Do birds select the plastics debris used for nest construction? A case study in a Mediterranean agricultural landscape.

Plastic pollution is becoming a global problem due to its ubiquitous occurrence and the impacts detected for many species. However, the research about plastics in nests of terrestrial bird species has remained relatively overlooked in comparison to those devoted to marine ecosystems. Here we study the occurrence and patterns of use of anthropogenic material in nests of two passerine birds, the Eurasian magpie (Pica pica) and the European serin (Serinus serinus), breeding in an orange tree cultivation in Mediterranean Spain. Our results show that both species use extensively plastic debris as nest material; almost 71% of the European serin nests and 96% of nests of Eurasian magpies contained plastic debris. Furthermore, by analyzing the plastic debris availability in the agricultural landscape surveyed we confirmed a selection pattern in the two species. Thus, both species preferably select plastic filaments over other plastic debris. The Eurasian magpie does not select plastic based on size or color but the European serin avoid black plastics prefer smaller fragments in comparison to the average size available. Moreover, we suggest the apparent similarity of plastic filaments with the natural materials typically used by these species, as well as how they use the plastic in their nests could influence their selection behavior. More studies focused on terrestrial birds inhabiting human modified habitats could offer a deeper approach to how plastic debris interacts with wildlife in different ways.

Side-Selective Solid-Phase Metallaphotoredox N(in)-Arylation of Peptides.

Postsynthetic diversification of peptides through selective modification of endogenous amino acid side chains has enabled significant advances in peptide drug discovery while expanding the biological and medical chemistry space. However, current tools have been focused on the modification of reactive polar and ionizable side chains, whereas the decoration of aromatic systems (e.g., the N(in) of the tryptophan) has been a long-standing challenge. Here, we introduce metallaphotocatalysis in solid-phase peptide synthesis for the on-resin orthogonal N-arylation of relevant tryptophan-containing peptides. The protocol allows the chemoselective introduction of a new C(sp2)-N bond at the N(in) of tryptophan in biologically active protected peptide sequences in the presence of native redox-sensitive side chains. The fusion of metallaphotocatalysis with solid-phase peptide synthesis opens new perspectives in diversifying native amino acid side chains.

Metal-Mediated Organocatalysis in Water: Serendipitous Discovery of Aldol Reaction Catalyzed by the [Ru(bpy)2(nornicotine)2]2+ Complex.

The [Ru(bpy)2(Nor)2]2+ complex (Nor = nornicotine) is an efficient catalyst for the aldol reaction of acetone with activated benzaldehydes in a buffered aqueous solution. The metal plays the role of an activator for the nornicotine organocatalyst ligands. The resulting catalytic activity is potentiated by a factor of about 4.5 as compared to free nornicotine. Similar rate enhancements can be achieved by using Zn(II) cations as the activator. The observations are rationalized with the reduced basicity of the pyrrolidine N in nornicotine due to the enhanced electron withdrawal of the metal-complexed pyridyl moiety.

Photooxidation Responsive Elastin-Like Polypeptide Conjugates for Photodynamic Therapy Application.

Stimuli-responsive recombinant elastin-like polypeptides (ELPs) are artificial protein polymers derived from the hydrophobic domain of tropoelastin that have attracted significant interest for drug delivery and tissue engineering applications. In the present study, we have conjugated a photosensitizer (PS) to a hydrophobic methionine-containing ELP scaffold, which upon reaction with singlet oxygen (1O2) is transformed into a hydrophilic sulfoxide derivative facilitating the disassembly of photosensitizer-delivery particles during the photodynamic therapy (PDT) process. A peripherally substituted carboxy-Zn(II)-phthalocyanine derivative (TT1) bearing a carboxyl group directly linked to the Pc-ring, and presenting an absorption maximum around 680 nm, was selected as PS which simultaneously acted as a photooxidation catalyst. A TT1-ELP[M1V3-40] conjugate was prepared from ELP[M1V3-40] modified with an alkyne group at the N-terminal chain end, and from TT1-amide-C3-azide by copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction. This innovative model photooxidation sensitive PS delivery technology offers promising attributes in terms of temperature-controlled particle formation and oxidation-triggered release, narrow molar mass distribution, reproducibility, scalability, non-immunogenicity, biocompatibility, and biodegradability for pharmaceutical applications in an effort to improve the clinical effectiveness of PDT treatments.

Electrochemical Installation of CFH2 -, CF2 H-, CF3 -, and Perfluoroalkyl Groups into Small Organic Molecules.

Electrosynthesis can be considered a powerful and sustainable methodology for the synthesis of small organic molecules. Due to its intrinsic ability to generate highly reactive species under mild conditions by anodic oxidation or cathodic reduction, electrosynthesis is particularly interesting for otherwise challenging transformations. One such challenge is the installation of fluorinated alkyl groups, which has gained significant attention in medicinal chemistry and material science due to their unique physicochemical features. Unsurprisingly, several electrochemical fluoroalkylation methods have been established. In this review, we survey recent developments and established methods in the field of electrochemical mono-, di-, and trifluoromethylation, and perfluoroalkylation of small organic molecules.

Optical Supramolecular Sensing of Creatinine.

Calix[4]pyrrole phosphonate-cavitands were used as receptors for the design of supramolecular sensors for creatinine and its lipophilic derivative hexylcreatinine. The sensing principle is based on indicator displacement assays of an inherently fluorescent guest dye or a black-hole quencher from the receptor's cavity by means of competition with the creatinine analytes. The systems were thermodynamically and kinetically characterized regarding their 1:1 binding properties by means of nuclear magnetic resonance spectroscopy (1H and 31P NMR), isothermal titration calorimetry, and optical spectroscopies (UV/vis absorption and fluorescence). For the use of the black-hole indicator dye, the calix[4]pyrrole was modified with a dansyl chromophore as a signaling unit that engages in Förster resonance energy transfer with the indicator dye. The 1:1 binding constants of the indicator dyes are in the range of 107 M-1, while hexylcreatinine showed values around (2-4) × 105 M-1. The competitive displacement of the indicators by hexylcreatinine produced supramolecular fluorescence turn-on sensors that work at micromolar analyte concentrations that are compatible with those observed for healthy as well as sick patients. The limit of detection for one of the systems reached submicromolar ranges (110 nM).

Visible Light-Gated Organocatalysis Using a RuII -Photocage.

The light-gated organocatalysis via the release of 4-N,N-dimethylaminopyridine (DMAP) by irradiation of the [Ru(bpy)2 (DMAP)2 ]2+ complex with visible light was investigated. As model reaction the acetylation of benzyl alcohols with acetic anhydride was chosen. The pre-catalyst releases one DMAP molecule on irradiation at wavelengths longer than 455 nm. The photochemical process was characterized by steady-state irradiation and ultrafast transient absorption spectroscopy. The latter enabled the observation of the 3 MLCT state and the spectral features of the penta-coordinated intermediate [Ru(bpy)2 (DMAP)]2+ . The released DMAP catalyzes the acetylation of a wide range of benzyl alcohols with chemical yields of up to 99 %. Control experiments revealed unequivocally that it is the released DMAP which takes the role of the catalyst.

One-pot organocatalytic/multicomponent approach for the preparation of novel enantioenriched non-natural selenium-based peptoids and peptide-peptoid conjugates.

A combined organocatalytic and multicomponent synthetic approach was designed for the preparation of selenium-based peptoids and peptide-peptoid conjugates. This single-step synthetic protocol comprises the organocatalytic asymmetric insertion of phenylselenium in the aldehyde moiety followed by the Ugi four-component reaction which results in obtaining the desired compounds in good-to-moderate yields and with good-to-excellent levels of stereoselectivity.

Photocaged Competitor Guests: A General Approach Toward Light-Activated Cargo Release From Cucurbiturils.

A general approach toward the light-induced guest release from cucurbit[7]uril by means of a photoactivatable competitor was devised. An o-nitrobenzyl-caged competitor is photolyzed to generate a competitive guest that can displace cargo from the host macrocycle solely based on considerations of chemical equilibrium. With this method the release of terpene guests from inclusion complexes with cucurbit[7]uril was demonstrated. The binding of the herein investigated terpenes, all being lead fragrant components in essential oils, has been characterized for the first time. They feature binding constants of up to 108  L mol-1 and a high differential binding selectivity (spanning four orders of magnitude for the binding constants for the particular set of terpenes). By fine-tuning the photoactivatable competitor guest, selective and also sequential release of the terpenes was achieved.

Universal access to megastigmanes through controlled cyclisation towards highly substituted cyclohexenes.

We report the selective formation of cyclohexenes with a tetrasubstituted double bond, the structural key element of megastigmanes. For this purpose the ZrCl4-mediated epoxide ring opening of epoxy-geranylacetone was employed. This approach provides a universal entry to the preparation of the members of the megastigmane family, which was exemplified in the asymmetric synthesis of tectoionol B.

Homocoupling versus reduction of radicals: an experimental and theoretical study of Ti(III)-mediated deoxygenation of activated alcohols.

A detailed experimental and theoretical study corroborates that the reductive deoxygenation of activated (allylic or benzylic) alcohols with excess Ti(III) proceeds via an allyl(benzyl)-radical and allyl(benzyl)-Ti, which is protonated, regioselectively in the case of allylic derivatives. The H atom of the newly formed C-H bond in the product originates from the -OH group of the starting material. The deoxygenation of lithium alkoxides or alcohols by using 1.0 mol of Ti(III) leads to the corresponding dimerization products in good yields. An excellent agreement with the experimental data was obtained by using a reaction kinetics simulator to discriminate between competing reactions.

Easy access to a cyclic key intermediate for the synthesis of trisporic acids and related compounds.

The synthesis of a cyclohexane skeleton possessing different oxygenated functional groups at C-3, C-8 and C-9, and a D1,6-double bond has been accomplished in 10 steps with an overall 17% yield. This compound is a key intermediate for access to a wide range of compounds of the bioactive trisporoid family. The synthetic sequence consists of the preparation of a properly functionalized epoxygeraniol derivative, and its subsequent stereoselective cyclization mediated by Ti(III). This last step implies a domino process that starts with a homolytic epoxide opening followed by a radical cyclization and regioselective elimination. This concerted process gives access to the cyclohexane moiety with stereochemical control of five of its six carbon atoms.

Trial of complete weaning from immunosuppression for liver transplant recipients: factors predictive of tolerance.

Recipients of liver transplantation (LT) may develop immunological tolerance. Factors predictive of tolerance are not clearly understood. Transplant recipients with normal liver function tests and without active viral hepatitis or autoimmune disease who presented with side effects of immunosuppression or a high risk of de novo malignancies were selected to participate in this prospective study. Twenty-four patients fulfilled the inclusion criteria and, therefore, underwent a gradual reduction of immunosuppression. Tolerance was defined as normal liver function tests after immunosuppression withdrawal. Basal clinical and immunological characteristics, including lymphocyte counts and subpopulations (T, B, natural killer, CD4(+) , CD8(+) , and regulatory T cells) and the phytohemagglutinin stimulation index (SI), were compared for tolerant and nontolerant patients. Fifteen of the 24 patients (62.5%) were tolerant at a median of 14 months (interquartile range = 8.5-22.5 months) after complete immunosuppression withdrawal. Tolerant patients had a longer median interval between transplantation and inclusion in the study (156 for tolerant patients versus 71 months for nontolerant patients, P = 0.003) and a lower median SI (7.49 for tolerant patients versus 41.73 for nontolerant patients, P = 0.01). We identified 3 groups of patients with different probabilities of tolerance: in the first group (n = 7 for an interval > 10 years and an SI < 20), 100% reached tolerance; in the second group (n = 10 for an interval > 10 years and an SI > 20 or an interval < 10 years and an SI < 20), 60% reached tolerance; and in the third group (n = 7 for an interval < 10 years and an SI > 20), 29% reached tolerance. In conclusion, a high proportion of select LT recipients can reach tolerance over the long term. Two simple basal variables-the time from transplantation and the SI-may help to identify these patients.

First total synthesis of (+)-apotrisporin E and (+)-apotrientriols A-B: a cyclization approach to apocarotenoids.

The first total synthesis of the natural apocarotenoids (+)-apotrisporin E (1) and (+)-apotrientriols A and B (2-3) has been accomplished. The structure, relative stereochemistry and the assignation of the absolute configuration have been confirmed. This is a fast and easy access to this family of natural products whose key steps are a diastereoselective cyclization and a HWE olefination to attach the dienic side chain. This work also opens the door to the synthesis of other apocarotenoids such as trisporols and trisporic acids.

Soil Thermophiles and Their Extracellular Enzymes: A Set of Capabilities Able to Provide Significant Services and Risks.

During this century, a number of reports have described the potential roles of thermophiles in the upper soil layers during high-temperature periods. This study evaluates the capabilities of these microorganisms and proposes some potential consequences and risks associated with the activity of soil thermophiles. They are active in organic matter mineralization, releasing inorganic nutrients (C, S, N, P) that otherwise remain trapped in the organic complexity of soil. To process complex organic compounds in soils, these thermophiles require extracellular enzymes to break down large polymers into simple compounds, which can be incorporated into the cells and processed. Soil thermophiles are able to adapt their extracellular enzyme activities to environmental conditions. These enzymes can present optimum activity under high temperatures and reduced water content. Consequently, these microorganisms have been shown to actively process and decompose substances (including pollutants) under extreme conditions (i.e., desiccation and heat) in soils. While nutrient cycling is a highly beneficial process to maintain soil service quality, progressive warming can lead to excessive activity of soil thermophiles and their extracellular enzymes. If this activity is too high, it may lead to reduction in soil organic matter, nutrient impoverishment and to an increased risk of aridity. This is a clear example of a potential effect of future predicted climate warming directly caused by soil microorganisms with major consequences for our understanding of ecosystem functioning, soil health and the risk of soil aridity.

Functional vitamin B12 deficiency: Improving methylmalonic acid reference intervals in urine.

BACKGROUND-AIM: Most laboratory requests focus on the detection of possible vitamin B12 deficiency. In this context, methylmalonic acid (MMA) is reported as the best biomarker. The aim of our study was to establish the biological reference interval for MMA in urine, and assess the influence of age, sex, and vitamin B12 status on MMA concentrations. METHODS: This is a prospective observational study considering individuals with normal results for blood count and liver and kidney function. Individuals who presented supplementation, any pathology or treatment that could cause cobalamin metabolism disorders, and pregnant women were excluded. Likewise, individuals whose vitamin B12 result presented antibody-mediated interference were excluded. Individuals were grouped by age-group and sex. Reference intervals were determined by non-parametric calculation (percentiles 1-99). RESULTS: It was established a single reference interval [0.52 (CI90%: 0.50-0.54) - 5.75 (CI90%: 5.57-6.17) mmolMMA/mol creatinine], with 100 % of individuals with MMA above the upper limit of reference presenting a total vitamin B12 concentration ≤ 238 pmol/L. CONCLUSION: The establishment of optimal reference intervals for methylmalonic acid excretion in urine is crucial in individuals with a suspicion of functional vitamin B12 deficiency. However, the possibility of establishing a cut-off value for total vitamin B12 suggesting subclinical deficiency remains a challenge for this magnitude.

Eating in the city: Experimental effect of anthropogenic food resources on the body condition, nutritional status, and oxidative stress of an urban bioindicator passerine.

Urban areas provide a constant and predictable supply of anthropogenic processed food. The House Sparrow (Passer domesticus Linnaeus, 1758), a declining urban bioindicator species, has recently been reported to have a high level of oxidative stress, with urban diet or pollutants proposed as the potential cause. In this study, we aimed to experimentally determine the effects of two urban trophic resource types (bar snack food leftovers and pet food) on sparrows' physical condition, plasma biochemical nutritional parameters, and blood oxidative status in captivity. To exclude the potential previous effect of urban pollutants, 75 House Sparrows were captured from a rural area in SE Spain and kept in outdoor aviaries. Individuals were exposed to one of three diet treatments: control diet (fruit, vegetables, poultry grain mixture), bar snack diet (ultra-processed snacks), or cat food diet (dry pellets) for 20 days. Blood samples were collected before and after diet treatments to analyze the relative change rates of 12 variables, including physical condition, nutritional status, and oxidant-antioxidant status. A principal component analysis was run to identify gradients of variables covariation, and Generalized Linear Mixed Models were used to determine the effect of diets on each selected PC and on raw variables. The bar snack diet led to signs of anemia and malnutrition, and females tended to lose body condition. The cat food diet increased oxidative stress indicators and protein catabolism. Unbalanced urban diets can affect the body condition and nutritional physiology of House Sparrows and may also induce oxidative stress despite the absence of environmental pollution.

Photofunctional Scope of Fluorescent Dithienylethene Conjugates with Aza-Heteroaromatic Cations.

A series of dithienylethene (DTE) photoswitches with aza-heteroaromatic cationic moieties is synthesized. The switches are characterized regarding their photochemical and photophysical properties in acetonitrile and in water. The efficiency of the switching and the photostationary state composition depend on the degree of π-conjugation of the heteroaromatic systems. Thus, DTEs with acridinium-derived moieties have very low quantum yields for the ring-closing process, which is in contrast to switches with pyridinium and quinolinium moieties. All switches emit fluorescence in their open forms. The involved electronic transitions are traced back to an integrative picture including the DTE core and the cationic arms. The emission can be fine-tuned by the π-conjugation of the heteroaromatic cations, reaching the red spectral region for DTEs with acridinium moieties. On ring-closing of the DTEs the fluorescence is not observable anymore. Theoretical calculations point to rather low-lying energy levels of the highly conjugated ring-closed DTEs, which would originate near-infrared emission (> 1200 nm). The latter is predicted to be very weak due to the concurrent non-radiative deactivation, according to the energy-gap law. In essence, an ON-OFF fluorescence switching as the result of the electrocyclic ring-closing reaction is observed.

Apocarotenoids in the sexual interaction of Phycomyces blakesleeanus.

A simple genetic test allowed us to carry out the first systematic study of the apocarotenoids in the Mucorales. We have identified 13 apocarotenoids in the culture media of the fungus Phycomyces blakesleeanus (Mucoromycota, Mucorales). Three of these compounds were novel apocarotenoids: (2S,8R,E)-8,14-epoxycyclofarnesa-4,6,9-triene-2,11-diol (6), (2S,6E,8E)-cyclofarnesa-4,6,8-triene-2,10,11-triol (7), and its 6Z isomer (8). Four of the remaining compounds have been reported previously from this fungus and six from other Mucorales. All of them belong to three families, the 18-carbon trisporoids, the 15-carbon cyclofarnesoids, and the 7-carbon methylhexanoids, derived from the three fragments that result when ß-carotene is cleaved at its 11',12' and 12,13 double bonds. The apocarotenoids were more varied and more abundant in mated cultures of strains of opposite sex than in single cultures. The presence of acetate in the medium blocked the production of many apocarotenoids while having little effect on the concentrations of the remaining ones.

Plastic Debris in Nests of Two Water Bird Species Breeding on Inland Saline Lakes in a Mediterranean Biosphere Reserve.

Despite more studies being carried out to know the impacts associated with plastic debris and much effort being spent on marine ecosystems, the impacts of plastics on terrestrial and freshwater species remain largely unknown. Here, we explored the presence of anthropogenic materials in nests of two wader species, the gull-billed tern (Gelochelidon nilotica) and the black-winged stilt (Himantopus himantopus), breeding on the inland salt lakes in the "La Mancha Húmeda" Biosphere Reserve, Central Spain. We revealed the presence of anthropogenic debris, mainly macroplastics (>5 mm), in 2.4% and 12.5% of the sampled nests of the gull-billed tern and the black-winged stilt, respectively. The fragments found in nests ranged from 8 mm to 257 mm for the gull-billed tern and from 7 mm to 19 mm for the black-winged stilt. This debris showed no clear pattern of color or size and probably originated both in the agricultural activities in the surroundings and domestic refuse. Although we did not detect any pernicious impacts on adults or chicks (e.g., entangled, injured, or dead individuals), the presence of plastics and other human waste directly placed in nests located in a protected area should warn us about the ubiquity of these pollutants, and the endocrine and immunological effects, among others, that may reduce the recruitment of new animals to the population should be assessed.