The likelihood of detecting abnormal karyotypes in fetuses with a single major anomaly or "soft" marker on ultrasonographic scanning.

OBJECTIVE: Fetuses with abnormal karyotypes often exhibit distinctive ultrasonographic markers, including major anomalies and "soft" markers, indicating potential chromosomal issues. A crucial consideration arises when a single fetal anomaly is detected, raising the question of whether karyotyping is warranted, given the associated procedural risks. Our objective was to establish correlations between single fetal anomalies identified through ultrasound and chromosomal abnormalities. METHODS: A cross-sectional study analyzed the karyotype of 1493 fetuses and detected a single ultrasonographic anomaly over a 16-year period. Karyotyping was performed using the standard karyotype technique. Moreover, data regarding the type of anomaly detected ultrasonographically, karyotype results, and outcomes following interventions were collected. Among other methods, the use of positive likelihood ratios (LR+) was used to evaluate the diagnostic accuracy of ultrasound compared to karyotyping. RESULTS: In total, an aberrant karyotype was identified in 99 fetuses (6.6%). This was most commonly observed in cases involving a "soft" marker, occurring in 27 out of 218 fetuses (12.4%). The most frequently detected aberrant karyotype resulted from aneuploidies (80.6% of cases), notably trisomy 21 (50.5%). "Soft" markers predicted chromosomal issues (LR+ = 1.9; OR = 2.4), and isolated polyhydramnios (LR+ = 1.54; OR = 1.6) showed significance in predicting fetal chromosomal aberrations. CONCLUSION: When assessing the necessity for karyotyping in fetuses with single major anomalies or "soft" markers, it is crucial to consider individual risks for chromosomopathies, including the LR+ of the detected marker. In cases where fetuses exhibit isolated anomalies with a normal karyotype, additional diagnostic measures, such as molecular cytogenetic and molecular genetics techniques, may become necessary.

On the Role of Digital Twins in Data Spaces.

Industry 4.0 supports the vision of networked machines in decentralized production plants across the value chain. Hence, it requires highly connected partners exchanging relevant data about products, processes, and production resources. This paper proposes the usage of data spaces and digital twins to enable this Industry 4.0 vision and investigates the building blocks to realize a data space for Industry 4.0, e.g., the integration of digital twins inside the data space based upon the latest specification of the Industry 4.0 Asset Administration Shell. A prototypical implementation shows the feasibility of storing product carbon footprints inside a digital twin and sharing it over a data space with other partners.

Increasing Interoperability between Digital Twin Standards and Specifications: Transformation of DTDL to AAS.

Although standards and specifications for digital twins aim to create interoperability in Industry 4.0, each standard has its own goals, focuses and representations for digital twins. This paper examines an approach to increasing interoperability between established digital twin specifications by transformation. Accordingly, several specifications are presented and requirements for transformation are examined. Following the feasibility analysis, a mapping between the Digital Twin Definition Language (DTDL) and Asset Administration Shell (AAS) was created. To examine the feasibility of this approach, the transformation was implemented and tested for a physical asset. This paper demonstrates that a generic mapping between DTDL and AAS can be applied for transformation in use cases where DTDL models are provided while AAS is required.

Open-Source Implementations of the Reactive Asset Administration Shell: A Survey.

The use of open-source software is crucial for the digitalization of manufacturing, including the implementation of Digital Twins as envisioned in Industry 4.0. This research paper provides a comprehensive comparison of free and open-source implementations of the reactive Asset Administration Shell (AAS) for creating Digital Twins. A structured search on GitHub and Google Scholar was conducted, leading to the selection of four implementations for detailed analysis. Objective evaluation criteria were defined, and a testing framework was created to test support for the most common AAS model elements and API calls. The results show that all implementations support at least a minimal set of required features while none implement the specification in all details, which highlights the challenges of implementing the AAS specification and the incompatibility between different implementations. This paper is therefore the first attempt at a comprehensive comparison of AAS implementations and identifies potential areas for improvement in future implementations. It also provides valuable insights for software developers and researchers in the field of AAS-based Digital Twins.

Competition between ultralong organic phosphorescence and thermally activated delayed fluorescence in dichloro derivatives of 9-benzoylcarbazole.

Optoelectronic materials based on metal-free organic molecules represent a promising alternative to traditional inorganic devices. Significant attention has been devoted to the development of the third generation of OLEDs which are based on the temperature-activated delayed fluorescence (TADF) mechanism. In the last few years, several materials displaying ultra-long organic phosphorescence (UOP) have been designed using strategies such as crystal engineering and halogen functionalisation. Both TADF and UOP are controlled by the population of triplet states and the energy gaps between the singlet and triplet manifolds. In this paper, we explore the competition between TADF and UOP in the molecular crystals of three dichloro derivatives of 9H-carbazol-3-yl(phenyl)methanone. We investigate the excited state mechanisms in solution and the crystalline phase and address the effects of exciton transport and temperature on the rates of direct and reverse intersystem crossing under the Marcus-Levich-Jortner model. We also analyse how the presence of isomeric impurities and the stabilisation of charge transfer states affect these processes. Our simulations explain the different mechanisms observed for the three derivatives and highlight the role of intramolecular rotation and crystal packing in determining the energy gaps. This work contributes to a better understanding of the connection between chemical and crystalline structures that will enable the design of efficient materials.

Newton-X Platform: New Software Developments for Surface Hopping and Nuclear Ensembles.

Newton-X is an open-source computational platform to perform nonadiabatic molecular dynamics based on surface hopping and spectrum simulations using the nuclear ensemble approach. Both are among the most common methodologies in computational chemistry for photophysical and photochemical investigations. This paper describes the main features of these methods and how they are implemented in Newton-X. It emphasizes the newest developments, including zero-point-energy leakage correction, dynamics on complex-valued potential energy surfaces, dynamics induced by incoherent light, dynamics based on machine-learning potentials, exciton dynamics of multiple chromophores, and supervised and unsupervised machine learning techniques. Newton-X is interfaced with several third-party quantum-chemistry programs, spanning a broad spectrum of electronic structure methods.

Emission Quenching in Tetraphenylfuran Crystal: Why This Propeller-Shaped Molecule Does Not Emit in the Condensed Phase.

Due to their substantial fluorescence quantum yields in the crystalline phase, propeller-shaped molecules have recently gained significant attention as potential emissive materials for optoelectronic applications. For the family of cyclopentadiene derivatives, light-emission is highly dependent on the nature of heteroatomic substitutions. In this paper, we investigate excited state relaxation pathways in the tetraphenyl-furan molecule (TPF), which in contrast with other molecules in the family, shows emission quenching in the solid-state. For the singlet manifold, our calculations show nonradiative pathways associated with C-O elongation are blocked in both vacuum and the solid state. A fraction of the population can be transferred to the triplet manifold and, subsequently, to the ground state in both phases. This process is expected to be relatively slow due to the small spin-orbit couplings between the relevant singlet-triplet states. Emission quenching in crystalline TPF seems to be in line with more efficient exciton hopping rates. Our simulations help clarify the role of conical intersections, population of the triplet states and crystalline structure in the emissive response of propeller-shaped molecules.

Role of Conical Intersections on the Efficiency of Fluorescent Organic Molecular Crystals.

Organic molecular crystals are attractive materials for luminescent applications because of their promised tunability. However, the link between the chemical structure and emissive behavior is poorly understood because of the numerous interconnected factors which are at play in determining radiative and nonradiative behaviors at the solid-state level. In particular, the decay through conical intersection dominates the nonadiabatic regions of the potential energy surface, and thus, their accessibility is a telling indicator of the luminosity of the material. In this study, we investigate the radiative mechanism for five organic molecular crystals which display a solid-state emission, with a focus on the role of conical intersections in their photomechanisms. The objective is to situate the importance of the accessibility of conical intersections with regards to emissive behavior, taking into account other nonradiative decay channels, namely, vibrational decay, and exciton hopping. We begin by giving a brief overview of the structural patterns of the five systems within a larger pool of 13 crystals for a richer comparison. We observe that because of the prevalence of sheet like and herringbone packing in organic molecular crystals, the conformational diversity of crystal dimers is limited. Additionally, similarly spaced dimers have exciton coupling values of a similar order within a 50 meV interval. Next, we focus on three exemplary cases, where we disentangle the role of nonradiative decay mechanisms and show how rotational minimum energy conical intersections in vacuum lead to puckered ones in the crystal, increasing their instability upon crystallization in typical packing motifs. In contrast, molecules with puckered conical intersections in vacuum tend to conserve this trait upon crystallization, and therefore, their quantum yield of fluorescence is determined predominantly by other nonradiative decay mechanisms.

On the origin of the shift between vertical excitation and band maximum in molecular photoabsorption.

The analysis of the photoabsorption spectra of molecules shows that the band maximum is usually redshifted in comparison to the vertical excitation. We conducted a throughout analysis of this shift based on low-dimensional analytical and numerical model systems, showing that its origin is rooted in the frequency change between the ground and the excited states in multidimensional systems. Moreover, we deliver a benchmark of ab initio results for the shift based on a comparison of vertical excitations and band maxima calculated with the nuclear ensemble approach for the 28 organic molecules in the Mülheim molecular dataset. The mean value of the shift calculated over 60 transitions is 0.11 ± 0.08 eV. The mean value of the band width is 0.32 ± 0.14 eV. Graphical abstract .

Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores.

Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.

Nonadiabatic Dynamics of Cycloparaphenylenes with TD-DFTB Surface Hopping.

We implemented a version of the decoherence-corrected fewest switches surface hopping based on linear-response time-dependent density functional tight binding (TD-DFTB), enhanced by transition density analysis. The method has been tested for the gas-phase relaxation dynamics of two cycloparaphenylene molecules, [8]CPP and [10]CPP, explaining some important features of their nonadiabatic dynamics, such as the origin of their long fluorescence lifetimes (related to the slow radiative emission from the S1 state) and the trend of increasing the fluorescence rate with the molecular size (related to an increase in the S1-S0 energy gaps and oscillator strengths in the larger molecule). The quality of the TD-DFTB electronic structure information was assessed through four quantities: excitation energies; charge-transfer (CT) numbers, which estimate the charge transfer character of states; participation ratio (PR), which describes delocalization of electronic density; and participation ratio of natural transition orbitals (PRNTO), which describes the multiconfigurational character of states. These quantities were computed during dynamics and recomputed for the same geometries with the higher-level long-range-corrected TD-LC-DFTB and a lower-level single-determinant approximation for the excited states, SD-(LC)-DFTB. Taking TD-LC-DFTB as the standard, TD-DFTB underestimates the excitation energies by ∼0.5 eV and overestimates CT and PR. SD-DFTB underestimates excitation energies and overestimates CT to the same extent that TD-DFTB does, but it predicts reasonable PR distributions. SD-LC-DFTB leads to an extreme overestimation of the excitation energies by ∼3 eV, overestimates the charge transfer character of the state, but predicts the PR values very close to those obtained with TD-LC-DFTB.

UV excitations of halons.

In the present study, we examined the UV excitations of a newly introduced molecular set, Halons-9, composed of nine gaseous halon molecules. The performance of the density functional-based multi-reference configuration interaction method (DFT/MRCI) and time-dependent density functional theory with CAM-B3LYP functional (TD-CAM-B3LYP) in the computation of singlet and triplet excited states of this set was evaluated against coupled-cluster with singles and doubles (CCSD). Excited states up to the corresponding ionization limits, including both localized and delocalized excitations, have been benchmarked. TD-CAM-B3LYP significantly underestimates excitation energies of the higher mixed valence-Rydberg and Rydberg states, with computed mean absolute deviations from the equation of motion (EOM)-CCSD results 1.06 and 0.76 eV, respectively. DFT/MRCI gives a significantly better description of higher excited states, albeit still poor, compared to the TD-CAM-B3LYP. The mean absolute deviations of mixed valence-Rydberg and Rydberg states from the reference EOM-CCSD values are 0.66 and 0.47 eV, respectively. The performance of DFT/MRCI for description of strongly correlated states with valence-Rydberg mixing is still not satisfactory enough. On the other hand, oscillator strengths of most of singlet states obtained with both methods are close to the EOM-CCSD values. The largest deviations, occurring in the case of several high-lying multiconfigurational states, are of an order of magnitude.

New Insights into the State Trapping of UV-Excited Thymine.

After UV excitation, gas phase thymine returns to a ground state in 5 to 7 ps, showing multiple time constants. There is no consensus on the assignment of these processes, with a dispute between models claiming that thymine is trapped either in the first (S1) or in the second (S2) excited states. In the present study, a nonadiabatic dynamics simulation of thymine is performed on the basis of ADC(2) surfaces, to understand the role of dynamic electron correlation on the deactivation pathways. The results show that trapping in S2 is strongly reduced in comparison to previous simulations considering only non-dynamic electron correlation on CASSCF surfaces. The reason for the difference is traced back to the energetic cost for formation of a CO π bond in S2.

Application of digital radiography for measuring in clinical dental practice.

INTRODUCTION: The recent literature data points out a rising application of digital radiography--radiovisiography (RVG)--in dental clinical practice. OBJECTIVE: The aim of this study was to apply and compare RVG with the conventional radiographic technique (CRDG) in terms of accuracy in linear measurement in dentistry. METHODS: Measurements were done on the mandibular dogs teeth considering incisors crown width and height of the surrounding alveolar bone using RVG and CRDG.The control technique (CONT) involved values obtained by direct gauging in dogs mouth. Each measuring was done by two examiners. RESULTS: Considering the incisors' crown width, there were no significant statistical difference in measurement using CRDG, RVG and CONT technique (p > 0.01). Concerning the alveolar height gauging there were no significant difference in recorded values between the two radiographic techniques (p > 0.01). The high level of inter-examiner agreement was observed for scoring in all techniques (CRDG, RVG and CONT). CONCLUSION: Although RVG did not expose more accuracy comparing to CRDG, having opulent tool service the first technique contributed more comfortable work during measuring procedures in this study.

A cephalometric analysis of the cranial base and frontal part of the face in patients with mandibular prognathism.

BACKGROUND/AIM: The literature suggests different views on the correlation between the cranial base morphology and size and saggital intermaxillary relationships. The aim of this study was to investigate the cranial base morphology, including the frontal facial part in patients with mandibular prognathism, to clarify a certain ambiguities, in opposing viewspoints in the literature. METHODS: Cephalometric radiographies of 60 patients were analyzed at the Dental Clinic of the Military Medical Academy, Belgrade, Serbia. All the patients were male, aged 18-35 years, with no previous orthodontic treatment. On the basis of dental and sceletal relations of jaws and teeth, the patients were divided into two groups: the group P (patients with mandibular prognathism) and the group E (the control group or eugnathic patients). A total of 15 cephalometric parametres related to the cranial base, frontal part of the face and sagittal intermaxillary relationships were measured and analyzed. RESULTS: The results show that cranial base dimensions and the angle do not play a significant role in the development of mandibular prognathism. Interrelationship analysis indicated a statistically significant negative correlation between the cranial base angle (NSAr) and the angles of maxillary (SNA) and mandibular (SNB) prognathism, as well as a positive correlation between the angle of inclination of the ramus to the cranial base (GoArNS) and the angle of sagittal intermaxillary relationships (ANB). Sella turcica dimensions, its width and depth, as well as the nasal bone length were significantly increased in the patients with mandibular prognathism, while the other analyzed frontal part dimensions of the face were not changed by the malocclusion in comparison with the eugnathic patients. CONCLUSION: This study shows that the impact of the cranial base and the frontal part of the face on the development of profile in patients with mandibular prognathism is much smaller, but certainly more complex, so that morphogenetic tests of the maxillomandibular complex should be included in further assessment of this impact.

Orthodontic-surgical treatment of the skeletal class III malocclusion: a case report.

BACKGROUND: Class III malocclusions are considered to be ones of the most difficult problems to treat. Their causes are multifactorial and include genetic and/or environmental factors. Class III malocclusions are generally classified into 2 categories: skeletal and dental. The diagnosis is important due to the different treatment approaches. Generally a dental class III can be treated with orthodontics alone, while a true skeletal class III requires a combination of orthodontics and surgery. CASE REPORT: We presented a female patient with skeletal Class III malocclusion. The treatment was complete with positive overbite and acceptable occlusion using a combination of fixed orthodontic appliance treatment as well as the surgical operation. The patient was happy with her new appearance and function. CONCLUSION: Class III discrepancy should be diagnosed and classified according to its etiology and treated with appropriate surgery, including, if necessary, not only mandibular, but also maxillary surgery, in order to achieve a normal facial appearance. In any case, as the field of orthodontics continues to develop technologically and philosophically, we can expect that advances in diagnosis and treatment planning are im minent and inevitable.

Theoretical study of hyperfine interactions in small arsenic-containing radicals.

Various density functional theory (DFT) and ab initio MP2 and CCSD methods were employed in calculations of arsenic isotropic and anisotropic hyperfine parameters in three small radicals, AsH(2), AsO(2), and H(2)AsO. Convergent basis sets for these calculations were specially derived starting from Dunning's correlation-consistent sets. DFT methods proved to be particularly appropriate choice, because the results obtained with the suitable functionals are in accordance with the available experimental values. Additionally, mechanisms of hyperfine couplings were investigated by examining individual orbital contributions to spin density. The spin polarization mechanism in AsH(2) was studied by evaluating one- and two-electron integrals in spin-restricted and unrestricted case. Apart from nonrelativistic, scalar-relativistic Douglas-Kroll-Hess DFT calculations were performed to examine relativistic impacts on spin density distribution.

Application of radiovisiography (digital radiology) in dental clinical practice.

INTRODUCTION: Radiovisiography (RVG) as the latest imaging technique in dentistry with the minimal radiation exposure of the patient and numerous possibilities to process the images has many advantages over classic radiography. CASE REPORT: We presented an interesting clinical endodontic case of primary posted diagnosis of traumatic periodontitis of upper right canine upon orthodontics treatment. As the patient previously had been exposed to alleged high dose of radiation the patient agreed to minimal exposition using digital RVG. The options of the tool bar of RVG Trophy device enabled the solving of ethiologic factor of presented periodontitis. The enigma of the symptoms on the 'overfilled' root canal was solved zooming and 3-D analysis avoiding periapical surgery owing to the patience of the patient and the dentist in a couple of days. CONCLUSION: By applying RVG technique the time for diagnostic procedure is much shorter in comparison with traditional dental radiography enabling archiving and follow-up the presented case in the course of time.

Ab initio study of the 1 2Delta-X 2Pi electronic transition of C2As.

We report the results of ab initio calculations on the 1 (2)Delta-X (2)Pi spectral system of C(2)As. The present study is closely related to the recent comprehensive experimental and theoretical work by Wei et al. [J. Chem. Phys. 129, 134307 (2008)]. By means of the state-average complete active space self-consistent field and multireference configuration interaction approach, we computed the vertical excitation energies to the low-lying doublet electronic species, potential surfaces and spin-orbit constants for the X (2)Pi and 1 (2)Delta states, as well as the components of the electric dipole moment for the transition between these two species. Using these data, we calculated the vibronic energy levels, the spin-orbit structure of the spectrum, and the vibronic transition moments of the X (2)Pi-1 (2)Delta system. The results of the present study for the X (2)Pi state agree with those derived from experimental findings by Wei et al., they elucidate the vibronic and spin-orbit structure in the 1 (2)Delta species, and offer predictions for experimental searches of heretofore unobserved electronic states.

Cephalometric indicators of the vertical dimension of occlusion.

The aim of this investigation was to establish precise indicators of the vertical dimension of occlusion (VDO) which could be used as objective parameters in prosthodontic treatment providing exact control of the reconstructed vertical dimension of occlusion, early detection of errors and correction of the vertical dimension of occlusion during complete denture manufacturing. A total of 60 lateral cephalometric radiographs of subjects with natural dentition and class I skeletal jaw relationship, of Serbian nationality from the region of Vojvodina, were included in the investigation. Thirty subjects were males, and thirty females, their age range was 20 to 29 years. Cephalometric analysis was performed by using "Dr. Ceph" computer software (FYI Technologies, GA, USA). By evaluation of the craniofacial complex in subjects with natural dentition, horizontal dentofacial developmental growth was established in the examined sample and it was based on the relationship between the posterior and anterior total facial height (S-Go:N-Me, female X=68.96%, male X=72.8%) and statistically significant differences were found between the sexes in almost all linear dimensions and in the relation between the posterior and the anterior total facial height. Highly significant differences (p<0.001) between the sexes were found in regard to anterior total facial height (N-Me, male X=120.75 mm, female X=112.72 mm) and the anterior lower facial height (ANS-Me, male X=67.87 mm, female X=61.50 mm) (p<0.05). The proportions of the upper and lower anterior facial heights (N-ANS:ANS-Me, male X=79.36%, female X=80.63%) were within normal values in both sexes. Facial harmony existed both in men and women. Cephalometric study of the subjects with complete natural dentition included in this study provided important and specific parameters for optimal reconstruction of vertical dimension of occlusion in the treatment of edentulous patients.