Experimental and theoretical investigations on the optical and electrochemical properties of π-conjugated donor-acceptor-donor (DAD) compounds toward a universal model.

A series of nine (9) donor-acceptor-donor (DAD) π-conjugated small molecules were synthesized via palladium catalyzed Stille aromatic cross-coupling reactions by the combination of six (6) heterocycle building blocks (thiophene, furan, thiazole, 2,1,3-benzothiadiazole, 2,1,3-pyridinothiadiazole, thienothiadiazole) acting as electron donating (thiazole, furan, thiophene) and electron deficient (benzothiadiazole, pyridinethiadiazole, thienothiadiazole) units. These model compounds enable determining the correspondence between the theoretical and experimental optical and electrochemical properties for the first time, via Density Functional Theory (DFT), time-dependent DFT, UV-Vis spectroscopy, and cyclic voltammetry, accordingly. The obtained theoretical models can be utilized for the design and synthesis of new DAD structures with precise optical bandgaps, absorption maxima, and energy levels suitable for different optoelectronic applications.

An Electron-Transporting Thiazole-Based Polymer Synthesized Through Direct (Hetero)Arylation Polymerization.

In this work, a new n-type polymer based on a thiazole-diketopyrrolopyrrole unit has been synthesized through direct (hetero)arylation polycondensation. The molar mass has been optimized by systematic variation of the the monomer concentration. Optical and electrochemical properties have been studied. They clearly suggested that this polymer possess a high electron affinity together with a very interesting absorption band, making it a good non-fullerene acceptor candidate. As a consequence, its charge transport and photovoltaic properties in a blend with the usual P3HT electron-donating polymer have been investigated.

Screening mixed depression and bipolarity in the postpartum period at a primary health care center.

INTRODUCTION: Mixed depression is a clinical condition accompanied by the symptoms of (hypo)mania and is considered to be a predictor for bipolar disorder. Compared to pure major depression, mixed depression is worse in progress. There are limited data on the prevalence of mixed depression since it is a relatively new entity. Therefore, the present study aimed to investigate the prevalence of mixed depression during the postpartum period which is risky for mood disorders. METHODS: The study included 63 postpartum women. The participants were administered Beck Depression Scale, Edinburgh Postnatal Depression Scale (EPDS), Mood Disorders Questionnaire (MDQ), and Modified Hypomania Symptom Checklist-32 (mHCL-32). RESULTS: The MDQ scores of the women with expected depression according to the EPDS cut-off scores, were significantly higher than the women with lower EPDS scores (t=-4.968; p<0.001). The modified hypomania scores were significantly higher in the women with higher depression scores compared to the women under EPDS cut-off scores (t=-4.713; p<0.001). According to the EPDS and BDS results, 27 (42.9%) and 14 (22.2%) women needed additional clinical examination for depression, respectively. In addition, 3 (4.8%) women require additional clinical examination for bipolar disorder. The scores for the first item of MDQ were above the cut-off value in 11 (17.5%) women. According to the mHCL-32 results, 50 (79.4%) women had at least 1 symptom, 45 (71.4%) women had at least 3 symptoms, and 43 (68.3%) women had at least 5 symptoms of mixed depression. CONCLUSION: Postpartum mixed depression should be promptly diagnosed by using appropriate diagnostic tools, particularly by primary health care physicians. Patients with mixed depression should be closely monitored to avoid manic switch.

Investigation of the Efficacy of Bilateral Osteoligamentous Decompression via Hemilaminectomy in Cervical Spondylotic Myelopathy: A Clinical Study.

OBJECTIVE: Cervical stability may deteriorate and kyphotic spinal deformities may develop in cervical spondylotic myelopathy (CSM) after laminectomy or laminoplasty. This study aimed to investigate the therapeutic efficacy of the "bilateral osteoligamentous decompression via unilateral hemilaminectomy approach (UHBOLD)" technique in CSM patients. METHODS: The study included 34 adult patients who underwent UHBOLD surgery for CSM between 2016 and 2022. A record was made for all patients of age, gender, number of operated levels, preoperative and postoperative long-term follow-up VAS scores, Nurick grade values and mJOA scores, kyphosis angles measured on X-ray, and spinal canal areas measured on T2-weighted MR axial images. RESULTS: Preoperative VAS scores of the patients were 6 (4-9), Nurick grade values were 3 (2-5), mJOA scores were 10.50 ± 3.42, kyphosis angles were -13.34 ± 13.69° and spinal canal areas were 87.11 ± 28.30 mm2. In postoperative long-term follow-up of these patients, VAS scores were 2 (1-5), Nurick grade values were 1 (0-5), mJOA scores were 13.94 ± 3.09, kyphosis angles were -15.07 ± 12.78° and spinal canal areas were 149.65 ± 42.57 mm2. A statistically significant difference was determined between the preoperative and the postoperative long-term follow-up VAS scores, Nurick grade values, mJOA scores, and spinal canal areas (P < 0.001). Kyphosis angles were not different (P = 0.198), and no instability was observed in any patient in long-term follow-up. CONCLUSIONS: The UHBOLD technique performed in multilevel CSM patients did not cause any change in cervical lordosis angle in long-term follow-up, did not cause cervical kyphotic deformity or cervical instability, and significantly improved Nurick grade values, and VAS and mJOA scores.

Analysis of radiological measurement parameters that can predict the type of treatment to be applied in odontoid fractures: Clinical research.

Introduction: Although various conservative and surgical treatment methods have been proposed, treatment options for patients with odontoid fractures remain controversial. This study was conducted to determine some demographic and radiological measurement parameters that can predict treatment options in patients with odontoid fractures. Materials and Methods: The patients were separated into the surgery (-) group (n = 9) and the surgery (+) group (n = 10). Patient data were recorded of age, gender, type of odontoid fracture, morphological measurement results obtained from computed tomography images, treatment regimens, duration of stay in the hospital, and mortality rate. In the operating room, a halo-vest corset or Philadelphia-type cervical collar was applied to the surgery (-) patients after the reduction of the fracture under fluoroscopy. Anterior odontoid lag screw fixation was performed on surgery (+) patients. Results: The amount of displacement of the fractured odontoid, the distance between the C1 vertebra and the odontoid process, the angle between the posterior wall of the odontoid process and the posterior wall of the clivus, the slip angle, and the anterior to posterior width of the spinal canal were not different between the groups. No difference was determined between the groups in respect of the amount of lateral displacement of the odontoid process in the spinal canal in the axial plane and the angle of the fractured odontoid process with the C2 vertebral body. Conclusion: This preliminary study showed that the demographic data and radiological measurement parameters analyzed in the present study could not be used as predictive markers either in decision-making for treatment modality or mortality risk.

The impact of spin-orbit coupling on fine-structure and spin polarisation in photoexcited porphyrin triplet states.

The photoexcited triplet states of porphyrins show great promise for applications in the fields of opto-electronics, photonics, molecular wires, and spintronics. The magnetic properties of porphyrin triplet states are most conveniently studied by time-resolved continuous wave and pulse electron spin resonance (ESR). This family of techniques is singularly able to probe small yet essential details of triplet states: zero-field splittings, g-anisotropy, spin polarisation, and hyperfine interactions. These characteristics are linked to spin-orbit coupling (SOC) which is known to have a strong influence on photophysical properties such as intersystem crossing rates. The present study explores SOC effects induced by the presence of Pd2+ in various porphyrin architectures. In particular, the impact of this relativistic interaction on triplet state fine-structure and spin polarisation is investigated. These properties are probed using time-resolved ESR complemented by electron-nuclear double resonance. The findings of this study could influence the future design of molecular spintronic devices. The Pd2+ ion may be incorporated into porphyrin molecular wires as a way of controlling spin polarisation.

Predictive Markers in Decision-Making for Screwing the Fractured Thoracolumbar Vertebra in the Short-Segment Instrumentation.

Introduction: In this study, it is aimed to compare the long-term results of patients with short-segment instrumentation where screws were inserted into the fractured vertebra with those of patients with long-segment instrumentation applied by skipping the fractured vertebra and reveal the predictive markers in decision-making for screwing fractured vertebra. Methods: Patients were separated into two groups, namely, Group A (patients in which the fractured vertebra and vertebrae above and below the fractured vertebra were screwed (short-segment instrumentation, n=22) and Group B (patients in whom the fractured vertebra was not screwed, whereas two vertebrae above and below the fractured vertebra were screwed (long-segment instrumentation, n=27). Results: The presence of pedicle fracture, AOSpine Classification Scale score, the height of the fractured vertebra, vertebra height below the fractured vertebra, spinal canal diameter, and duration of stay in hospital were different between the groups, preoperatively (p<0.05). Fractured vertebra height, vertebra height below the fractured vertebra, and Karnofsky Performance Scale score were different between the groups in long-term follow-up (p<0.05). The preoperative measurement values were similar to each group's postoperative long-term follow-up results. Logistic regression analysis revealed that the presence of pedicle fracture, AOSpine Classification Scale score, vertebra height below the fractured vertebra, and spinal canal diameter could be the best parameters in decision-making for screwing fractured vertebra (p<0.05). Conclusions: Both instrumentation procedures were observed to have similar effectiveness in preventing a collapse in fractured vertebra during long-term follow-up. It was thought that the AOSpine Classification Scale score, presence of pedicle fracture, vertebra height below the fractured vertebra, and spinal canal diameter could be used as predictive markers in decision-making for screwing fractured vertebrae. Consequently, it was concluded that patients with pedicle fractures, more height loss in the vertebra below the fractured vertebra, and narrow spinal canal would not be suitable for screwing the fractured vertebra.

Towards efficient near-infrared fluorescent organic light-emitting diodes.

The energy gap law (EG-law) and aggregation quenching are the main limitations to overcome in the design of near-infrared (NIR) organic emitters. Here, we achieve unprecedented results by synergistically addressing both of these limitations. First, we propose porphyrin oligomers with increasing length to attenuate the effects of the EG -law by suppressing the non-radiative rate growth, and to increase the radiative rate via enhancement of the oscillator strength. Second, we design side chains to suppress aggregation quenching. We find that the logarithmic rate of variation in the non-radiative rate vs. EG is suppressed by an order of magnitude with respect to previous studies, and we complement this breakthrough by demonstrating organic light-emitting diodes with an average external quantum efficiency of ~1.1%, which is very promising for a heavy-metal-free 850 nm emitter. We also present a novel quantitative model of the internal quantum efficiency for active layers supporting triplet-to-singlet conversion. These results provide a general strategy for designing high-luminance NIR emitters.

Analysis of biochemical laboratory values to determine etiology and prognosis in patients with subarachnoid hemorrhage: a clinical study.

OBJECTIVES: The aim of this study was to establish prognostic and predictive markers in patients with subarachnoid hemorrhage (SAH) using simple laboratory methods. METHODS: A retrospective examination was made of patients with SAH diagnosed secondary to isolated head trauma, isolated anterior communicating artery aneurysm rupture, and angiography-negative SAH. Age, gender, Glasgow Coma Scale (GCS) scores, and Fisher's grade scores, Glasgow Outcome Scale (GOS) scores, leukocyte count, neutrophil count, lymphocyte count, platelet count, neutrophil-lymphocyte ratio (NLR) and platelet-lymphocyte ratio results (PLR) were evaluated. RESULTS: NLR and PLR values, which were similar in patients with spontaneous SAH, were significantly high in patients with traumatic SAH. NLR and PLR values could be 80% sensitive and 75% specific for distinguishing traumatic SAH from spontaneous SAH. Eosinophil count was lower in patients with angiography-negative SAH and patients with aneurysmal SAH than in patients with traumatic SAH. Initially measured GCS score, Fisher's grade score, eosinophil, neutrophil and lymphocyte counts could be prognostic in all patients with SAH. Moreover, it was concluded that the initially measured number of eosinophils might be directly related to patient prognosis. The eosinophil count was generally found to be high in traumatic SAH patients and it was observed that this parameter could be predictive for these patients. Lymphocyte count and NLR values could be prognostic markers in patients with angiography-negative SAH. CONCLUSION: NLR, PLR and eosinophil count values could be predictive for etiological factors (traumatic SAH or spontaneous SAH) of patients who were admitted unconscious to the emergency room with SAH detected on radiological imaging.

Metal Atom Markers for Imaging Epitaxial Molecular Self-Assembly on Graphene by Scanning Transmission Electron Microscopy.

Direct imaging of single molecules has to date been primarily achieved using scanning probe microscopy, with limited success using transmission electron microscopy due to electron beam damage and low contrast from the light elements that make up the majority of molecules. Here, we show single complex molecule interactions can be imaged using annular dark field scanning TEM (ADF-STEM) by inserting heavy metal markers of Pt atoms and detecting their positions. Using the high angle ADF-STEM Z1.7 contrast, combined with graphene as an electron transparent support, we track the 2D monolayer self-assembly of solution-deposited individual linear porphyrin hexamer (Pt-L6) molecules and reveal preferential alignment along the graphene zigzag direction. The epitaxial interactions between graphene and Pt-L6 drive a reduction in the interporphyrin distance to allow perfect commensuration with the graphene. These results demonstrate how single metal atom markers in complex molecules can be used to study large scale packing and chain bending at the single molecule level.

Rational Engineering of BODIPY-Bridged Trisindole Derivatives for Solar Cell Applications.

Boron dipyrromethene (BODIPY) and its derivatives are known to be efficient photon-harvesting chromophores. However, their study as active materials in bulk heterojunction (BHJ) solar cells is still scarce. In this study, the development of new synthetic ways to design original BODIPY-based dumbbell-shape molecules, including a first 2,3,5,6-tetravinyl aromatic BODIPY molecule, is reported. High fill factors can be obtained in BHJ solar cells when blended with a fullerene derivative, leading to a new record BODIPY-based power conversion efficiency of 5.8 %.