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We describe synthesis of a symmetric protein triad comprising a genetically fused recombinant hemoglobin(di-α/Cβ120) center and human serum albumin sides [rHb(di-α/Cβ120)–HSA2]. This trimer is not ...

Mechanochromic luminescent materials, exhibiting a change in luminescence behavior under external stimuli have emerged as one of the promising candidates for upcoming efficient OLEDs. Recently mechanochromic luminescence was reported in a donor-acceptor-donor (D-A-D) triad featuring two phenothiazine units separated by a dibenzo[ a, j ] phenazine motif. The triad follows different emissive routes ranging from phosphorescence to TADF based on the conformational switching of the D units. In this article, we investigate such conformation-dependent photophysical behavior of this triad through theoretical calculations. By analyzing the nature of ground state, excited state and factors determining the reverse ISC crossing rates associated with the relative orientation of the D and A units, we delineate the effect of the conformational changes on their photophysical properties. Our findings reveal that axial orientation of both the donor groups enhances the overlap between HOMO and LUMO leading to a large singlet-triplet gap (Δ E ST ) which drives phosphorescence emission. On the contrary, the equatorial orientation of the donor groups minimizes Δ E ST to facilitate rISC making the conformers TADF active. The role of several geometric factors affecting the photophysical properties of the conformers is also highlighted. Finally, we show how to regulate the population difference among the conformers by functionalizing the triad to harvest the maximum TADF efficiency.

Peptic ulcers are one of the world's major gastrointestinal disorders, embracing both gastric and duodenal ulcers, and affecting 10% of the world population. The current study aimed to investigate the possible protective effect of tadalafil and pentoxifylline (PTX) on indomethacin-induced peptic ulcers. Male albino rats were divided into five groups: control group; ulcerated group; Indomethacin + Tadalafil, in which animals were pretreated with tadalafil orally before indomethacin; Indomethacin+ PTX, in which animals were pretreated with PTX orally before indomethacin; and Indomethacin + Tadafil + PTX. Indomethacin treatment revealed histopathological changes and ulcer scoring and ulcer index were markedly increased. Serum levels of prostaglandin and heme oxygenase-1 were significantly decreased. The ulcerogenic also induced marked oxidative stress as evident from the increased malondialdehyde, decreased in gastric glutathione content and superoxide dismutase activity, while the gastric myeloperoxidase was increased. Gastric nitric oxide content was decreased and the expression of vascular endothelial growth factor was downregulated while the tumor necrosis factor α (TNF-α) level was dramatically increased. Pretreatment of the ulcerative group by either tadalafil or PTX or their combination improved all these pathological changes. Tadalafil or PTX may have a role in protecting gastric mucosa damage caused by indomethacin which may be useful in the future for the treatment of gastric ulceration.

In this work, a novel triad nanocomposites containing trititanate nanotubes, Ag nanoparticles and dopamine were prepared and the SERS properties were measured experimentally. Control over the size and position of the Ag nanoparticles in the TiNT-dop-Ag system, along with the localised surface plasmon resonance (LSPR) of the Ag particles matching the Raman excitation wavelength, gives a SERS enhancement greater than 6 orders of magnitude. Electromagnetic modelling was used to provide a theoretical basis for these results.

2,7-Bis(2-phenyl-1H-imidazol-4-yl)fluorenone (BPIFO) was synthesized as a new fluorenone derivative bearing two imidazole moieties, and it exhibited remarkable and reversible changes in photo physi...

A 3-phase Golay complementary triad (GCT) is a set of three sequences over the 3-phase alphabet {1, ω, ω2}, where $\omega =e^{\frac {2\pi \sqrt {-1}}{3}}$ is a 3rd root of unity, whose aperiodic autocorrelations sum up to zero for each out-of-phase non-zero time-shifts. Recent results by Avis and Jedwab proved the non-existence of 3-phase GCTs of length N ≡ 4 (mod 6). In this paper, we introduce 3-phase Z-complementary triads (ZCTs) and almost-complementary triads (ACTs). We present systematic constructions of 3-phase ZCTs for various lengths including the case when N ≡ 4 (mod 6). We also analyse the peak-to-mean envelope power ratio (PMEPR) upper-bounds of the proposed ZCTs and ACTs.

Graphical abstract, For the whole GFP family, a few cases, when a single mutation in the chromophore environment strongly inhibits maturation, were described. Here we study EYFP-F165G – a variant of the enhanced yellow fluorescent protein – obtained by a single F165G replacement, and demonstrated multiple fluorescent states represented by the minor emission peaks in blue and yellow ranges (~470 and ~530 nm), and the major peak at ~330 nm. The latter has been assigned to tryptophan fluorescence, quenched due to excitation energy transfer to the mature chromophore in the parental EYFP protein. EYFP-F165G crystal structure revealed two general independent routes of post-translational chemistry, resulting in two main states of the polypeptide chain with the intact chromophore forming triad (~85%) and mature chromophore (~15%). Our experiments thus highlighted important stereochemical role of the 165th position strongly affecting spectral characteristics of the protein. On the basis of the determined EYFP-F165G three-dimensional structure, new variants with ~ 2-fold improved brightness were engineered.

Donor–acceptor–donor (DAD) triad systems are commonly applied as active materials in ambipolar organic field-effect transistors, organic solar cells, and NIR-emitting organic light-emitting diodes. Often, these triads utilize oligothiophenes as donors, whereas their oxygen-containing analogs, oligofurans, are far less studied in this setup. Here we introduce a family of DAD triads in which the donors are oligofurans and the acceptor is benzothiadiazole. In a combined computational and experimental study, we show that these triads display optical bandgaps similar to those of their thiophene analogs, and that a bifuran donor is sufficient to produce emission in the NIR spectral region. The presence of a central acceptor unit increases the photostability of oligofuran-based DAD systems compared with parent oligofurans of the similar length.

Fasteners are commonly used in construction industry for parts joining purpose. There are many types of construction fasteners such as stud, bolt, anchor, nut, screw, and washer. The major problem of the fastener made by carbon steel is the poor resistance to corrosion. Electroplating is a simple yet low-cost tool to give a strong corrosion protection coating layer on the carbon steel. This study was performed to investigate the effect of current and deposition time on the iron triad (cobalt-nickel-iron) electroplating on the fastener washer. The experiment was conducted at 50 °C, pH 1-3 and at different electroplating time (30 minutes to 90 minutes) and current (0.2 A to 0.5 A). Burnt-out surface coating was observed on the fastener washer when the current was more than 0.4 A. A field test was carried out for 60 days to observe the corrosion behavior and performance of the products. Scanning electron microscope (SEM) analysis showed that a thin protection layer with 5.64 µm was formed at 60 minutes of electroplating time and 0.4 A of current. The surface roughness of the fastener washer was increased by increasing the electroplating time and current. The hardness was also improved with higher current and electroplating time if compared to the original fastener washer. The result of this study confirmed that a strong adhesive corrosion resistant layer to the fastener washer was using the current of 0.4 A (77 mA/cm2) and the electroplating time of 60 minutes.

Objective To analyze the risk factors of elbow stiffness following open reduction and internal fixation of the terrible triad of the elbow joint. Methods A retrospective study was conducted of 100 patients with the terrible triad of the elbow joint, who had been treated at our hospital from January 2015 to December 2018. All patients were treated with a loop plate to repair the ulnar coronoid process. According to the severity of the injury, the radial head was either fixed or replaced, and the lateral collateral ligament was repaired with an anchor. According to the range of motion of the elbow during the last follow‐up, the patients were divided into two groups. The stiffness group (displayed extension–flexion or pronation–supination 1 week (OR = 2.714, 95% CI 1.029–7.159, P = 0.044), and postoperative immobilization time (OR = 3.237, 95% CI 1.176–8.908, P = 0.023) were independent risk factors of elbow stiffness after surgery for the terrible triad of the elbow. Conclusion High‐energy injury, the time from injury to surgery > 1 week, and postoperative joint immobilization time > 2 weeks are the independent risk factors of elbow stiffness after surgery of the terrible triad of the elbow, which should be treated carefully in clinical treatment., The patient is a 35‐year‐old female with traffic injury. The terrible triad of the right elbow, the ulnar coronal process was fixed with loop steel plate, the radial head was fixed with countersunk head nail, and the lateral ligament complex was repaired with thread rivet. Preoperative X‐ray examination of elbow joint (A, B) CT examination of (C)). X‐ray examination of elbow joint on the second day after operation (D, E).

Introduction: The medial collateral ligament (MCL) is the most commonly injured ligament of the knee joint; however, its displacement into the medial knee compartment is rare. Traumatic posterior root of medial meniscus (PRMM) tears are commonly found in high-grade injuries involving anterior cruciate ligament (ACL) or posterior cruciate ligament (PCL) tears along with MCL tears. Diagnosis of these injuries can be made by a preoperative magnetic resonance imaging (MRI), but they can be missed at times due to severe soft-tissue swelling in the acute phase. Case Report: A 25-year-old gentleman presented with injury to the front of his left knee 5 days back. On examination, he had a Grade 3 effusion with valgus stress test and posterior drawer test being positive and medial joint line tenderness was present. A firm localized swelling was palpable on the medial joint line. MRI scan revealed a mid-substance PCL tear, ACL sprain, PRMM tear, and tibial side rupture of superficial MCL with proximally migrated wavy MCL fibers lying below the medial meniscus confirmed on arthroscopy. Medial meniscus root repair by pull through technique and PCL reconstruction with a 3-strand peroneus longus graft followed by open MCL repair with augmentation using a semitendinosus graft was performed. Postoperatively, the knee was kept in a straight knee brace for 4 weeks, followed by a hinged knee brace and appropriate physiotherapy were started. At 2 years follow-up, the patient had attained full range of knee motion with good quadriceps strength, tibial step off maintained, and negative posterior drawer test and valgus stress test. Displacement of torn MCL into the medial knee compartment is an extremely rare injury. Proximal or distal avulsion of MCL with intra-articular incarceration has been reported in isolation or associated with ACL tear. Such an injury triad as reported here has not been reported in the literature to the best of our review. Conclusion: In our case, we report a very unusual injury triad of PCL tear, PRMM tear, and distal MCL tear with intra-articular entrapment below the medial meniscus operated by a single-stage surgery with excellent outcomes.

We demonstrated that a synthetic ligand NA, which selectively binds to a 5′-CAG-3′/5′-CAG-3′ triad, induced repeat contractions during DNA polymerase-mediated primer extension through the CAG repeat template. A thorough capillary electrophoresis and sequencing analysis revealed that the d(CAG)20 template gave shortened nascent strands mainly containing 3–6 CTG units in the presence of NA.

Fluorescent labels and probes constitute an important class of organic materials used in the development of sensor systems and imaging platforms for various chemical and molecular biology applications. In the development of fluorescent labels and probes, multichromic environment-sensitive fluorophores are very important. In this work, novel triad systems, including subphthalocyanine, BODIPY and thiophene/thianaphthene units, were prepared and their molecular structures were identified using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and 1H and 13C NMR spectroscopy. The optical properties of the subphthalocyanine–BODIPY–thiophene/thianaphthene triads were determined using UV-vis absorption and fluorescence (2D and 3D) spectroscopic methods and quantum chemical calculations. The data were analyzed by comparing the results of the final properties to those of the BODIPY- and subphthalocyanine-alone units. The compounds were also evaluated in live cell imaging using a breast cancer cell line. The novel subphthalocyanine–BODIPY–thiophene/thianaphthene triads displayed dual color emission, which is critically important for the development of novel systems particularly in biomedical applications such as bioimaging and cellular sensor systems.

Two supramolecular cobalt(II) porphyrin–fullerene systems, (PyC60)2CoDTBCP/(Py2C70)CoDTBCP, self-assembled via axial coordination of 1-N-methyl-2-(pyridin-4-yl)-3,4-fullero[60]pyrrolidine and 2,5-di-(pyridin-2-yl)-3,4-fullero[70]pyrrolidine by (5,15-bis[3,5-bis(tert-butyl)phenyl]-10,20-bis[4,6-(4-(3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)pyrimidin-5-yl]porphinato)cobalt(II), respectively, were prepared and characterized for the first time. Target carbazole-functionalized cobalt(II) porphyrin was synthesized by direct metallation of the corresponding porphyrin that was in its turn obtained by tetra-substitution of 5,15-bis[4,6-dichloropyrimidin-5-yl]porphyrin with 4-(3,6-di-tert-butyl-9H-carbazol-9-yl)phenol. All compounds synthesized were fully characterized by mass spectrometry and UV-vis, IR, and 1H NMR spectroscopy. Chemical structure and spectral properties of the triad/dyad were additionally described using chemical thermodynamics, kinetics, and DFT calculations. The analysis of the geometric and electronic structures of the (PyC60)2CoDTBCP and (Py2C70)CoDTBCP FMOs in the ground state and the study of their femtosecond transient absorption spectra points to the existence of photoinduced electron transfer in the triad and dyad. The data obtained are required for further photoelectrochemical study of the triad/dyad and determining their potential in the building of photovoltaic devices.

Background Few reliable methods to simulate and evaluate the intersegmental plane have been reported. We introduce intersegmental plane simulation based on the bronchus-vein-artery triad in three-dimensionally reconstructed images from patients who underwent segmentectomy for early lung cancer. Methods We collected clinical data of consecutive patients with early-stage lung cancer who underwent three-dimensional imaging-guided single-port thoracoscopic segmentectomy at Department No. 1 of Thoracic Surgery at Fujian Medical University Fujian Union Hospital from January 2019 to July 2019. Patients were divided into two groups according to the application of intersegmental plane simulation and nodule analysis: the intersegmental plane group and the non-intersegmental plane group. General clinical characteristics, operation status, and postoperative recovery were compared between groups. The three-dimensional reconstruction results in the intersegmental plane group were analyzed and summarized. Results A total of 120 patients were included (61 in the intersegmental plane group and 59 in the non-intersegmental plane group). There were no significant differences between the two groups in general characteristics (all P>0.05). All target lesions were resected in both groups. There were no significant differences between groups in operation characteristics or postoperative recovery, with the exception of the duration of chest drainage and the rate of gross margin insufficiency. There were five cases of gross margin insufficiency in the non-intersegmental plane group. With three-dimensional imaging reconstruction, a total of 131 intersegmental veins could be used to evaluate the simulated intersegmental plane in 61 patients, with an average of 2.1±0.5 veins per patient. Two patients (3.3%) had one vein that could be used to evaluate the intersegmental plane, 50 patients (82.3%) had two, seven patients (11.3%) had three, and two patients (3.3%) had four. The total number of intersegmental veins located on the simulated intersegmental plane was 124 (94.7%), with an average of 2.0±0.6 veins per patient. The accuracy of intersegmental plane simulation was 91.8% (56/61). Conclusions The bronchus-vein-artery triad in intersegmental plane simulation can assist surgeons in preoperative planning and can facilitate complete resection of early lung cancer with sufficient surgical margins.

By utilizing the bipolarity of 1,2-diphenylphenanthroimidazole (PPI), two types of asymmetrical tripartite triads (PPI-TPA and PPI-PCz) were designed with triphenylamine (TPA) and 9-phenylcarbazole (PCz). These triads are deep-blue luminescent materials with a high fluorescence quantum yield of nearly 100 %. To trace the photophysical behaviors of these triads, their excited-state evolution channels and interchromophoric interactions were investigated by ultrafast time-resolved transient absorption and excited-state theoretical calculations. The results suggest that the electronic nature, asymmetrical tripartite structure, and electron-hole distance of these triads, as well as solvent polarity, determine the lifetime of intramolecular charge transfer (ICT). Interestingly, PPI-PCz triads show anti-Kasha ICT, and the charge-transfer direction among the triads is adjustable. For the PPI-TPA triad, the electron is transferred from TPA to PPI, whereas for the PPI-PCz triad the electron is pushed from PPI to PCz. Exploration of the excited-state ICT in these triads may pave the way to design better luminescent materials in the future.

Centronuclear myopathies (CNMs) are a subtype of congenital myopathies characterized by skeletal muscle weakness and an increase in the number of central myonuclei. SPEG (striated preferentially expressed protein kinase) has been identified as the sixth gene associated with CNM, and it has been shown that striated muscle-specific Speg-knockout (KO) mice have defective triad formation, abnormal excitation-contraction coupling, and calcium mishandling. The impact of SPEG deficiency on the survival and function of myogenic cells remains to be deciphered. In this study, the authors examined the overall population, proliferation, and differentiation of myogenic cells obtained from striated muscle-specific Speg-KO mice and compared them with wild-type (WT) controls. SPEG-deficient skeletal muscles contained fewer myogenic cells, which on further study demonstrated reduced proliferation and delayed differentiation compared with those from WT muscles. Regenerative response to skeletal muscle injury in Speg-KO mice was compared with that of WT mice, leading to the identification of similar abnormalities including fewer satellite cells, fewer dividing cells, and an increase in apoptotic cells in KO mice. Overall, these results reveal specific abnormalities in myogenic cell number and behavior associated with SPEG deficiency. Similar satellite cell defects have been reported in mouse models of MTM1- and DNM2-associated CNM, suggestive of shared underlying pathways.

The effect of salt on the electrostatic interaction of a protein is an important issue, because addition of salt affects protein stability and association/aggregation. Although adding salt is a generally recognized strategy to improve protein stability, this improvement does not necessarily occur. The lack of an effect upon the addition of salt was previously confirmed for the tenth fibronectin type III domain from human fibronectin (FN3) by thermal stability analysis. However, the detailed molecular mechanism is unknown. In the present study, by employing the negatively charged carboxyl triad on the surface of FN3 as a case study, the molecular mechanism of the inefficient NaCl effect on protein stability was experimentally addressed using spectroscopic methods. Complementary analysis using Raman spectroscopy and 8-anilino-1-naphthalenesulfonic acid fluorescence revealed the three-phase behavior of the salt-protein interaction between NaCl and FN3 over a wide salt concentration range from 100 mM to 4.0 M, suggesting that the Na+-specific binding to the negatively charged carboxyl triad causes a local conformational change around the binding site with an accompanying structural change in the overall protein, which contributes to the protein's structural destabilization. This spectroscopic evidence clarifies the molecular understanding of the inefficiency of salt to improve protein stability. The findings will inform the optimization of formulation conditions.

With the aim of designing new photoactive donor–acceptor dyads, self-assembly in the (ethoxy)(oxo)(5,10,15,20-(4-methylphenyl)porphinato)molybdenum(V) (O=Mo(OEt)TTP)–2[Formula: see text]-(pyridin-4-yl)-5[Formula: see text]-(pyridin-2-yl)-1[Formula: see text]-(pyridin-2-yl-methyl)pyrrolidino[60]fullerene (Py3F)-toluene systems was quantitatively studied using spectral methods (UV-vis, IR,1H NMR, mass spectrometry), chemical thermodynamics, and chemical kinetics. Interaction between O=Mo(OEt)TTP and pyridine (Py) proceeding as step equilibriums was preliminarily studied to model the processes above. The novel donor–acceptor triad based on O=Mo(OEt)TTP and Py3F is represented with both quantitative description of its formation and conformation of the chemical structure. Prospects for the study of the triad as a photosynthetic antenna imitator and an active layer in organic solar cells are substantiated by a fluorescence method. Along with this, it has been demonstrated that O=Mo(OEt)TTP is a good candidate for use as an optical and fluorescent chemosensor of volatile organic compounds and nitrogen bases — the building blocks of pharmaceuticals, food components and environmental pollutants.

In the recently published researches in the object localization field, 3D object localization takes the largest part of this research due to its importance in our daily life. 3D object localization has many applications such as collision avoidance, robotic guiding and vision and object surfaces topography modeling. This research study represents a novel localization algorithm and system design using a low-resolution 2D ultrasonic sensor array for 3D real-time object localization. A novel localization algorithm is developed and applied to the acquired data using the three sensors having the minimum calculated distances at each acquired sample, the algorithm was tested on objects at different locations in 3D space and validated with acceptable level of precision and accuracy. Polytope Faces Pursuit (PFP) algorithm was used for finding an approximate sparse solution to the object location from the measured three minimum distances. The proposed system successfully localizes the object at different positions with an error average of ±1.4 mm, ±1.8 mm, and ±3.7 mm in x-direction, y-direction, and z-direction, respectively, which are considered as low error rates.

To explore the efficient way of assembling electron donating (D) and accepting (A) moieties in small molecule donors (SMDs) for organic solar cells, ADA and DAD type triad donor molecules were synt...

Iron-containing metalloenzymes that contain the 2-His-1-Carboxylate facial triad at their active site are well known for their ability to activate molecular oxygen and catalyse a broad range of oxidative transformations. Many of these reactions are synthetically challenging, and developing small molecular iron-based catalysts that can achieve similar reactivity and selectivity remains a long-standing goal in homogeneous catalysis. This review focuses on the development of bioinspired facial N,N,O ligands that model the 2-His-1-Carboxylate facial triad to a greater degree of structural accuracy than many of the polydentate N-donor ligands commonly used in this field. By developing robust, well-defined N,N,O facial ligands, an increased understanding could be gained of the factors governing enzymatic reactivity and selectivity.

Nests of three silanol groups are located on the internal pore surface of calcined zeolite SSZ‐70. 2D 1H double/triple‐quantum single‐quantum correlation NMR experiments enable a rigorous identification of these silanol triad nests. They reveal a close proximity to the structure directing agent (SDA), that is, N,N′‐diisobutyl imidazolium cations, in the as‐synthesized material, in which the defects are negatively charged (silanol dyad plus one charged SiO− siloxy group) for charge balance. It is inferred that ring strain prevents the condensation of silanol groups upon calcination and removal of the SDA to avoid energetically unfavorable three‐rings. In contrast, tetrad nests, created by boron extraction from B‐SSZ‐70 at various other locations, are not stable and silanol condensation occurs. Infrared spectroscopic investigations of adsorbed pyridine indicate an enhanced acidity of the silanol triads, suggesting important implications in catalysis., Silanol defects determine adsorption and catalysis in zeolites by their hydrophilic properties, but they can also contribute to catalytic reactions through their weak acidities or cooperative effects with other active sites. Well‐defined silanol defect clusters (see structure: cyan H, red O, black Si) with distinct size in topologically related zeolites, SSZ‐70 and ITQ‐1 are identified by NMR spectroscopy.

A multimodular donor-acceptor conjugate featuring silicon phthalocyanine (SiPc) as the electron donor, and two electron acceptors, namely tetrachloroperylenediimide (PDI) and C60 , placed at the opposite ends of the SiPc axial positions, was newly designed and synthesized, and the results were compared to the earlier reported PDI-SiPc-C60 triad. Minimal intramolecular interactions between the entities was observed. Absorption, fluorescence, computational and electrochemical studies were performed to evaluate the excitation energy, geometry and electronic structure, and energy levels of different photoevents. Steady-state absorption, fluorescence and excitation spectral studies revealed efficient singlet-singlet energy transfer from 1 PDI* to SiPc in the PDI-SiPc dyad and the PDI-SiPc-C60 triad. The measured rates for these photochemical events were found to be much higher than those reported earlier for the triad, due to closer proximity between the PDI and SiPc entities. The distance also affected the charge separation path in which involvement of PDI, and not C60 , in charge separation in the present triad was witnessed. The present investigation brings out the importance of donor-acceptor distances in channeling photochemical events in a multimodular system.

The study utilized finite element method to determine displacements and stresses in a set of Pauwels Type III femoral neck fractures repaired using 3 techniques (cannulated screws (Triad), sliding hip screw (SHS), and a Hybrid (SHS + cannulated screws). The research found that shear displacement doubled between the 65° and 75° fracture angles regardless of fixation construct. The SHS alone was the least stable construct, with highest construct stresses and shear displacement along the fracture plane. The stability of the Hybrid and Triad constructs were similar, but stress in the Hybrid was lower suggesting it would provide a higher load to failure than the Triad.

Amphiphilic Ru(bpy)32+ complex (DC17Ru)���citratoperoxotitanate (CPT) ���ditetradecylviologen (DC14V) triad nano-film was fabricated on quartz slab optical waveguide by organic-inorganic hybrid Langmuir-Blodgett method. Transient phosphorescence of the DC17Ru monolayer at 610 nm excited by 532 nm pulsed laser was observed by SOWG spectroscopy. The phosphorescence was partly quenched by the CPT layer and the quenching was enhanced by the DC14V monolayer underneath the CPT layer in the DC17Ru-CPT nano-film. Energy levels of the components, DC17Ru, CPT and DC14V suggests an exergonic cascade electron transfer mechanism from the excited state of DC17Ru to DC14V via the CPT.

Background: Studies examining the physiological consequences associated with deficits in energy availability (EA) for male athletes are sparse.Purpose: To examine male athlete triad components; low energy availability (LEA) with or without an eating disorder risk (ED), reproductive hormone [testosterone (T)], and bone mineral density (BMD) in endurance-trained male athletes during different training periods.Methods: A cross-sectional design with 14 participants (age: 26.4 ± 4.2 years; weight: 70.6 ± 6.4 kg; height: 179.5 ± 4.3 cm; BMI: 21.9 ± 1.8 kg/m2) were recruited from the local community. Two separate training weeks [low (LV) and high (HV) training volumes] were used to collect the following: 7-day dietary and exercise logs, and blood concentration of T. Anthropometric measurements was taken prior to data collection. A one-time BMD measure (after the training weeks) and VO2max-HR regressions were utilized to calculate EEE.Results: Overall, EA presented as 27.6 ± 10.7 kcal/kgFFM·d-1 with 35% (n = 5) of participants demonstrating increased risk for ED. Examining male triad components, 64.3% presented with LEA (≤ 30 kcal/kgFFM·d-1) while participants presented with T (1780.6 ± 1672.6 ng/dl) and BMD (1.31 ±.09 g/cm2) within normal reference ranges. No differences were found across the 2 training weeks for EI, with slight differences for EA and EEE. Twenty-five participants (89.3%) under-ingested CHO across both weeks, with no differences between weeks.Conclusion: Majority of endurance-trained male athletes presented with one compromised component of the triad (LEA with or without ED risk); however, long-term negative effects on T and BMD were not demonstrated. Over 60% of the participants presented with an EA ≤ 30 kcal/kgFFM·d-1, along with almost 90% not meeting CHO needs. These results suggest male endurance-trained athletes may be at risk to negative health outcomes similar to mechanistic behaviors related to EA with or without ED in female athletes.

Terrible triad of the elbow injury is difficult to manage, and the role of the coronoid process in instability is very important. We describe a simple, modified suture technique to fix a coronoid process fragment using suture anchor fixation.Eight patients (three female and five male) with coronoid process injuries with the fragment involving50% of the total height (Regan-Morrey type I/II) in terrible triad of elbow injury were included. Patients were treated operatively via a lateral Kocher's approach, and coronoid process fractures were repaired with a single pulley double-strand suture technique. Structures were addressed in a sequential fashion-the coronoid process, radial head, lateral ulnar collateral ligament.All patients were treated with the single pulley double-strand anchor suture technique and the coronoid process fragment was found to be in good contact with the original avulsion site using the method. The final Mayo Elbow Performance Score was excellent (90) in six patients and good (between 85 and 89) in two patients after operation 6 months.The single pulley double-strand suture tie method using a suture anchor is a less invasive and simpler fixation method for the repair of coronoid process fractures in patients with terrible triad of the elbow injuries and results in good outcomes.

Funding Acknowledgements Type of funding sources: None. Introduction In a previous retrospective study it was demonstrated that an electrophysiological triad was able to identify critical isthmus in atrial flutter (AFL) patients. This triad is based in the Carto® electroanatomical mapping (EAM) version 7, which displays a histogram of the local activation times (LAT) of the tachycardia cycle length (TCL), in addition to the activation and voltage maps. This study aimed to prospectively assess the ability of an electrophysiological triad to identify and localize the AFL’s critical isthmus. Methods Prospective analysis of a unicentric registry of individuals who underwent left AFL ablation with Carto® EAM. All patients with non-left AFL, lack of high-density EAM, less than 2000 collected points or lack of mapping in any of the left atrium walls or structures were excluded. Ablation sites of arrhythmia termination were compared to an electrophysiological triad constituted by: areas of low-voltage (0.05 to 0.3mV), sites of deep histogram valleys (LAT-Valleys) with less than 20% density points relative to the highest density zone and a prolonged LAT-Valley duration that included 10% or more of the TCL. The longest LAT-Valley was designated as the primary valley, while additional valleys were named as secondary. Results A total of 12 patients (9 men, median age 72 IQR 67-75 years) were included. All patients presented with left AFL and 67% had a previous atrial fibrillation and/or flutter ablation. The median TCL and number collected points were 250 (230─290) milliseconds and 3150 (IQR 2340─3870) points, respectively. All AFL presented with at least 1 LAT-Valley in the analysed histograms, which corresponded to heterogeneous low-voltage areas (0.05 to 0.3mV) and encompassed more than 10% of TCL. Eleven of the 12 patients presented with at least 1 secondary LAT-Valley. All arrhythmias were effectively terminated after undergoing radiofrequency ablation in the primary or the secondary LAT-Valley location. Conclusion In a prospective analysis, an electrophysiological triad was able to identify the AFL critical isthmus in all patients. Further studies are needed to assess the usefulness of this algorithm to improve catheter ablation outcomes.

A bisthienylethene-dipyrimido[2,1-b][1,3]benzothiazole (BTE-2PBT) triad has been designed and synthesized based on our recent discovery of PBTs as atypical propeller-shaped novel AIEgens. The triad not only maintains the photochromic properties of BTE moiety in solution, film, and solid state but also exhibits remarkable AIE properties. Moreover, the fluorescence of BTE-2PBT PMMA film could be modulated with high contrast by alternate UV and visible light irradiation. Photoerasing, rewriting, and non-destructive readout of fluorescent images on BTE-2PBT PMMA film well demonstrate its potential application as optical memory media.

International audience; The synthesis of a methanofullerene platform bearing on one side an alkyne and on the other a protected alkyne is reported. This clickable fullerene building block was functionalized by two distinct BODIPY azido derivatives using a 1 st CuAAC/alkyne deprotection /2 nd CuAAC, sequence, through either stepwise or one-pot processes in an efficient manner. The triad displays strong absorption from 300 to 700 nm. The strong fluorescence quenching observed for the two BODIPYs within the triad is probably due to photo-induced energy and/or electron transfer events.

In skeletal muscle, proteins of the calcium release complex responsible for the excitation-contraction (EC) coupling are exclusively localized in specific reticulum–plasma membrane (ER-PM) contact points named triads. The CRC protein triadin (T95) is localized in the sarcoplasmic reticulum (SR) subdomain of triads where it forms large multimers. However, the mechanisms leading to the steady-state accumulation of T95 in these specific areas of SR are largely unknown. To visualize T95 dynamics, fluorescent chimeras were expressed in triadin knockout myotubes, and their mobility was compared with the mobility of Sec61β, a membrane protein of the SR unrelated to the EC coupling process. At all stages of skeletal muscle cells differentiation, we show a permanent flux of T95 diffusing in the SR membrane. Moreover, we find evidence that a longer residence time in the ER-PM contact point is due to the transmembrane domain of T95 resulting in an overall triad localization.

A-pattern exotropia, superior oblique muscle overaction, and dissociated vertical deviation may coexist and are referred to as triad exotropia. The present study evaluated the postoperative stability of horizontal ocular alignment of triad exotropia and possible prognostic factors. Medical records of patients with triad exotropia who had one-step triple surgery of superior oblique muscle weakening, superior rectus muscle recession, and lateral rectus muscle recession were reviewed. The horizontal alignment and postoperative drift of triad exotropia were analyzed and compared with constant exotropia. The triad exotropia showed a mean of 7.7△ (± 8.5△) eso-drift, while the constant exotropia was (3.5△ ± 3.4△) exo-drift. Multiple linear regression analysis showed that the degree of superior oblique muscle overaction after surgery (P = 0.011) was the only factor associated with horizontal drift. Patients with superior oblique muscle underaction showed larger eso-drift when compared to patients without superior oblique muscle underaction (− 18.0△ ± 11.1△ vs. − 5.1△ ± 5.7△; P = 0.024). The final success rates of the triad exotropia and constant exotropia groups were 53.3% and 69.2%, respectively, and the overcorrection rates were 26.7% and 2.6% (P = 0.035). An overall trend of eso-drift in primary position occurred in triad exotropia after triple surgery up to a follow-up of 25 months. Patients presenting superior oblique muscle underaction after surgery seemed to have large angles of eso-drift, which might be taken into account in surgical planning and follow-up.

Oxidation of M(CO)6 (M = Cr, Mo, W) with the synergistic oxidative system Ag[WCA]/0.5 I2 yields the fully characterized metalloradical salts [M(CO)6]+˙[WCA]− (weakly coordinating anion WCA = [F-{Al(ORF)3}2]−, RF = C(CF3)3). The new metalloradical cations with M = Mo and W showcase a similar structural fluxionality as the previously reported [Cr(CO)6]+˙. Their reactivity increases from M = Cr < Mo < W and their syntheses allow for in-depth insights into the properties of the group 6 carbonyl triad. Furthermore, the reaction of NO+[WCA]− with neutral carbonyl complexes M(CO)6 gives access to the heteroleptic carbonyl/nitrosyl cations [M(CO)5(NO)]+ as salts of the WCA [Al(ORF)4]−, the first complete transition metal triad of their kind., The triad of group VI metalloradicals is now finally accessible via the oxidation of Cr/Mo/W(CO)6 with the synergistic oxidative system Ag[F-{Al(ORF)3}2]/0.5 I2.

Structure-property relationships of donor-π-acceptor (D-π-A) type molecular dyad (pp-AD) and triads (pp-ADA and Me-pp-ADA) based on benzodithiophene and BODIPY with biphenyl spacers have been reported. Rotors pp-AD and pp-ADA showed efficient twisted intramolecular charge transfer (TICT) with near infrared (NIR) emissions at ∼712 nm and ∼725 nm with (pseudo-)Stokes shifts of ∼208 nm and ∼221 nm, respectively, and prominent solvatochromism. A structurally similar triad, Me-pp-ADA, with tetramethyl substituents on the BODIPY core instead was TICT inactive and exhibited excitation energy transfer with a transfer efficiency of ∼88% as revealed using steady state emission and transient absorption measurements. Rotors pp-AD and pp-ADA showed NIR emission with an enhancement in intensity with the addition of water in THF solution as well as a pronounced change in emission intensity with temperature and viscosity variations, which justify their utility as temperature and viscosity sensors. Furthermore, the linear correlation of lifetime with fluorescence intensity ratios of the donor and acceptor justifies the rigidochromic behaviour of these rotors.

A multichromophoric triad, ZnP–OxP–C60 containing porphyrin (ZnTPP hereafter ZnP), oxoporphyrinogen (OxP) and fullerene (C60) has been synthesized to probe the intramolecular dynamics of its electron and energy transfer in relation to the presence of the closely linked electron deficient OxP–C60 ‘special pair’, constructed as a mimic of the naturally occurring photosynthetic antenna-reaction center. The DFT optimized structure of the triad reveals the relative spatial remoteness of the ZnP entity with proximal OxP/C60 entities. Free-energetics of different energy and electron transfer events were estimated using spectral, computational and electrochemical studies, according to the Rehm–Weller approach. Femtosecond transient absorption spectral studies revealed energy transfer from 1ZnP* to OxP to yield ZnP–1OxP*–C60, and electron transfer to yield ZnP˙+–OxP–C60˙− and/or ZnP–OxP˙+–C60˙− charge seperated states. That is, the ZnP entity in the triad operates as both antenna and electron donor to generate relatively long-lived charge separated states thus mimicking the early photoevents of natural photosynthesis.

The oxidation of Fe(CO)5 with the [NO]+ salt of the weakly coordinating perfluoroalkoxyaluminate anion [F‐{Al(ORF)3}2]− (RF=C(CF3)3) leads to stable salts of the 18 valence electron (VE) species [Fe(CO)4(NO)]+ and [Fe(CO)(NO)3]+ with the Enemark–Feltham numbers of {FeNO}8 and {FeNO}10. This finally concludes the triad of heteroleptic iron carbonyl/nitrosyl complexes, since the first discovery of the anionic ([Fe(CO)3(NO)]−) and neutral ([Fe(CO)2(NO)2]) species over 80 years ago. Both complexes were fully characterized (IR, Raman, NMR, UV/Vis, scXRD, pXRD) and are stable at room temperature under inert conditions over months and may serve as useful starting materials for further investigations., Ready to use…! Two novel iron carbonyl/nitrosyl cations in the elusive oxidation state +I are now easily accessible as stable salts of the weakly coordinating anion [F‐{Al(ORF)3}2]−. They may serve as simple model systems for the investigation of the nature of the Fe−NO bond to further understand the (bio‐)chemistry of iron nitrosyl complexes.

A new family of ten dinuclear Ru(II) complexes based on the bis[pyrrolyl Ru(II)] triad scaffold, where two Ru(bpy)2 centers are separated by a variety of organic linkers, was prepared to evaluate the influence of the organic chromophore on the spectroscopic and in vitro photodynamic therapy (PDT) properties of the compounds. The bis[pyrrolyl Ru(II)] triads absorbed strongly throughout the visible region, with several members having molar extinction coefficients (e) ≥ 104 at 600–620 nm and longer. Phosphorescence quantum yields (Φp) were generally less than 0.1% and in some cases undetectable. The singlet oxygen quantum yields (ΦΔ) ranged from 5% to 77% and generally correlated with their photocytotoxicities toward human leukemia (HL-60) cells regardless of the wavelength of light used. Dark cytotoxicities varied ten-fold, with EC50 values in the range of 10–100 μM and phototherapeutic indices (PIs) as large as 5400 and 260 with broadband visible (28 J cm−2, 7.8 mW cm−2) and 625 nm red (100 J cm−2, 42 mW cm−2) light, respectively. The bis[pyrrolyl Ru(II)] triad with a pyrenyl linker (5h) was especially potent, with an EC50 value of 1 nM and PI > 27 000 with visible light and subnanomolar activity with 625 nm light (100 J cm−2, 28 mW cm−2). The lead compound 5h was also tested in a tumor spheroid assay using the HL60 cell line and exhibited greater photocytotoxicity in this more resistant model (EC50 = 60 nM and PI > 1200 with 625 nm light) despite a lower dark cytotoxicity. The in vitro PDT effects of 5h extended to bacteria, where submicromolar EC50 values and PIs >300 against S. mutans and S. aureus were obtained with visible light. This activity was attenuated with 625 nm red light, but PIs were still near 50. The ligand-localized 3ππ* state contributed by the pyrenyl linker of 5h likely plays a key role in its phototoxic effects toward cancer cells and bacteria.

Metalloenzymes catalyze many important reactions by managing the proton and electron flux at the enzyme active site. The motifs utilized to facilitate these transformations include hemilabile, redox-active, and so called proton responsive sites. Given the importance of incorporating and understanding these motifs in the area of coordination chemistry and catalysis, we highlight recent milestones in the field. Work incorporating the triad of hemilability, redox-activity, and proton responsivity into single ligand scaffolds will be described.

Objective: This work aimed at synthesizing tridentates asymmetrical Schiff base ligands containing sulfur atom and using them for preparing metal complexes with the iron triad metals. The prepared compounds were assayed in vitro for antimicrobial potential and in vivo molluscicidal activity. Methods: The unsymmetrical tridentate Schiff bases (SL1, SL2, and SL3) were prepared using 2-aminothiophenol as primary amine and condensed with 2-carboxybenzaldehyde, 2-hydroxy-1-naphthaldehyde, and 7-formyl-8-hydroxyquinoline. These ligands were used in preparing metal complexes with iron triad metals. The synthesized Schiff base ligands and their corresponding metal complexes were characterized and their proposed structures were confirmed using different physical and spectroscopic analytical techniques. All ligands and their corresponding metal complexes were assayed against different bacterial and fungal strains using the agar disk-diffusion technique. The molluscicidal activity was performed according to the standard reported methods as cited in the literature and by observing the toxicity and lethal dose according to the WHO guidelines. Results: The synthesized ligands behave as tridentate (NOS) ligands and form mononuclear complexes with the general formula [M(SL)2] with an octahedral geometry around the central metal ion. Metal complexes were non-electrolytic in nature. The in vitro antibacterial and antifungal examination results showed weak activity of the ligands, and there was enhanced activity with the complexes. The in vivo molluscicidal activity of the tested compounds showed good activity. Conclusion: The targeted compounds were prepared successfully, characterized, and showed some biological activity but lower than the standard reference drugs.

We report a self-assembled triad for artificial photosynthesis composed of a chromophore, carbon-dioxide reduction catalyst, and hydrogen-oxidation complex, which is designed to operate without conventional sacrificial redox equivalents. Excitation of the zinc-porphyrin chromophore of the triad results in ultrafast charge transfer between a tungsten-alkylidyne donor and a rhenium diimine tricarbonyl acceptor, producing a charge-separated state that persists on the time scale of tens of nanoseconds and is thermodynamically capable of the primary dihydrogen and carbon dioxide binding steps for initiating the reverse water-gas shift reaction. The charge-transfer behavior of this system was probed using transient absorption spectroscopy in the visible, near-infrared, and mid-infrared spectral regions. The behavior of the triad was compared with that of the zinc-porphyrin-rhenium-diimide dyad; the triad was found to have a significantly longer charge-separated lifetime than other previously reported porphyrin-rhenium diimine compounds.

Regioisomeric acceptor-donor (AD) molecular rotors (p-AD, m-AD and m-ADA) were synthesized and characterized, wherein dyads p-AD and m-AD, and triad m-ADA contained 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) and benzodithiophene (BDT) as electron-acceptor and electron-donor, respectively. In all the compounds, the donor and acceptor moieties are electronically decoupled by a phenyl spacer, either through a para coupling or through a meta coupling. The dyad counterparts p-AD and m-AD showed distinct photophysical characteristics in which dyad p-AD showed TICT band at ca. 654 nm characterized by a Stokes shift of ca. 150 nm and prominent solvatochromism. However, meta regioisomeric triad m-ADA showed well-defined aggregation in solution. Notably, because of the temperature-tunable and solvent-viscosity-dependent emission, efficient ratiometric temperature sensing with positive and negative temperature coefficients and viscosity sensing was observed for all compounds. Interestingly, the fluorescence of dyad m-AD (in 10/90 v/v THF/water) revealed a near-white light emission with CIE chromaticity coordinates (x, y) of (0.32, 0.29). Furthermore, the fluorescence emission of p-AD in THF at 0 °C also showed a near-white light emission with chromaticity coordinates (x, y) of (0.34, 0.27). Such multifunctional rotors with readily tunable emission in the red region and prominent temperature- and viscosity-sensing abilities are promising for sensing and bioimaging applications.

The tactics of targeting copolymer composition (CC) and molecular weight (MW) via semibatch controlled radical polymerization (CRP) have been extensively studied. However, little effort is made to target copolymer sequence length (CSL) and its triad sequence, which are among the key microstructures determining material properties of the copolymers. This work presents a method to design and synthesize targeted CSL and copolymer triads in a reversible addition–fragmentation chain transfer radical mini-emulsion copolymerization system (RAFT) through a semibatch chain and sequence model coupled with Alfrey Mayo model. The kinetic model was first derived and correlated with experimental results of the batch St/BA copolymerizations. The semibatch RAFT model was then employed to calculate the feed-rate to target CSL and their triads. St/BA copolymers with different uniform CSLs and their triads are synthesized through the programmed semibatch RAFT mini-emulsion copolymerization processes.

Muscle contraction requires specialized membrane structures with precise geometry and relies on the concerted interplay of electrical stimulation and Ca 2+ release, known as excitation-contraction coupling (ECC). The membrane structure hosting ECC is called triad in skeletal muscle and dyad in cardiac muscle, and structural or functional defects of triads and dyads have been observed in a variety of myopathies and cardiomyopathies. Based on their function, the proteins localized at the triad/dyad can be classified into three molecular pathways: the Ca 2+ release complex (CRC), store-operated Ca 2+ entry (SOCE), and membrane remodeling. All three are mechanistically linked, and consequently, aberrations in any of these pathways cause similar disease entities. This review provides an overview of the clinical and genetic spectrum of triad and dyad defects with a main focus of attention on the underlying pathomechanisms.