Cyclic Complexes Research Articles

COMPARISON OF CONSERVATIVE METHODS OF PREVENTION OF PATHOLOGICAL SCARING OF THE HEAD AND NECK

Wound healing is one of the most common and complex processes, which includes five phases: hemostasis, inflammation, proliferation, re-epithelialization, and remodeling. Each stage of wound healing requires the complex synchronization and regulation of multiple cell populations. Violation of the link of any of these processes can lead to the appearance of complications and increase the likelihood of the formation of pathological scars. To study the research materials, we used the bibliosemantic and analytical method, with the help of which we processed the literary data, as well as the materials of clinical studies, which were posted on the Internet. There are many conservative methods of prevention of the pathological scars formation in the area of head and neck, one of the main links is occupied by ointments with different components. Thus, a clinical study by Marquardt Y showed that the local application of dexpanthenol in the form of an ointment contributes to better healing of superficial and postoperative wounds. According to foreign scientists, silicone products, both in the form of sheets and gel, are considered to be the first line in the prevention and treatment of hypertrophic and keloid scars. Goutos I., suggested the use of corticosteroid tape, which is a painless alternative to corticosteroid injections. Japanese scientists Ogawa R and co-authors note the good clinical experience and results of using corticosteroid tape and patch. Recent research by Powell HM., 2022 on the use of pressure therapy for lacerations has shown that tension relief is a powerful strategy to prevent scar formation in the head and neck area. Ud-Din S et al., proposed photodynamic therapy, which has a good evidence base for the effectiveness of this method. Over the past decade, many high-quality studies have been conducted, increasing the level of evidence base for many prevention or treatment regimens. The article reflects modern methods of conservative prevention, however, taking into account ethnic differences, predisposition to pathological scars, algorithms for prevention and treatment should be refined and optimized.

Syn-Selective Chlorosulfonylation of Alkynes via a Copper-Powder-Initiated Atom Transfer Radical Addition Reaction and Mechanistic Studies.

Copper-powder-catalyzed syn-selective chlorosulfonylation of readily available alkynes by an atom transfer radical addition (ATAR) process has been developed, providing straightforward access to a broad range of (Z)-β-chlorovinylsulfones in good yields under mild conditions. In addition, this method is ligand-free and features excellent stereoselectivity and high atom economy. Moreover, the product was obtained without an apparent loss of yield when the reaction was performed on the gram scale at a low catalyst loading. In this reaction, the copper powder not only acts as a sulfone radical initiator but also produces the catalytically active CuCl species. Mechanistic investigations and DFT calculation studies revealed that the stereoselectivity is controlled by the thermodynamic stabilities of the in situ-generated cyclic alkenyl CuII complex intermediate, which can serve as a chlorine atom transfer agent.

Vector sensor imaging

Several methods have been proposed for reconstructing the target image using a linear image sensor with detectors arranged in one dimension. However, they have problems with illumination time, reconstruction time, and complex synchronization between pattern illumination and measuring light intensity data. Here, we propose a one-shot imaging and classification method using a linear sensor and diffuser, called vector sensor imaging. We constructed two deep neural networks for this purpose and demonstrated their effectiveness through simulations and experiments.

The role of oligomerization in the optimization of cyclohexadienyl dehydratase conformational dynamics and catalytic activity.

The emergence of oligomers is common during the evolution and diversification of protein families, yet the selective advantage of oligomerization is often cryptic or unclear. Oligomerization can involve the formation of isologous head-to-head interfaces (e.g., in symmetrical dimers) or heterologous head-to-tail interfaces (e.g., in cyclic complexes), the latter of which is less well studied and understood. In this work, we retrace the emergence of the trimeric form of cyclohexadienyl dehydratase from Pseudomonas aeruginosa (PaCDT) by introducing residues that form the PaCDT trimer-interfaces into AncCDT-5 (a monomeric reconstructed ancestor of PaCDT). We find that single interface mutations can switch the oligomeric state of the variants and that trimerization corresponds with a reduction in the KM value of the enzyme from a promiscuous level to the physiologically relevant range. In addition, we find that removal of a C-terminal extension present in PaCDT leads to a variant with reduced catalytic activity, indicating that the C-terminal region has a role in tuning enzymatic activity. We show that these observations can be rationalized at the structural and dynamic levels, with trimerization and C-terminal extension leading to reduced sampling of non-catalytic conformational substates in molecular dynamics simulations. Overall, this work provides insight into how neutral sampling of distinct oligomeric states along an evolutionary trajectory can facilitate the evolution and optimization of enzyme function.

Analisa dan Perancangan Sistem E-Voting Pemilu Raya BEM di Universitas Ichsan Gorontalo

The Student Executive Board (BEM) is among the organizations in universities formed by students. Through BEM, students can learn to socialize, politics and democracy. Every year Ichsan University conducts BEM ELECTION activities to elect BEM Presidential Candidates. In the process, there is a problem where the BEM ELECTIONS have decreased student political participation because students have to come to campus, and the process of recapitulation of vote counting is quite long. The purpose of the study was to design a web-based e-voting application that all active students can use to participate in the UNISAN BEM ELECTION without having to come directly to campus. The process and results of the UNISAN BEM ELECTIONS were fast, effective and transparent. Data collection techniques carried out observations, interviews and literature studies with system development using the waterfall method. The system design is in the form of a UML diagram. Creation with PHP and MySQL languages for databases. The test results resulted in cyclomatic complexity. In the calculation of cyclomatic complexity, if V(G) = E-N+2, the result is equal to V(G) = P+1. The results of the UNISAN BEM ELECTION research were fast, effective and transparent.

An empirical evaluation of the “Cognitive Complexity” measure as a predictor of code understandability

Background:Code that is difficult to understand is also difficult to inspect and maintain and ultimately causes increased costs. Therefore, it would be greatly beneficial to have source code measures that are related to code understandability. Many “traditional” source code measures, including for instance Lines of Code and McCabe’s Cyclomatic Complexity, have been used to identify hard-to-understand code. In addition, the “Cognitive Complexity” measure was introduced in 2018 with the specific goal of improving the ability to evaluate code understandability. Aims:The goals of this paper are to assess whether (1) “Cognitive Complexity” is better correlated with code understandability than traditional measures, and (2) the availability of the “Cognitive Complexity” measure improves the performance (i.e., the accuracy) of code understandability prediction models. Method:We carried out an empirical study, in which we reused code understandability measures used in several previous studies. We first built Support Vector Regression models of understandability vs. code measures, and we then compared the performance of models that use “Cognitive Complexity” against the performance of models that do not. Results:“Cognitive Complexity” appears to be correlated to code understandability approximately as much as traditional measures, and the performance of models that use “Cognitive Complexity” is extremely close to the performance of models that use only traditional measures. Conclusions:The “Cognitive Complexity” measure does not appear to fulfill the promise of being a significant improvement over previously proposed measures, as far as code understandability prediction is concerned.

Heterogeneous Fe(IV)[dbnd]O mediated fenton-like process on Fe-Zr heterojunction for selective oxidation of organic pollutants at near neutral pH

Remarkable heterogeneous Fe(IV)O (≡Fe(IV)O) mediated Fenton-like process on (1 1 0)-(1 0 0) heterojunction of Fe-Zr bimetallic oxide was proposed in this work for selective oxidation of organic pollutants under near-neutral conditions. The formation of heterojunction shortened the Fe-O bond length by 0.14 Å and increased the binding energy of Fe 2p3/2 orbital by 0.8 eV on Fe-Zr (1 1 0)-(1 0 0) interface, compared with that on Fe2O3 (1 1 0) facet. This will promote the cyclic complexes of Fe(II)-[OOH]+ formation on Fe-Zr (1 1 0)-(1 0 0) interface. Besides, energy barrier of Fe(II)-[OOH]+ on (1 1 0)-(1 0 0) heterojunction was 10.6 kJ mol−1 lower than that on Fe2O3 (1 1 0) facet. It will facilitate the inner two-electron transfer process to generate Fe(IV)O. And electrostatic repulsion and electrophilic addition enable Fe(IV)O to selectively oxidize target organic pollutants in the system containing ions and humic acids. This work provides a fundamental information toward the structure-performance relationship between heterojunction structure and Fe(IV)O formation, and it will enlighten the selective oxidation of pollutants in wastewater treatment.

Characterization of zinc(II) complex of 1,4,7,10-tetrazacyclododecane and deprotonated 5-fluorouracil (FU) in crystalline/solution states and evaluation of anticancer activity: Approach for improving the anticancer activity of FU

Structural and biological properties of 5-fluorouracil (FU) bound zinc(II)–cyclen complex (FU––ZnL2+, L = cyclen; 1,4,7,10-tetrazacyclododecane) were studied in to develop an anticancer drug candidate. The complex formation was analyzed by X-ray crystallography and pH-titration study, and the anticancer activity was investigated by cytotoxicity examination against HL-60 cells. The crystal structure revealed that FU– and ZnL+ form the complex with 1:1 stoichiometry. The pH titration study proved that FU– has a strong affinity to ZnL+ at the physiological pH range (6.5–9.0). The IC50 values of FU––ZnL2+ against HL-60 cells growth was 132 μM in a quantitating cellular ATP levels. These results provide the basis for designing novel anticancer drug complexes and controlling FU release.

The Integration of Hadoop and a Smart Utility Scoring with a Case-Based Reasoning System for Managing Large and Complex Medical Case Base

In case-based reasoning structure, the quality and the complexity of the case data play a significant role in searching, retrieving, updating, and holding distinct case data at or from distinct databases for various purposes. However, managing the very complex and large case-data sets is not easy. Furthermore, the complex algorithm for maintaining case-based reasoning (CBR) structure makes it more critical and increases the time complexity considerably when the dataset is large and complex. Consequently, distinct available techniques related to the maintenance of the CBR system concentrate on deleting the less important and very complex case data to reduce the number of cases. At the same time, it reduces the efficiency and effectiveness of handling the CBR system. Hence, this research employs an integrated platform with the combination of the Hadoop parallel platform and an intelligent utility scoring mechanism. The smart indexing system and the parallel processing capacity of Hadoop reduce the time complexity for processing large and complex datasets. The distributed storage capability effectively manages the data repository and retrieval system for enormous case datasets without compromising case data. The intelligent utility scoring system employs supervised learning and a unique CBR system to quickly and efficiently retrieve the effective solution for each particular case. Furthermore, Hadoop offers a distributed structure that helps the user to access the case data and update the database through the network. This research uses distinct healthcare text-based datasets for testing the performances of the proposed integrated technique in different aspects. The experimental results show the superiorities in producing a higher percentage of accuracy with consuming less Retrieval time over other related techniques. It further shows its time efficiency by offering higher throughput and lower Cyclomatic Complexity with lower read and write Latency Times. Finally, the performances of the proposed technique in these various aspects have been compared with distinct existing techniques and the performances of various databases in managing large and complex medical data to establish its superiority over them.

Improvement of Vulnerable Code Dataset Based on Program Equivalence Transformation

Code vulnerability dataset plays an important role in the development and evaluation of vulnerability detection tools. Aiming at the problem that programs in existing vulnerability datasets usually have simple structures and small scales, which is not satisfying for testing, we proposed a generator of complex code vulnerability dataset based on program equivalence transformation in this paper. It improves the complexity of program structure and code size while preserving the labels of the original case. Based on the PHP vulnerability test suite in Software Assurance Reference Dataset (SARD), a large number of complex cases were constructed and tested using two open-source PHP vulnerability detection tools RIPS and WAP. Experimental results show that the cyclomatic complexity and code size of the generated cases increase by about five times after transformation. The detection accuracy of the tools on the generated dataset decreases significantly compared with the results on the original dataset. The false positive rate increases by about 30%, and the false negative rate increases by about 10%.

Intermittent regimes as a synchronization phenomenon in two sets of nonlinear chemical oscillators.

Systems of nonlinear chemical oscillators can exhibit a large diversity of non-trivial states depending on the parameters that characterize them. Among these, a synchronization phenomenon is of special interest due to its direct link with chemical and biological processes in nature. We carry out numerical experiments for two different sets of chemical oscillators with different properties and immersed in a Belousov-Zhabotinsky solution. We document the emergence of different states of synchronization that depend on the parameters characterizing the solution. We also show that, in the interface regions, this system generates a stable dynamics of intermittency between the different synchronization states where interesting phenomena, such as the "devil's staircase," emerge. In general, the added complexity introduced with the additional set of oscillators results in more complex non-trivial synchronization states.

Nonlinear interaction of parametric excitation and self-excited vibration in a 4 DoF discontinuous system

Interaction between parametric excitation and self-excited vibration has been subjected to numerous investigations in continuous systems. The ability of parametric excitation to quench self-excited vibrations in such systems has also been well documented. But such effects in discontinuous systems do not seem to have received comparable attention. In this article, we investigate the interaction between parametric excitation and self-excited vibration in a four degree of freedom discontinuous mechanical system. Unlike majority of studies in which oscillatory nature of stiffness accounts for parametric excitation, we consider a much more practical case in which parametric excitation is provided by a massless rotor of rectangular cross section with a cylinder-like mass concentrated at the center. The rotor arrangement is placed on a friction-induced self-excited support in the form of a frame placed on a belt moving with constant velocity. This frame is connected to a supplementary mass. A Stribeck friction model is considered for the mass in contact with the belt. The frictional force between the mass and the belt is oscillatory in nature because of the variation of normal force due to parametric excitation from the rotor. Our investigations reveal mutual synchronization of parametric excitation and self-excited vibration in the system for specific parameter values. The existence of a stable limit cycle with constant synchronized fundamental frequency, for a range of parametric excitation frequencies, is established numerically. Investigation based on frequency spectra and Lissajous curves reveals complex synchronization patterns owing to the presence of higher harmonics. The system is also shown to exhibit Neimark–Sacker bifurcations under the variation of belt velocity. Furthermore, variation in belt velocity and coupling stiffness is seen to cause a breakup of quasi-periodic torus with small-amplitude oscillations to form large amplitude chaotic orbits. This points toward the possibility of vibration suppression in the system by tuning the parameters for stabilizing the small-amplitude quasi-periodic response. An example of co-existence of different attractors in the system is also presented.

Adaptive aromaticity in osmapentalene and osmapyridinium complexes with carbone ligands

AbstractDiscovery of species with adaptive aromaticity, being aromatic in both the lowest‐lying singlet and triplet states (S0 and T1), is a significant challenge because cyclic conjugated complexes are commonly aromatic in one state only according to Hückel's and Baird's rules. On other hand, the carbone ligands containing two lone pair electrons at the carbon(0) atom have attracted considerable attention from both theoretical and experimental chemists recently. Here, we carry out density functional theory (DFT) calculations on osmapentalene and osmapyridinium complexes with carbone ligands to examine their aromaticity in both the S0 and T1 states. It is found that these complexes can possess adaptive aromaticity, supported by various aromaticity indices including the harmonic oscillator model of aromaticity (HOMA), nucleus‐independent chemical shift (NICS), anisotropy of the induced current density (ACID), electron density of delocalized bonds (EDDB), and the change of heat of hydrogenation (∆∆H). Our findings expand the scope of the concept of adaptive aromaticity, inviting experimental chemists' verification to enrich aromatic organometallic chemistry.

Asynchronously intermittent decentralized control for synchronization of stochastic delayed networks

This paper studies the asynchronously intermittent decentralized control for the synchronization of stochastic complex delayed networks, where the “asynchronously intermittent” means that the intermittent control for each subsystem is activated asynchronously, i.e., each subsystem possesses its own work or rest time. By designing an auxiliary timer and using a graph-theoretic technique as well as the Halanay’s inequality for piecewise continuous function, we obtain a novel synchronization criterion that is independent of the bound of time-varying delay. Finally, a class of coupled heterogeneous neural networks is considered to show the effectiveness and the superiority of the main result.

DIGITAL TRANSFORMATION IN THE FIELD OF HR PROCESSES: DIRECTIONS, PROBLEMS AND OPPORTUNITIES

The purpose of the article. The development of provisions regarding the formation and use, directions, problems and opportunities of digital transformation in the field of digitalization of HR processes in business under modern business conditions is considered. The article examines the peculiarities of the development of digitalization in the management of the development of personnel potential among domestic enterprises, which requires the application of the experience of foreign countries, which are focused on business optimization, effective IT solutions, and ensuring the quality of personnel. The main directions of the development of management systems in the conditions of digitalization of management are determined, such as: promoting the acceleration of innovative initiatives, prognostic monitoring of the market environment, assessment of factors affecting the company's competitiveness, development of road maps based on industry priorities and customer experience. Along with this, the formation of personnel potential, complex synchronization of all types of activities, development of culture and competencies of information exchange, modernization of IT systems, application of analytics and Big Data are considered. An organic combination of digital HR with mobile applications, social networks, cloud technologies, virtual reality, artificial intelligence to create favorable conditions for improving the work of employees, recruiting and firing personnel, etc. has been determined. Methodology. Digital transformation of HR is a change in the functioning of HR through the use of data in all areas: payroll, performance management, learning and development, profit, compensation, motivation and recruiting. The data on the priorities of HR specialists regarding investments in recruitment activities are shown. As can be seen from the statistics, corporate websites are considered the most important element of recruiting, while the application tracking system is the next priority. Results. Implementation of human resources management strategy is an important stage of the strategic management process. For it to be successful, the organization's management must adhere to the following rules: first, the goals, strategies, tasks of personnel management must be carefully and timely communicated to all employees of the organization in order to obtain from them not only understanding of service personnel management of the organization, but also informal involvement in the implementation of strategies, in particular, the development of obligations of employees to the organization to implement the strategy; secondly, the general management of the organization and the heads of the personnel management service must not only ensure the timely use of all necessary resources (material, equipment, office equipment, financial, etc.), but also have a plan for implementing the strategy in the form of targeted guidelines for the state and development of labor potential and record the achievement of each goal. Digitalization is a necessary process of development of modern enterprises in the conditions of the neo-economy. It is designed to simplify and speed up work with large databases, to ensure the automation of all types of activities (main and auxiliary operational, investment, financial), to improve communication with customers, suppliers and partners and all institutions of the external environment, to form new principles of interaction within the enterprise – between divisions, employees, management, transition to new organizational forms of management. Practical implications. Today, the development of ICT (digitalization) is a factor that changes the pace of enterprise development. ICT contributes to the increase of the motivation of employees, development of their creative thinking, also allows to save working time, multimedia tools and interactivity contribute to a better presentation and, at the same time, the information presented is also assimilated. Modern ICT maximally changes management methods – workplace, type of activity, interests, circle of partners. It is appropriate to single out the following means of mass introduction of fundamentally new ICTs, which caused qualitative changes in enterprise management: mainframes; personal computers; Internet; specialized global networks; cloud computing; Internet sensors, etc. Using all the opportunities of ICT and turning them into a real competitive force becomes the main task for managers. Value/originality. Updated practices, supported by a new type of manager with a new way of thinking, help to strengthen and develop innovative teams. In terms of capabilities, HR provides digital transformation by offering technologies capable of monitoring workforce performance in real time, implementing innovations, and "using feedback to make informed decisions by managers". Digitalization of society has radically changed people's lives and opened up new opportunities in the field of HR. At whatever stage of digital development each individual organization is, the strategy of people management and IT personnel occupy a central place in its strategic priorities, which determines the conditions for long-term development. The digital transformation of HR affects all types of businesses, from the largest corporations to the smallest micro-firms. It includes the transition from long-standing and traditionally used resources, tools and processes (such as filing cabinets and contact lists) to digital means of information storage.

A Cyclen-Functionalized Cobalt-Substituted Sandwich-Type Tungstoarsenate with Versatility in Removal of Methylene Blue and Anti-ROS-Sensitive Tumor Cells.

Oxidative degradation by using reactive oxygen species (ROS) is an effective method to treat pollutants. The synthesis of artificial oxidase for the degradation of dyes is a hot spot in molecular science. In this study, a nanoscale sandwich-type polyoxometalate (POM) on the basis of a tetra-nuclear cobalt cluster and trivacant B-α-Keggin-type tungstoarsenate {[Co(C8H20N4)]4}{Co4(H2O)2[HAsW9O34]2}∙4H2O (abbreviated as CAW, C8H20N4 = cyclen) has been synthesized and structurally examined by infrared (IR) spectrum, ultraviolet–visible (UV–Vis) spectrum, X-ray photoelectron spectrum (XPS), single-crystal X-ray diffraction (SXRD), and bond valence sum (Σs) calculation. According to the structural analysis, the principal element of the CAW is derived from modifying sandwich-type polyanion {Co4(H2O)2 [HAsW9O34]2}8– with four [Co(Cyclen)]2+, in which 1,4,7,10-tetraazacyclododecane (cyclen) is firstly applied to modify POM. It is also demonstrated that CAW is capable of efficiently catalyzing the production of ROS by the synergistic effects of POM fragments and Co–cyclen complexes. Moreover, CAW can interfere with the morphology and proliferation of sensitive cells by producing ROS and exhibits ability in specifically eliminating methylene blue (MB) dyes from the solution system by both adsorption and catalytic oxidation.

Copper-Catalyzed Coupling of Alkyl Vicinal Bis(boronic Esters) to an Array of Electrophiles.

A neighboring boronate group in the substrate provides a dramatic rate acceleration in transmetalation to copper and thereby enables organoboronic esters to participate in unprecedented site-selective cross-couplings. This cross-coupling operates under practical experimental conditions and allows for coupling between vicinal bis(boronic esters) and allyl, alkynyl, and propargyl electrophiles as well as a simple proton. Because the reactive substrates are vicinal bis(boronic esters), the cross-coupling described herein provides an expedient new method for the construction of boron-containing reaction products from alkenes. Mechanistic experiments suggest that chelated cyclic ate complexes may play a role in the transmetalation.

Noise-induced complex dynamics and synchronization in the map-based Chialvo neuron model

The paper considers a stochastic version of the conceptual map-based Chialvo model of neural activity. Firstly, we focus on the parametric zone where this model exhibits mono- and bistability with coexistence of equilibria and oscillatory spiking attractors forming closed invariant curves. Stochastic effects of excitement and generation of bursting are studied both numerically and analytically by confidence ellipses. A phenomenon of the noise-induced transition to chaos in a localized two-parametric zone is discussed. Besides, we also study the phenomenon of synchronization between neurons by using a two-neuron network with a small coupling. In this scenario, we have found critical values of noise for which we obtain a good performance for the synchronization between the neurons of the network.

Insights into the electrochemiluminescence process of a hydrogen bonding iridium(III) complex

• An Ir III complex ( 1 ) and pyrimido-[4,5-c]isoquinolin-3-amine ( 3 )complex 1•3 based on the hydrogen-bonding interaction was investigated. • It was discovered that the complex 1•3 displayed a new reduction upon the mixture of 1 and 3 . • The hydrogen-bonding complex 1•3 demonstrated an ECL enhancement. • Our report provides insights into the ECL processes of this hydrogen-bonding complex. Hydrogen-bonding has been reported as a smart strategy in electrochemiluminescence (ECL) mechanism studies and sensing applications. However, the insights into the hydrogen-bonding effect on ECL behavior have never been clearly demonstrated. This work reports ECL of complex 1•3 based on the hydrogen-bonding interaction between an Ir III complex ( 1 ) and pyrimido-[4,5-c]isoquinolin-3-amine ( 3 ). In their cyclic voltammograms (CVs), both complex 1 and compound 3 did not show any reductions; however, the hydrogen-bonding complex 1•3 displayed a new reduction upon the mixture of 1 and 3 , which could be significantly weakened by the addition of DMF. In a co-reactant ECL pathway with BPO, exciplex [PhCO 2 •1] and excimer [3•3] were produced, which were demonstrated by PL and ECL spectroscopies. Furthermore, benzoate radical PhCO 2 could also react with the hydrogen-bonding complex 1•3 to form [PhCO 2 •1•3] and generate the same ECL emission as [PhCO 2 -1] . Our report provides insights into the ECL processes of this hydrogen-bonding complex.

Transmission Mysteries: Art and Technophilia

Transmission Mysteries: Art and Technophilia