Background And Objectives: Deescalation strategies omitting anthracyclines (AC) have been explored in early human epidermal growth factor receptor 2-positive breast cancer (HER2+ EBC), showing similar efficacy regarding pathological complete response (pCR) and long-term outcomes as AC-containing regimens. The standard treatment for this tumor subtype is based on chemotherapy and dual HER2 blockade with trastuzumab and pertuzumab, with AC-containing regimens remaining a frequent option for these patients, even in non-high-risk cases. The primary aim of this study was to assess and compare the effectiveness of neoadjuvant regimens with and without AC used in the treatment of HER2+ EBC in the clinical practice according to the pCR achieved with each.
View Article and Find Full Text PDFThe main causes of food spoilage come from the process of oxidation and the contamination by microorganisms. For the purpose of increasing food shelf-life the industries employ different techniques, being the addition of preservatives, one of the most used. The aim of this contribution was to investigate the potential antioxidant properties of tyrosol (4-hydroxyphenethyl alcohol, 4-OH) and tyrosol derived isomers (2-hydroxyphenethyl alcohol, 2-OH and 3-hydroxyphenethyl alcohol, 3-OH) against reactive oxygen species (ROS) and the antimicrobial effect on Staphylococcus aureus and Escherichia coli.
View Article and Find Full Text PDFThe exposure of fatty products to environmental light can trigger lipid oxidation in food through a sensitized-photooxidation process, which involves the participation of the species singlet oxygen (O(Δ)). Therefore, preservation of food quality represents a subject of great economic interest to the food industry. In this sense, the phenolic compounds are natural antioxidants widely used in food industry.
View Article and Find Full Text PDFReactive oxygen species (ROS) have been described in their double physiological function, helping in the maintenance of health as well as contributing to oxidative stress. Diabetes mellitus is a chronical disease nearly related to oxidative stress, whose treatment (in type II variant) consists in the administration of antidiabetic compounds (Andb) such as Gliclazide (Gli) and Glipizide (Glip). In this context, as Andb may be exposed to high ROS concentrations in diabetic patients, we have studied the potential ROS-mediated degradation of Gli and Glip through photosensitized processes, in the presence of Riboflavin (Rf) vitamin.
View Article and Find Full Text PDFObjectives: Catechins are important components of human diet and have received special attention due to their antioxidant capacity. The purpose of this paper was to study the antioxidant action of (+)-catechin (CTQ) in the presence of vitamin B (riboflavin) as light-absorbing agent. Furthermore, two model compounds, catechol (CTC) and resorcinol (RSC), were selected in order to elucidate the reactive target of the CTQ molecule.
View Article and Find Full Text PDFUnlabelled: Sensitized photooxidation processes in the presence of natural pigments may provide an alternative to antibiotics degradation since these compounds are transparent to natural light irradiation, therefore, they can be degraded by the action of photosensitizers which absorb light and produce highly reactive species, especially those derived from molecular oxygen (ROS). Most antibiotics used currently belong to a group of pharmaceutical substances that have been considered a new type of contaminants due to their persistence and bioaccumulation in the environment.
Objective: In this context, we decided to investigate the kinetic and mechanistic aspects of Vancomycin (Vanco) photosensitized degradation in the presence of the natural pigment Riboflavin (Vitamin B2, Rf) and the artificial dye Rose Bengal (RB) for comparative purposes.
Objectives: The study was focused on the activity of propolis from Amaicha del Valle, Argentina (ProAV) as a promoter and scavenger of Riboflavin (Rf)--photogenerated reactive oxygen species (ROS).
Methods: Through a kinetic and mechanistic study, employing stationary and time-resolved photochemical and electrochemical techniques, the protecting activity of ProAV was investigated.
Results: In the absence of light and Rf, ProAV exerted a relatively efficient inhibitory effect on 1,1-diphenyl-2-picrylhydrazyl radicals and acts as a protector of artificially promoted linoleic acid oxidation.
Trace amounts of the widely used β-lactam antibiotics (Atbs) in waste water may cause adverse effects on the ecosystems and contribute to the proliferation of antibiotic-resistant bacteria. On these grounds, kinetic and mechanistic aspects of photosensitized degradation of Ceftriaxone (Cft) and Cefotaxime (Ctx), have been studied in pure water by stationary and time-resolved techniques. Additionally, possible implications of these photoprocesses on the antimicrobial activity of the Atbs have also been investigated.
View Article and Find Full Text PDFThe complexity depicted by disease scenarios as diabetes mellitus, constitutes a very interesting field of study when drugs and biologically relevant components may be affected by such environments. In this report, the interaction between the protein Human Serum Albumin (HSA) and two antidiabetics (Andb), Gliclazide (Gli) and Glipizide (Glip) was studied through fluorescence and docking assays, in order to characterize these systems. On the basis that HSA and Andb can be exposed in vivo at high Reactive Oxygen Species (ROS) concentrations in diabetic patients, the degradative process of the protein free and bound to Andb, in presence of the species singlet molecular oxygen (O2((1)Δg)), was evaluated.
View Article and Find Full Text PDFSome organic contaminants dissolved in natural waters tend to adsorb on suspended particles and sediments. In order to mimic the photodegradation routes in natural waters of bromoxynil (BXN) adsorbed on silica, we here prepare and characterize silica nanoparticles modified with BXN (NP-BXN). We measure the direct photolysis quantum yield of aqueous BXN at 307 nm (0.
View Article and Find Full Text PDFThe production of dichlorophen (2,2'-methylenebis(4-chlorophenol), DCP) and its use as an anthelmintic and in pesticide products result in its direct release to the environment. To the purpose of modelling the possible photodegradation routes of DCP sorbed on sediments or suspended particles, the synthesis and characterization of silica nanoparticles modified with DCP (NP-DCP) is reported. The reactivity of NP-DCP with the excited states of riboflavin, a sensitizer usually present in natural waters, and with singlet oxygen were investigated.
View Article and Find Full Text PDFDiflunisal (DFNS) and Indomethacin (IMTC) are two profusely employed NSAIDs that provide anti-inflammatory and analgesic effects in humans. The scavenging of reactive oxygen species (ROS) by both NSAIDs was systematically studied in pH 7 aqueous solution. The ROS O2 ((1)Δg), O2(•-) and H2O2, generated by visible light irradiation of Riboflavin (Rf) in the presence of DFNS and IMTC, are deactivated by the NSAIDs.
View Article and Find Full Text PDFAmoxicillin (Amx) and cephalexin (Cfx) are β-lactam antibiotics widely used in human and veterinary medicine. Two points of interest surrounding these molecules are the photodegradation of the molecules and their microbiological implications, as well as the persistence and bioaccumulation in the environment which may cause resistance to bacterial strains. The kinetic and mechanistic aspects of the photosensitized degradation of Amx and Cfx have been studied in water at pH 7.
View Article and Find Full Text PDFThe kinetic and mechanistic aspects of the visible-light-mediated photodegradation of the phenolic antioxidants (PA), propyl gallate (PG), and t-butylhydroquinone (TBHQ), employing riboflavin (Rf) as photosensitizer, have been studied by time-resolved and stationary techniques. The photosensitizer Rose Bengal (RB) was used for auxiliary experiments. Results show the occurrence of chemical transformations on PA with the participation of electronically excited states of Rf and different reactive oxygen species (ROS) generated from these states.
View Article and Find Full Text PDFIt is well known that endogenous daylight-absorbing compounds produce the sensitized photodegradation of biologically relevant substrates. In this context the photostability of a mixture of the indole neurotransmitter serotonin (Sero) and vitamin B2 (riboflavin, Rf) upon visible-light irradiation and the possible role of Sero and related compounds as generators or deactivators of reactive oxygen species (ROS) was investigated through a kinetic and mechanistic study. The work was done at pH 7 and under experimental conditions in which only the vitamin absorbs photoirradiation.
View Article and Find Full Text PDFWithin the context of environmentally friendly methods for the elimination of surface-water pollutants, the photodegradation of the phenolic pesticides bromoxynil (BXN) and dichlorophen (DCP) under simulated natural conditions has been studied. The work was done in the presence of the visible-light absorber photosensitizer riboflavin (Rf), usually present in trace quantities in natural waters. Under aerobic conditions, an efficient photooxidation of both pesticides was observed.
View Article and Find Full Text PDFKinetic and mechanistic aspects on the stability of the flavones (FL) quercetin (Que), morin (Mor) and rutin (Rut), in methanolic solution and in the presence of reactive oxygen species (ROS) generated by visible light-promoted riboflavin (Rf, vitamin B(2)) photoirradiation were studied. The system was chosen as a model for the evaluation of the in vivo protective effect of biological targets by the flavones. The overall picture includes the vitamin as an endogenous natural photosensitizer.
View Article and Find Full Text PDFKinetic and mechanistic aspects of the vitamin B2 (riboflavin [Rf])-sensitized photo-oxidation of the imidazoline derivates (IDs) naphazoline (NPZ) and tetrahydrozoline (THZ) were investigated in aqueous solution. The process appears as important on biomedical grounds, considering that the vitamin is endogenously present in humans, and IDs are active components of ocular medicaments of topical application. Under aerobic visible light irradiation, a complex picture of competitive interactions between sensitizer, substrates and dissolved oxygen takes place: the singlet and triplet ((3)Rf*) excited states of Rf are quenched by the IDs: with IDs concentrations ca.
View Article and Find Full Text PDFVisible-light photo-irradiation of the commercial phenolic antioxidants (PhAs) butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT), in the presence of vitamin B2 (riboflavin, Rf), in methanolic solutions and under aerobic conditions, results in the photo-oxidation of the PhAs. The synthetic dye photosensitiser Rose Bengal was also employed for auxiliary experiments. With concentrations of riboflavin and PhAs of ca.
View Article and Find Full Text PDFThe kinetics of rose bengal-sensitized photooxidation of tyrosine and several tyrosine-derivatives (tyr-D) named tyrosine methyl ester, tyrosine ethyl ester and tyrosine benzyl ester was studied in buffered pH 11 water, and buffered pH 11 micellar aqueous solutions of 0.01 M cetyltrimethylammonium chloride (CTAC) and 0.01 M-octylphenoxypolyethoxyethanol [triton X100 (TX100)].
View Article and Find Full Text PDFThe kinetics and mechanism of the oxidation of Glycine (Gly), Alanine (Ala), Tyrosine (Tyr), Tryptophan (Trp) and some di-(Gly-Gly, Ala-Ala, Gly-Ala, Gly-Trp, Trp-Gly, Gly-Tyr, Tyr-Gly), tri-(Gly-Gly-Gly, Ala-Gly-Gly) and tetrapeptides (Gly-Gly-Gly-Gly) mediated by sulfate (SO(4) (-)) and hydrogen phosphate (HPO(4) (-)) radicals was studied, employing the flash-photolysis technique. The substrates were found to react with sulfate radicals (SO(4) (-), produced by photolysis of the S(2)O(8)(2-)) faster than with hydrogen phosphate radicals (HPO(4) (-), generated by photolysis of P(2)O(8)(4-) at pH = 7.1).
View Article and Find Full Text PDFThe kinetics and mechanistic aspects of the riboflavin-photosensitised oxidation of the topically administrable ophthalmic drugs Timolol (Tim) and Pindolol (Pin) were investigated in water-MeOH (9:1, v/v) solution employing light of wavelength > 400 nm. riboflavin, belonging to the vitamin B(2) complex, is a known human endogenous photosensitiser. The irradiation of riboflavin in the presence of ophthalmic drugs triggers a complex picture of competitive reactions which produces the photodegradation of both the drugs and the pigment itself.
View Article and Find Full Text PDFThe kinetics and mechanism of the Riboflavin (Rf)-promoted photochemical degradation with visible light of the herbicide Norflurazon (NF) has been studied by time-resolved and stationary techniques. Using light of wavelength higher than 400 nm--a region where NF is totally transparent--and with concentrations of Rf and NF of ca. 0.
View Article and Find Full Text PDFJ Photochem Photobiol B
October 2003
4-Hydroxyquinoline (4-OHQ) and 8-hydroxyquinoline (8-OHQ), two compounds of interest because of their bioactivity and their structural relation with bioactive products, are effectively photooxygenated when irradiated with visible light in the presence of riboflavin (Rf) (vitamin B2) in solution in air-saturated water-methanol (9:1). Rf behaves as a dye-sensitiser, since both quinolines are transparent to visible light. 8-OHQ degrades about five times faster than 4-OHQ.
View Article and Find Full Text PDFThe oxidation kinetics and mechanism of the phenolic derivatives of alpha,alpha,alpha-trifluorotoluene, 2-trifluoromethylphenol, 3-trifluoromethylphenol (3-TFMP), 4-trifluoromethylphenol and 3,5-bis(trifluoromethyl)phenol, mediated by singlet molecular oxygen, O2(1delta(g)), and hydrogen phosphate radicals were studied, employing time-resolved O2(1delta(g)) phosphorescence detection, polarographic determination of dissolved oxygen and flash photolysis. All the substrates are highly photo-oxidizable through a O2(1delta(g))-mediated mechanism. The phenols show overall quenching constants for O2(1delta(g)) of the order of 10(6) M(-1) s(-1) in D2O, while the values for the phenoxide ions in water range from 1.
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