Transcriptomics of Canine Inflammatory Mammary Cancer Treated with Empty Cowpea Mosaic Virus Implicates Neutrophils in Anti-Tumor Immunity.

Canine inflammatory mammary cancer (IMC) is a highly aggressive and lethal cancer in dogs serving as a valuable animal model for its human counterpart, inflammatory breast cancer (IBC), both lacking effective therapies. Intratumoral immunotherapy (IT-IT) with empty cowpea mosaic virus (eCPMV) nanoparticles has shown promising results, demonstrating a reduction in tumor size, longer survival rates, and improved quality of life. This study compares the transcriptomic profiles of tumor samples from female dogs with IMC receiving eCPMV IT-IT and medical therapy (MT) versus MT alone. Transcriptomic analyses, gene expression profiles, signaling pathways, and cell type profiling of immune cell populations in samples from four eCPMV-treated dogs with IMC and four dogs with IMC treated with MT were evaluated using NanoString Technologies using a canine immune-oncology panel. Comparative analyses revealed 34 differentially expressed genes between treated and untreated samples. Five genes (CXCL8, S100A9, CCL20, IL6, and PTGS2) involved in neutrophil recruitment and activation were upregulated in the treated samples, linked to the IL17-signaling pathway. Cell type profiling showed a significant increase in neutrophil populations in the tumor microenvironment after eCPMV treatment. These findings highlight the role of neutrophils in the anti-tumor response mediated by eCPMV IT-IT and suggest eCPMV as a novel therapeutic approach for IBC/IMC.

Advances in microalgal cell wall polysaccharides: a review focused on structure, production, and biological application.

Microalgae have been shown to be useful in several biotechnological fields due to their feasible cultivation and high-value biomolecules production. Several substances of interest produced by microalgae, such as: proteins, lipids, and natural colorants, have already been explored. Based on the continuing demand for new natural molecules, microalgae could also be a valuable source of polysaccharides. Polysaccharides are extremely important in aquaculture, cosmetics, pharmaceutical, and food industries, and have great economic impact worldwide. Despite this, reviews on microalgal polysaccharide production, biological activity, and chemical structure are not abundant. Moreover, techniques of microalgal cultivation, coupled with carbohydrate production, need to be clarified in order to develop forward-looking technologies. The present review provides an overview of the main advances in microalgal cell wall polysaccharide production, as well as their associated potential biological applications and chemical structure. Several studies on future prospects, related to microalgae are presented, highlighting the key challenges in microalgal polysaccharide production.

From Induced-Fit Assemblies to Ternary Inclusion Complexes with Fullerenes in Corannulene-Based Molecular Tweezers.

The participation of the tether moiety in fullerene recognition of corannulene-based molecular tweezers is known to be an important factor. In the present work, we describe the synthesis of a set of fullerene receptors bearing two corannulene units located at a suitable distance to effectively interact with C60 and C70. The tether comprises a fluorene-like scaffold where an assortment of different groups with variable electronic properties has been grafted. The photophysical and electrochemical properties of all final compounds have been unveiled and correlated to the donor/acceptor (DA) nature of the tether. Despite these strong variations, their affinity toward fullerenes cannot be correlated in any way to simple DA behavior as the main contribution to the interaction correspond to London dispersion forces. We found, however, that the sulfur-derived subfamily is able to adapt better to the fullerene outer surface slightly increasing the charge transfer and electrostatic attractive interactions being the most outstanding example the case of thiophene 4-S with C70 as it is capable of forming a ternary 2:1 inclusion complex in solution with an electronic binding energy that offsets entropy and desolvation penalties typically associated with higher-order inclusion complexes.

Epitheliosis is a histopathological finding associated with malignancy and poor prognosis in dogs with mammary tumors.

Canine mammary epitheliosis (ME) is a poorly studied dysplasia that may have premalignant potential. In this study, the clinicopathological relevance of ME was prospectively studied in 90 female dogs with mammary tumors (MTs) that underwent radical mastectomy. ME distribution, extent, and coexistence with benign and malignant MTs were evaluated for each case (505 mammary glands). ME was macroscopically undetectable and was present in 47/90 (52%) cases, frequently bilateral. In dogs with malignant MTs and ME, diffuse ME throughout the mammary chain was present in 10/39 (26%) cases. A histological ME-carcinoma transition was evident in certain histotypes. By immunohistochemistry (AE1/AE3, cytokeratin 14 [CK-14], CK-8/18, vimentin, calponin, p63, Ki-67, estrogen receptor, progesterone receptor, and human epidermal growth factor receptor 2), ME was a slow-growing, triple-negative process with a strong predominance of basal-like nonmyoepithelial cells. ME was associated with older dogs (P = .016), malignant tumors (P = .044), worse clinical stages (P = .013), lymph node metastasis (LNM, P = .021), higher histological grade tumors (P = .035), and shorter overall survival (OS) in univariate analysis (P = .012). Interestingly, ME was distantly located to the malignant tumor in most cases (P = .007). In multivariate analyses, LNM (P = .005), histological grade (P = .006), and tumor size (P = .006) were independent predictors of OS. For the pathologist, the observation of ME should be clearly stated in the MT biopsy report to alert the surgeon/oncologist. Given the differences between canine ME and its human histopathological counterpart (atypical ductal hyperplasia), "epitheliosis" should remain the preferred term for the dog.

Low-Power Transit Time-Based Gas Flow Sensor with Accuracy Optimization.

In this paper, a fully designed ultrasonic transit time-based gas flow sensor is presented. The proposed sensor has been optimized in terms of accuracy, sensitivity, and power consumption at different design stages: mechanical design of the sensor pipe, piezoelectric transducer configuration and validation over temperature, time of flight detection algorithm, and electronics design. From the optimization and integration of each design part, the final designed gas flow sensor is based on the employment of 200 kHz-piezoelectric transducers mounted in a V-configuration and on the implementation of a cross-correlation algorithm based on the Hilbert Transform for time-of-flight detection purposes. The proposed sensor has been experimentally validated at different flow rates and temperatures, and it fully complies with the accuracy specifications required by the European standard EN14236, placing the proposed design into the state of the art of ultrasonic gas flow sensors regarding cost, accuracy, and power consumption, the latter of which is crucial for implementing smart gas meters that are able to autonomously operate as IoT devices by extending their battery life.

Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes.

The use of antimony and bismuth in supramolecular chemistry has been largely overlooked in comparison to the lighter elements of Group 15, and the coordination chemistry of the tripodal ligands [Sb(3-py)3] and [Bi(3-py)3] (L) containing the heaviest p-block element bridgehead atoms has been unexplored. We show that these ligands form a common hybrid metal-organic framework (MOF) structure with Cu(I) and Ag(I) (M) salts of weakly coordinating anions (PF6-, SbF6-, and OTf-), composed of a cationic substructure of rhombic cage (M)4(L)4 units linked by Sb/Bi-M bonding. The greater Lewis acidity of Bi compared to Sb can, however, allows anion···Bi interactions to overcome Bi-metal bonding in the case of BF4-, leading to collapse of the MOF structure (which is also seen where harder metals like Li+ are employed). This study therefore provides insight into the way in which the electronic effects of the bridgehead atom in these ligand systems can impact their supramolecular chemistry.

Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers.

New 1,2-azolylamidino complexes cis-[Ru(bipy)2(NH═C(R)az*-κ2N,N)](OTf)2 (R = Me, Ph; az* = pz, indz, dmpz) are synthesized via chloride abstraction after a subsequent base-catalyzed coupling of a nitrile with the previously coordinated 1,2-azole. The synthetic procedure allows the easy obtainment of complexes having different electronic and steric 1,2-azoylamidino ligands. All of the compounds have been characterized by 1H, 13C, and 15N NMR and IR spectroscopy and by monocrystal X-ray diffraction. Photophysical studies support their phosphorescence, whereas their electrochemistry reveals reversible RuII/RuIII oxidations between +1.13 and +1.25 V (vs SCE). The complexes have been successfully used as catalysts in the photooxidation of different thioethers, the complex cis-[Ru(bipy)2(NH═C(Me)dmpz-κ2N,N)]2+ showing better catalytic performance in comparison to that of [Ru(bipy)3]2+. Moreover, the significant catalytic performance of the dimethylpyrazolylamidino complex is applied to the preparation of the drug modafinil, which is obtained using ambient oxygen as an oxidant. Finally, mechanistic assays suggest that the oxidation reaction follows a photoredox route via oxygen radical anion formation.

(1,2-Azole)bis(bipyridyl)ruthenium(II) Complexes: Electrochemistry, Luminescent Properties, And Electro- And Photocatalysts for CO2 Reduction.

New cis-(1,2-azole)-aquo bis(2,2'-bipyridyl)ruthenium(II) (1,2-azole (az*H) = pzH (pyrazole), dmpzH (3,5-dimethylpyrazole), and indzH (indazole)) complexes are synthesized via chlorido abstraction from cis-[Ru(bipy)2Cl(az*H)]OTf. The latter are obtained from cis-[Ru(bipy)2Cl2] after the subsequent coordination of the 1,2-azole. All the compounds are characterized by 1H, 13C, 15N NMR spectroscopy as well as IR spectroscopy. Two chlorido complexes (pzH and indzH) and two aquo complexes (indzH and dmpzH) are also characterized by X-ray diffraction. Photophysical and electrochemical studies were carried out on all the complexes. The photophysical data support the phosphorescence of the complexes. The electrochemical behavior of all the complexes in an Ar atmosphere indicate that the oxidation processes assigned to Ru(II) → Ru(III) occurs at higher potentials in the aquo complexes. The reduction processes under Ar lead to several waves, indicating that the complexes undergo successive electron-transfer reductions that are centered in the bipy ligands. The first electron reduction is reversible. The electrochemical behavior in CO2 media is consistent with CO2 electrocatalyzed reduction, where the values of the catalytic activity [icat(CO2)/ip(Ar)] ranged from 2.9 to 10.8. Controlled potential electrolysis of the chlorido and aquo complexes affords CO and formic acid, with the latter as the major product after 2 h. Photocatalytic experiments in MeCN with [Ru(bipy)3]Cl2 as the photosensitizer and TEOA as the electron donor, which were irradiated with >300 nm light for 24 h, led to CO and HCOOH as the main reduction products, achieving a combined turnover number (TONCO+HCOO-) as high as 107 for 2c after 24 h of irradiation.

Rice vinasse treatment by immobilized Synechococcus pevalekii and its effect on Dunaliella salina cultivation.

The development of new strategies in microalgal studies represents an outstanding opportunity to mitigate environmental problems coupled with biomass production at a reduced cost. Here we present a combined bioprocess for the treatment of rice vinasse using immobilized cyanobacteria Synechococcus pevalekii in alginate beads followed by the use of the treated vinasse as a culture medium for Dunaliella salina biomass production. Cyanobacterial-alginate beads showed a chlorophyll a production of 0.68 × 10-3 mg bead-1 and a total carotenoid production of 0.64 × 10-3 mg bead-1. The first step showed a decrease in nitrate (91%), total solids (29%), and ions. Addition of treated vinasse into D. salina cultivation resulted in a significant increase in cell replication of about 175% (optimized cultivation). The use of natural seawater drastically reduced the medium cost to US$4.75 per m3 and the addition of treated vinasse has the potential to reduce it even more (up to 69%). This study not only provides an insight on the use of cyanobacteria for rice vinasse treatment but also demonstrates a promising lower-cost medium for marine microalgal biomass production with biotechnological purposes.

Octapodal Corannulene Porphyrin-Based Assemblies: Allosteric Behavior in Fullerene Hosting.

An octapodal corannulene-based supramolecular system has been prepared by introducing eight corannulene moieties in a porphyrin scaffold. Despite the potential of this double picket fence porphyrin for double-tweezer behavior, NMR titrations show exclusive formation of 1:1 adducts. The system exhibits very strong affinity for C60 and C70 (K1 = (2.71 ± 0.08) × 104 and (2.13 ± 0.1) × 105 M-1, respectively), presenting selectivity for the latter. Density functional theory (DFT) calculations indicate that, in addition to the four corannulene units, the relatively flexible porphyrin tether actively participates in the recognition process, resulting in a strong synergistic effect. This leads to a very strong interaction with C60, which in turn also induces a large structural change on the other face (second potential binding site), leading to a negative allosteric effect. We also introduced Zn2+ in the porphyrin core in an attempt to modulate its flexibility. The resulting metalloporphyrin also displayed single-tweezer behavior, albeit with slightly smaller binding constants for C60 and C70, suggesting that the effect of the coordination of fullerene to one face of our supramolecular platform was still transmitted to the other face, leading to the deactivation of the second potential binding site.

Tris(2-pyridyl) Bismuthines: Coordination Chemistry, Reactivity, and Anion-Triggered Pyridyl Coupling.

A series of new tris(2-pyridyl) bismuthine ligands of the type [Bi(2-py')3] have been prepared, containing a range of substituents at various positions within their pyridyl rings (py'). They can act as intact ligands or, as a result of the low C-Bi bond energy, exhibit noninnocent reactivity in the presence of metal ions. Structural studies of Li+ and Ag+ complexes show that the coordination to metal ions using their pyridyl-N atoms and to anions using the Lewis acidity of their Bi(III) centers can be modified by the presence of substituents within the 2-pyridyl rings, especially at the 6- or 3-positions, which can block the donor-N or Lewis acid Bi sites. Electron withdrawing groups (like CF3 or Br) can also severely reduce their ability to act as ligands to metal ions by reducing the electron donating ability of the pyridyl-N atoms. Noninnocent character is found in the reactions with Cu+ and Cu2+, resulting in the coupling of pyridyl groups to form bipyridines, with the rate of this reaction being dependent on the anion present in the metal salts. This leads to the formation of Bi(III)/Cu(I) complexes containing hypervalent [X2Bi(2-R-py)]- (X = Cl, Br) anions. Alternatively, the tris(2-pyridyl) bismuthine ligands can act as 2-pyridyl transfer reagents, transferring 2-py groups to Au(I) and Fe(II).

Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts.

Cationic fac-[Re(CO)3(pz*H)(pypzH)]OTf (pz*H = pyrazole, pzH; 3,5-dimethylpyrazole, dmpzH; indazole, indzH; 3-(2-pyridyl)pyrazole, pypzH) were obtained from fac-[ReBr(CO)3(pypzH)] by halide abstraction with AgOTf and subsequent addition of the corresponding pyrazole. Successive deprotonation with Na2CO3 and NaOH gave neutral fac-[Re(CO)3(pz*H)(pypz)] and anionic Na{fac-[Re(CO)3(pz*)(pypz)]} complexes, respectively. Cationic fac-[Re(CO)3(pz*H)(pypzH)]OTf, neutral complexes fac-[Re(CO)3(pz*H)(pypz)], and fac-[Re(CO)3(pypz)2Na] were subjected to photophysical and electrochemical studies. They exhibit phosphorescent decays from a prevalently 3MLCT excited state with quantum yields (Φ) in the range between 0.03 and 0.58 and long lifetimes (τ from 220 to 869 ns). The electrochemical behavior in Ar atmosphere of cationic and neutral complexes indicates that the oxidation processes assigned to ReI → ReII occurs at lower potentials for the neutral complex compared to cationic complex. The reduction processes occur at the ligands and do not depend on the charge of the complexes. The electrochemical behavior in CO2 saturated media is consistent with CO2 electrocatalyzed reduction, where the values of the catalytic activity [icat(CO2)/icat(Ar)] ranged from 2.7 to 11.5 (compared to 8.1 for fac-[Re(CO)3Cl(bipy)] studied as a reference). Controlled potential electrolysis for the pyrazole cationic (3a) and neutral (4a) complexes after 1 h affords CO in faraday yields of 61 and 89%, respectively. These values are higher for indazole complexes and may be related to the acidity of the coordinated pyrazole.

Dual-Tweezer Behavior of an Octapodal Pyrene Porphyrin-Based System as a Host for Fullerenes.

The incorporation of eight pyrene units in a single porphyrin core exhibits a great synergistic effect, resulting in high affinity toward C60 and C70. This octapyrene porphyrin is easily accessible by a straightforward two-step synthetic approach that involves an octuple Suzuki reaction. The new supramolecular platform can present single- or double-tweezer fullerene hosting behavior. The switch from double- to single-tweezer behavior is triggered by the simple coordination of Zn2+ to the porphyrin. Both the octapyrene porphyrin 2HPOP and its zinc metalloporphyrin analogue ZnPOP show very high affinity for C60 and C70, while simultaneously allowing the discrimination of C70 over C60 in a C60/C70 mixture. The use of 2HPOP and ZnPOP for the enrichment of real fullerene mixtures is also demonstrated.

Copper Complexes in the Promotion of Aldol Addition to Pyridine-2-carboxaldehyde: Synthesis of Homo- and Heteroleptic Complexes and Stereoselective Double Aldol Addition.

CuCl2·2H2O and Cu(ClO4)2·6H2O are able to promote aldol addition of pyridine-2-carboxaldehyde (pyca) with acetone, acetophenone, or cyclohexenone under neutral and mild conditions. The general and simple one-pot procedure for the aldol addition to Cu(II) complexes accesses novel Cu complexes with a large variety of different structural motifs, from which the aldol-addition ligand can be liberated by treatment with NH3. Neutral heteroleptic complexes in which the ligand acts as bidentate, or homoleptic cationic complexes in which the ligand acts as tridentate can be obtained depending on the copper salt used. The key step in these reactions is the coordination of pyca to copper, which increases the electrophilic character of the aldehyde, with Cu(ClO4)2 leading to a higher degree of activation than CuCl2, as predicted by DFT calculations. A regio- and stereoselective double aldol addition of pyca in the reaction of Cu(ClO4)2·6H2O with acetone leads to the formation of a dimer copper complex in which the novel double aldol addition product acts as a pentadentate ligand. A possible mechanism is discussed. The work is supported by extensive crystallographic studies.

Potential Utilization of a Polysaccharide from the Marine Algae Gayralia oxysperma, as an Antivenom for Viperidae Snakebites.

Worldwide, snakebites have serious implications for human health. The administration of antivenom is the official treatment used to reverse the toxic activities of envenomation. However, this therapy is not efficient to treat the local effects, leading to the amputation or deformity of affected limbs. As such, alternative treatments are needed. Here, we analyze the ability of a polysaccharide from the green marine alga Gayralia oxysperma (Go3) to inhibit the effects of venom from Bothrops jararaca and Lachesis muta. B. jararaca or L. muta venoms were incubated together with sulfated heterorhamnans from Go3, and the in vitro (coagulation, proteolytic, and hemolytic) and in vivo (hemorrhagic, myotoxic, edematogenic, and lethal) activities of venoms were assessed. Additionally, Go3 was injected before and after the injection of venoms, and the toxic activities were further tested. When incubated with the venoms, Go3 inhibited all activities, though results varied with different potencies. Moreover, Go3 neutralized hemorrhagic, myotoxic, and edematogenic activities when injected before or after injection with B. jararaca and L. muta venom. Go3 also blocked the coagulation of plasma in mice caused by the venoms in an ex vivo test. Therefore, Go3 has the potential to be used as antivenom for B. jararaca and L. muta bites, notably exhibiting higher efficacy on L. muta venom.

Synergistic Effect of Tetraaryl Porphyrins Containing Corannulene and Other Polycyclic Aromatic Fragments as Hosts for Fullerenes. Impact of C60 in a Statistically Distributed Mixture of Atropisomers.

Symmetric meso-tetraarylporphyrins bearing phenanthrene, pyrene, and corannulene moieties in meta positions have been synthesized in a straightforward procedure under microwave irradiation by quadruple Suzuki-Miyaura reactions. Their (1)H NMR spectra showed the typical pattern of four atropisomers distributed according to their statistical ratio not properly separable due to their fast isomerization. Their ability to bind buckminsterfullerene has been tested with the whole mixture, and different behaviors have been found, α4 isomer corannulene-substituted porphyrins being the best hosts in the family.

In vitro photodynamic inactivation of conidia of the phytopathogenic fungus Colletotrichum graminicola with cationic porphyrins.

Photodynamic inactivation (PDI) is an efficient approach for the elimination of a series of microorganisms; however, PDI involving phytopathogenic filamentous fungi is scarce in the literature. In the present study, we have demonstrated the photoinactivating properties of five cationic meso-(1-methyl-4-pyridinio)porphyrins on conidia of the phytopathogen Colletotrichum graminicola. For this purpose, photophysical properties (photostability and (1)O2 singlet production) of the porphyrins under study were first evaluated. PDI assays were then performed with a fluence of 30, 60, 90 and 120 J cm(-2) and varying the porphyrin concentration from 1 to 25 µmol L(-1). Considering the lowest concentration that enabled the best photoinactivation, with the respective lowest effective irradiation time, the meso-(1-methyl-4-pyridinio)porphyrins herein studied could be ranked as follows: triple-charged 4 (1 µmol L(-1) with a fluence of 30 J cm(-2)) > double-charged-trans2 (1 µmol L(-1) with 60 J cm(-2)) > tetra-charged 5 (15 µmol L(-1) with 90 J cm(-2)) > mono-charged 1 (25 µmol L(-1) with 120 J cm(-2)). Double-charged-cis-porphyrin 3 inactivated C. graminicola conidia in the absence of light. Evaluation of the porphyrin binding to the conidia and fluorescence microscopic analysis were also performed, which were in agreement with the PDI results. In conclusion, the cationic porphyrins herein studied were considered efficient photosensitizers to inactivate C. graminicola conidia. The amount and position of positive charges are related to the compounds' amphiphilicity and therefore to their photodynamic activity.

Sulfated Galactan from Palisada flagellifera Inhibits Toxic Effects of Lachesis muta Snake Venom.

In Brazil, snakebites are a public health problem and accidents caused by Lachesis muta have the highest mortality index. Envenomation by L. muta is characterized by systemic (hypotension, bleeding and renal failure) and local effects (necrosis, pain and edema). The treatment to reverse the evolution of all the toxic effects is performed by injection of antivenom. However, such therapy does not effectively neutralize tissue damage or any other local effect, since in most cases victims delay seeking appropriate medical care. In this way, alternative therapies are in demand, and molecules from natural sources have been exhaustively tested. In this paper, we analyzed the inhibitory effect of a sulfated galactan obtained from the red seaweed Palisada flagellifera against some toxic activities of L. muta venom. Incubation of sulfated galactan with venom resulted in inhibition of hemolysis, coagulation, proteolysis, edema and hemorrhage. Neutralization of hemorrhage was also observed when the galactan was administered after or before the venom injection; thus mimicking a real in vivo situation. Moreover, the galactan blocked the edema caused by a phospholipase A2 isolated from the same venom. Therefore, the galactan from P. flagellifera may represent a promising tool to treat envenomation by L. muta as a coadjuvant for the conventional antivenom.

[Capsule endoscopy and obscure gastrointestinal bleeding: does the form of presentation matter?]. / Cápsula endoscópica y hemorragia digestiva de origen oscuro: ¿importa la forma de presentación?

INTRODUCTION: Obscure gastrointestinal bleeding (OGIB) is defined as bleeding from the gastrointestinal tract with no obvious cause after assessment with upper and lower gastrointestinal endoscopy. In these cases, the source is suspected to be in the small bowel. Obscure bleeding can be occult or overt. The aim of this study was to analyze the clinical and analytical characteristics and findings on capsule endoscopy in patients with OGIB and to determine the factors related to the detection of lesions in both forms of presentation. METHODS: We performed a retrospective study of capsule endoscopies carried out between November 2009 and November 2012 for OGIB. RESULTS: We analyzed 284 capsule endoscopies in 272 patients. Initially, 12 procedures could not be evaluated and were repeated. A total of 272 procedures were finally included in the analysis. The results of 114 (41.9%) capsule endoscopies were normal. Compared with patients with occult OGIB, those with overt OGIB were significantly older (70.2 vs. 67.5 years; p = 0.04), consumed more NSAID (24.2% vs. 11.9%; p = 0.01), had higher hemoglobin levels (9.3 vs. 10.4; p < 0,001) and more frequently required transfusion (64.5% vs 32.2%; p < 0.001). No differences were found between the two forms of presentation in the detection of canker sores-ulcers and polyps-masses. Vascular lesions were more frequently detected in overt than in occult OGIB (40.3% vs. 25.7%, respectively), (p < 0.05). When the total number of diagnoses carried out by capsule endoscopy was analyzed, no differences were found in diagnostic yield between overt OGIB (57%) and occult OGIB (54%), (p = 0.6). In overt OGIB, multivariate analysis showed that the variables that significantly predicted the detection of lesions on capsule endoscopy were consumption of medication NSAID (OR 2.75; p = 0.01), antiplatelets and anticoagulants (OR 2.64; p = 0.03) and analytical data hemoglobin (OR 3.23; p < 0.001) and INR (OR 1.8; p = 0.02). In occult OGIB, multivariate analysis showed that the factors significantly related to the detection of lesions on endoscopy were age (OR 1.9; p = 0.04) and NSAID consumption (OR 2.1; p = 0.01). CONCLUSIONS: Capsule endoscopy is essential in the assessment of OGIB. Although the diagnostic yield was similar in both forms of presentation, vascular lesions were more frequently detected in overt OGIB. The diagnostic yield of capsule endoscopy could be optimized by taking into account the form of presentation (overt vs. occult) and certain clinical and analytic data (age, drug consumption, hemoglobin).

Pyrazolylamidino ligands from coupling of acetonitrile and pyrazoles: a systematic study.

Mixed pyrazole-acetonitrile complexes, both neutral fac-[ReBr(CO)3(NCMe)(pz*H)] (pz*H = pzH, pyrazole; dmpzH, 3,5-dimethylpyrazole; or indzH, indazole) and cationic fac-[Re(CO)3(NCMe)(pz*H)2]A (A = BF4, ClO4, or OTf), are described. Their role as the only starting products to obtain final pyrazolylamidino complexes fac-[ReBr(CO)3(NH═C(Me)pz*-κ(2)N,N)] and fac-[Re(CO)3(pz*H)(NH═C(Me)pz*-κ(2)N,N)]A, respectively, is examined. Other products involved in the processes, such as fac-[ReBr(CO)3(pz*H)2], fac-[Re(CO)3(NCMe)(NH═C(Me)pz*-κ(2)N,N)]A, and fac-[Re(CO)3(pz*H)2(OTf)] are also described. Warming CD3CN solutions of fac-[Re(CO)3(NCMe)(pz*H)2]A at 40 °C gives cleanly the pyrazolylamidino complexes [Re(CO)3(pz*H)(NH═C(Me)pz*-κ(2)N,N)]A as the only products, pointing to an intramolecular process. This is confirmed by carrying out reactions in the presence of one equivalent of a pyrazole different from that coordinated, which affords complexes where the pyrazolylamidino ligand contains only the pyrazole previously coordinated. When the reactions lead to an equilibrium mixture of the final and starting products, the reverse reaction gives the same equilibrium mixture, which indicates that the coupling reaction of pyrazoles and nitriles to obtain pyrazolylamidino ligands is a reversible intramolecular process. A systematic study of the possible factors which may affect the reaction gives the following results: (a) the yields of the direct reactions are higher for lower temperatures; (b) the tendency of the pyrazoles to give pyrazolylamidino complexes follows the sequence indzH > pzH > dmpzH; and (c) the reaction rates do not depend on the nature of the anion even when a large excess is added. The presence of a small amount of aqueous solution of NaOH catalyzes the reaction. Thus, addition of 0.5-1% of NaOH (aq) to solutions of fac-[ReBr(CO)3(NCMe)(pz*H)] (in CD3CN) or fac-[Re(CO)3(NCMe)(pz*H)2]A (in CD3CN, CD3NO2 or (CD3)2CO) allowed the syntheses of the corresponding pyrazolylamidino complexes [ReBr(CO)3(NH═C(Me)pz*-κ(2)N,N)] or [Re(CO)3(pz*H)(NH═C(Me)pz*-κ(2)N,N)]A with better yields, more rapidly, and in milder conditions.