded with both Fe³⁺ and doxorubicin may constitute a good approach to target breast tumors.     

Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Use of citric acid for heavy metals extraction from contaminated sewage sludge for land application.

Recent studies revealed that organic acids such as citric and oxalic acids seemed to be more promising as chemical extracting agents for removal of heavy metals from contaminated sludge, since they are biodegradable and can attain a higher metal extraction efficiency at mildly acidic pH compared to other extracting agents. Results of a lab-scale study on the efficiency of citric acid in the extraction of chromium (Cr), copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn) from anaerobically digested sludge, revealed that citric acid seemed to be highly effective in extracting Cr (at 100%), Cu (at 88%), Ni (at 98%) and Zn (at 100%) at pH 2.33, mostly at 5 days leaching time except for Cu and Zn, which are at 1 day and 2 h contact times respectively. Lead removal at the same pH was also high at 95% but at a longer leaching time of 11 days. At pH 3, citric acid seemed to be highly effective in extracting Pb (at 100%) at 1 day leaching time, although higher removals were also attained for Ni (70%) and Zn (80%) at only 2 h leaching time. Chemical speciation studies showed that Cr, Cu and Ni in the sludge sample seem to predominate in residual fractions, while Pb and Zn were found mostly bound to organic and inorganic matter forms, hence the potential of the sludge for land application.     

Reaction of cytochrome P450 with cumene hydroperoxide: ESR spin-trapping evidence for the homolytic scission of the peroxide O-O bond by ferric cytochrome P450 1A2

ESR spin trapping was used to investigate the reaction of rabbit cytochrome P450 (P450) 1A2 with cumene hydroperoxide. Cumene hydroperoxide-derived peroxyl, alkoxyl, and carbon-centered radicals were formed and trapped during the reaction. The relative contributions of each radical adduct to the composite ESR spectrum were influenced by the concentration of the spin trap. Computer simulation of the experimental data obtained at various 5,5-dimethyl-1-pyrroline N-oxide (DMPO) concentrations was used to quantitate the contributions of each radical adduct to the composite ESR spectrum. The alkoxyl radical was the initial radical produced during the reaction. Experiments with 2-methyl-2-nitrosopropane identified the carbon-centered adducts as those of the methyl radical, hydroxymethyl radical, and a secondary carbon-centered radical. The reaction did not require NADPH-cytochrome P450 reductase or NADPH. It is concluded that the reaction involves the initial homolytic scission of the peroxide O-O bond to produce the cumoxyl radical. Methyl radicals were produced from the beta-scission of the cumoxyl radical. The peroxyl adduct was not observed in the absence of molecular oxygen. We conclude that the DMPO peroxyl radical adduct detected in the presence of oxygen was due to the methylperoxyl radical formed by the reaction of the methyl radical with oxygen. At a higher P450 concentration, a protein-derived radical adduct was also detected.     

EEG spectral abnormalities and psychosis as predictors of cognitive and functional decline in probable Alzheimer's disease

We examined whether either psychotic features (e.g., delusions and hallucinations) or EEG abnormalities are associated with more rapid progression of Alzheimer's disease (AD). AD patients with psychosis have exhibited more EEG abnormalities than those without psychosis, and both abnormal EEG and psychosis have been noted to be predictors of functional and cognitive decline in AD. Ninety-five probable AD patients participating in a longitudinal study of dementia had an EEG and a semistructured psychiatric interview at baseline. Using EEG spectral analysis, we classified records as normal/abnormal based on the parasagittal mean frequency. Patients with abnormal EEGs were more functionally (e.g., Blessed Rating Scale for activities of daily living) and cognitively (e.g., Mini-Mental State) impaired than patients with normal EEG. AD patients with psychosis were only more functionally impaired than patients without psychosis. A two-factor analysis showed no interaction between abnormal EEG and psychosis. In addition, using a Cox proportional hazard model adjusted for age and education, the presence of an abnormal EEG or psychotic symptom at study entry was associated with higher risk of reaching severe cognitive and functional impairment during follow-up. Neither abnormal EEG nor the presence of psychosis predicted death. These results indicate that both abnormal EEG and psychosis are independent predictors of disease progression but not of physical survival.     

PCR-based procedures in detection and DNA-fingerprinting of Salmonella from samples of animal origin

The usefulness of selected PCR-protocols for the detection of Salmonella in 117 samples of animal origin (17 raw minced meat, 27 raw chicken meat, 8 raw sausages, and 25 egg samples, as well as 18 poultry faecal, and caecal swabs samples) and DNA-fingerprinting typing is shown. To establish an accurate PCR-procedure for Salmonella detection the following parameters were evaluated: two pre-PCR concentration procedures, centrifugation and immunomagnetic separation (IMS) using Dynabeads anti- Salmonella; the specificity and sensitivity of 10 sets of primers; and different conditions of the amplification reaction. In light of the results obtained from the use of PCR-based procedures alone or in combination with conventional methods, the following findings can be underlined: First, IMS is more efficient than centrifugation in the recovery of Salmonella. Second, the selected IMS/PCR-detection protocol is less time-consuming (45 h) than the IMS/culture procedure (90 h), and a good concordance between them was found when the Kappa coefficient was calculated (0·87). Third, PCR-ribotyping technique showed a very low discrimination power, being able to differentiate only three profiles. Fourth, RAPD technique using specific primers supports previous works in which it was proposed as a simple and useful tool for discriminating isolates between and within serotypes. Fifth, The efficiency, rapidity, and flexibility of the PCR-protocols applied were high, and they can be performed using two PCR-programs and the same basic equipment.     

Retaining maximum antioxidative potency of wheat germ oil refined by molecular distillation

A process of physical refining wheat germ oil using the technique of molecular distillation (MD) is presented in this work. Wheat germ oil was obtained from the germ by solvent extraction using hexane and also by cold pressing. The oil extracted with hexane was degummed and bleached before deacidification in order to modify the parameters of phosphorus and color. The goal in carrying out the stage of physical refining by MD was to preserve the maximum amount of original antioxidative potential obtained from extraction of the crude oil. The effect of evaporation temperature of one‐stage MD on the efficiency of free fatty acid elimination was studied. The antioxidant portion was followed by means of analytic determination of tocopherols by high‐performance liquid chromatography. Tocopherol retention up to 98% was achieved in the oil extracted by pressing, and yields of up to 96% were achieved in the oil extracted with hexane. Copyright © 2007 Society of Chemical Industry     

Elimination of organic matter present in wastewaters from the cork industry by membrane filtration

BACKGROUND: The first stage of the cork industrial process generates great volumes of wastewater with moderate to high organic pollutant content that must be purified using different procedures, such as filtration by membranes. RESULTS: The tangential filtration of these wastewaters was studied using two different laboratory equipments. In the first one, three ultrafiltration (UF) membranes were tested, with molecular weight cut‐off (MWCO) 100 kDa and 30 kDa, and two operating modes were used: total recycling of permeate and retentate streams, and in continuous mode, without recycling both streams. In the total recycling UF experiments, the influence of the operating variables on the permeate flux was first established. The effectiveness of the different membranes was determined by evaluating the rejection coefficients for several parameters that measure the global pollutant content of the effluent. The values found for these rejection coefficients were in the following order: ellagic acid and color > absorbance at 254 nm > tannic content > COD (chemical oxygen demand). In the continuous mode experiments, the fouling mechanism for each membrane was established by fitting the experimental data to various filtration fouling models given in the literature. The operating mode in the second equipment was batch concentration, and additional experiments were carried out with an UF membrane (2 kDa), and with a NF membrane (with MWCO in the range 150–300 Da). CONCLUSIONS: The three operating modes tested provided different rejection levels of organic matter; among them, the most effective procedure tested was batch concentration mode using a NF membrane. Copyright © 2007 Society of Chemical Industry