Search

Steganography refers to the practice of hiding sensitive information inside seemingly unrelated data sets. Steganography in the video is one of the best methods available for hiding data without compromising the film's appearance. For improved security and compatibility, the traditional system uses different video steganography techniques with linear or precise positions. Traditional linear video steganography practices face vulnerability, a lack of security, limited embedding options, and inadequate compatibility. Here nonlinear frame(s) and pixel positions based information hiding techniques have been developed to overwhelm the following. Both the nonlinear frame positions and nonlinear pixel positions are selected for the video‐based steganography. In the beginning, the nonlinear frame positions are selected through the key and the key may be with any prescribed range and alphanumeric characters. A single or more frames may be selected through the key and that entirely depends upon the corresponding run‐through. Then the nonlinear pixel and bit positions are also selected through a similar key. The proposed method is also compared with some former techniques and gives a magnificent result. Furthermore, a security analysis of the suggested algorithm has also been conducted using the differential attack method. To validate the suggested method and ensure that it is accurate, the author of this article made use of a very specific and innovative methodology known as the linguistic response surface methodology (LRSM). This model is framed based on achieving a few steganography assessment measures like PSNR, SSIM, and MSE metric values after incorporating hidden text in various nonlinear frames' nonlinear pixel locations of the video. The analysis of the variance using LRSM for PSNR, SSIM, and MSE response reveals very substantial results with confirmation. [ABSTRACT FROM AUTHOR]

An alternative approach to synthesize bis‐indolylmethanes (BIMs) via a unique p‐toluenesulfonic acid (PTSA) catalyzed dual Csp3−Csp2 bond‐breaking reaction has been reported here. In the reported protocol, 1,3,5‐trimethoxybenzene (TMB), an electron‐rich and sterically bulky arene, acts as a carbon‐based leaving group which can be recovered after the completion of the reaction. In this process, several BIMs of various indole derivatives can be synthesized from symmetrical triarylmethanes (TRAMs) containing bis‐TMB motifs. By modifying the reaction conditions, we could control the sequential bond cleavage of two Csp3−Csp2 bonds in starting TRAM. [ABSTRACT FROM AUTHOR]

Goal setting and grade loss aversion have individually been found to be effective motivators for student performance. We combine these two strategies to investigate, in a university setting, the effectiveness of grade endowment within a goal-setting framework. Our participants set grade goals which some must earn the traditional way, thus framed as 'gains', while others are awarded their target grade upfront, thus framed as 'losses'. We find a positive impact of goal setting on student performance. We also find that the effect of grade goals framed as 'losses' is numerically, but not statistically, greater than those framed as 'gains'. [ABSTRACT FROM AUTHOR]

Background: Dengue fever, a viral illness spread mostly by Aedes mosquitoes, continues to pose a substantial public health issue in Dhaka city, Bangladesh. In Dhaka, climatic and socio-demographic factors like population density affect the spread of dengue. The dengue indexes are greatest in the residential mixed zone. Numerous environmental parameters, such as temperature, relative humidity, rainfall, and the air pollution index, have been linked to mosquito larvae, and dengue prevalence is correlated with urbanization, decreased vegetation, and population expansion. Methods: By using an extensive dataset that encompasses a range of years, we use spatial and temporal analytic methodologies to investigate the correlation between land use attributes, climatic variables, and the occurrence of dengue fever. To better understand the dynamics of dengue, the built environment and climatic factors are treated as independent variables in this study. ArcPy is a Python package that facilitates here for geographic data analysis and ArcMap 10.7 also used for visualizing spatial data. Results: The results of our study demonstrate that land use significantly influences the spatial patterns of Dengue incidence in Dhaka city. The dengue hotspot Thana are identified and these are Badda, Jatrabari, kadamtali, Mirpur, Mohammadpur, Sobujbagh, Shyampur, Tejgoan, Dhanmondi and Uttara. All of these areas' population density and residential use as land use is higher than the other Thana of Dhaka city. There exists a significant correlation between climatic characteristics, such as temperature (0.25), rainfall (.803), specific humidity (0.74), relative humidity (0.76), wind speed (0.4) and Dengue incidence patterns. This research emphasizes the structural use and climatic relationship in Dengue epidemics, with climatic conditions playing a significant role as drivers of these variations. Conclusions: This research demonstrates the complex relationship between land use, meteorological factors, and the spread of Dengue fever in Dhaka city. The results of this study have significant significance for several domains, including urban planning, public health measures, and vector control tactics. A comprehensive understanding of the temporal and geographical patterns of dengue transmission might aid in the development of accurate and effective prevention measures intended to lessen the effects of dengue in cities, such as Dhaka. [ABSTRACT FROM AUTHOR]

Technological innovation for re-identifying maritime vessels plays a crucial role in both smart shipping technologies and the pictorial observation tasks necessary for marine recon- naissance. Vessels are vulnerable to varying gradations of engaging in the marine environment, which is complicated and dynamic compared to the conditions on land. Fewer picture samples along with considerable similarity are characteristics of warships as a class of ship, making it more challenging to recover the identities of warships at sea. Consequently, a convolutional dynamic alignment network (CoDA-Net) re-identification framework is proposed in this research. To help the network understand the warships within the desired domain and increase its ability to identify warships, a variety of ships are employed as origin information. Simulating and testing the winning of war vessels at sea helps to increase the network's ability to recognize complexity so that users can better handle the effects of challenging maritime environments. The impact of various types of ships as transfer items is also highlighted. The research results demonstrate that the enhanced algorithm increases the overall first hit rate (Rank1) by approximately 5.9%; it also increases the mean average accuracy (mAP) by approximately 10.7% and the correlation coefficient by 0.997%. [ABSTRACT FROM AUTHOR]

The NO + CO reaction is considered a prototype reaction that portrays the abatement of NOx, the primary pollutant from automobile exhausts, catalyzed by metals like Pd, Pt, and Rh. The detailed mechanism of this reaction on the Pd(111) surface was devised by taking into account all probable elementary reactions with the aid of density functional theory calculations. The reaction steps under consideration include NO dissociation, N2 formation from N-N recombination, CO2 formation, N2O formation, and N2O dissociation, respectively. The adsorption energies, reaction energies, and activation energy barriers were calculated for all the elementary steps of the reaction. Depending on the lattice site, over which the intermediates of the elementary steps get adsorbed, adsorption energies vary significantly. Both N-N recombination and N2O decomposition were identified as the reaction pathways for N2 formation. The NO dissociation step could be regarded as the rate-determining step, bearing the highest activation energy barrier among all the elementary reactions. The reactivity of this step has been shown to increase with an increase in the surface temperature. It was also observed that N2 formation from N-N recombination controls the overall reaction rate to a certain extent. The influence of different Pd facets on NO dissociation was scrutinized, and it was found that (100) facet exhibits a lower activation energy barrier than (111) metal surface. The higher activity of (100) surface was explained with the help of the density of states plots. The model reaction NO + CO has been studied in detail on Pd (111) surface to understand Three Way Catalytic (TWC) converters. NO dissociation step was found to be the RDS. The surface temperature has been shown to affect the reactivity of the RDS. Pd(100) could be used for better performance. [ABSTRACT FROM AUTHOR]

The global healthcare sector continues to grow rapidly and is reflected as one of the fastest-growing sectors in the fourth industrial revolution (4.0). The majority of the healthcare industry still uses labor-intensive, time-consuming, and error-prone traditional, manual, and manpower-based methods. This review addresses the current paradigm, the potential for new scientific discoveries, the technological state of preparation, the potential for supervised machine learning (SML) prospects in various healthcare sectors, and ethical issues. The effectiveness and potential for innovation of disease diagnosis, personalized medicine, clinical trials, non-invasive image analysis, drug discovery, patient care services, remote patient monitoring, hospital data, and nanotechnology in various learning-based automation in healthcare along with the requirement for explainable artificial intelligence (AI) in healthcare are evaluated. In order to understand the potential architecture of non-invasive treatment, a thorough study of medical imaging analysis from a technical point of view is presented. This study also represents new thinking and developments that will push the boundaries and increase the opportunity for healthcare through AI and SML in the near future. Nowadays, SML-based applications require a lot of data quality awareness as healthcare is data-heavy, and knowledge management is paramount. Nowadays, SML in biomedical and healthcare developments needs skills, quality data consciousness for data-intensive study, and a knowledge-centric health management system. As a result, the merits, demerits, and precautions need to take ethics and the other effects of AI and SML into consideration. The overall insight in this paper will help researchers in academia and industry to understand and address the future research that needs to be discussed on SML in the healthcare and biomedical sectors. [ABSTRACT FROM AUTHOR]

Bone diseases are common and can result in various musculoskeletal conditions (MC). An estimated 1.71 billion patients suffer from musculoskeletal problems worldwide. Apart from musculoskeletal fractures, femoral neck injuries, knee osteoarthritis, and fractures are very common bone diseases, and the rate is expected to double in the next 30 years. Therefore, proper and timely diagnosis and treatment of a fractured patient are crucial. Contrastingly, missed fractures are a common prognosis failure in accidents and emergencies. This causes complications and delays in patients' treatment and care. These days, artificial intelligence (AI) and, more specifically, deep learning (DL) are receiving significant attention to assist radiologists in bone fracture detection. DL can be widely used in medical image analysis. Some studies in traumatology and orthopaedics have shown the use and potential of DL in diagnosing fractures and diseases from radiographs. In this systematic review, we provide an overview of the use of DL in bone imaging to help radiologists to detect various abnormalities, particularly fractures. We have also discussed the challenges and problems faced in the DL-based method, and the future of DL in bone imaging. [ABSTRACT FROM AUTHOR]

Retrieving mathematical expressions from scientific documents is a challenging task as mathematical expressions or formulae are quite different from the traditional text. Mathematical expressions are highly symbolic and complex. Moreover, the structure of a mathematical formula conveys a semantic meaning which cannot be overlooked. This paper proposes a scientific document retrieval system based on mathematical formula query. The paper explores the concept of Structure Encoded String (SES), which has been employed for mathematical expressions to capture the relations among the formula structures. A pattern based trie indexing scheme has been proposed for faster retrieval. The Jaro-Winkler Similarity has been adopted for matching and ranking. Experiments are conducted, results are reported using standard evaluation measures and compared with similar existing systems. [ABSTRACT FROM AUTHOR]

Retrieving mathematical expressions from scientific documents is a challenging task as mathematical expressions or formulae are quite different from the traditional text. Mathematical expressions are highly symbolic and complex. Moreover, the structure of a mathematical formula conveys a semantic meaning which cannot be overlooked. This paper proposes a scientific document retrieval system based on mathematical formula query. The paper explores the concept of Structure Encoded String (SES), which has been employed for mathematical expressions to capture the relations among the formula structures. A pattern based trie indexing scheme has been proposed for faster retrieval. The Jaro-Winkler Similarity has been adopted for matching and ranking. Experiments are conducted, results are reported using standard evaluation measures and compared with similar existing systems. [ABSTRACT FROM AUTHOR]

Purpose: We sought to exploit the heterogeneity afforded by patient-derived tumor xenografts (PDX) to first, optimize and identify robust radiomic features to predict response to therapy in subtype-matched triple negative breast cancer (TNBC) PDX, and second, to implement PDX-optimized image features in a TNBC co-clinical study to predict response to therapy using machine learning (ML) algorithms. Methods: TNBC patients and subtype-matched PDX were recruited into a co-clinical FDG-PET imaging trial to predict response to therapy. One hundred thirty-one imaging features were extracted from PDX and human-segmented tumors. Robust image features were identified based on reproducibility, cross-correlation, and volume independence. A rank importance of predictors using ReliefF was used to identify predictive radiomic features in the preclinical PDX trial in conjunction with ML algorithms: classification and regression tree (CART), Naïve Bayes (NB), and support vector machines (SVM). The top four PDX-optimized image features, defined as radiomic signatures (RadSig), from each task were then used to predict or assess response to therapy. Performance of RadSig in predicting/assessing response was compared to SUVmean, SUVmax, and lean body mass-normalized SULpeak measures. Results: Sixty-four out of 131 preclinical imaging features were identified as robust. NB-RadSig performed highest in predicting and assessing response to therapy in the preclinical PDX trial. In the clinical study, the performance of SVM-RadSig and NB-RadSig to predict and assess response was practically identical and superior to SUVmean, SUVmax, and SULpeak measures. Conclusions: We optimized robust FDG-PET radiomic signatures (RadSig) to predict and assess response to therapy in the context of a co-clinical imaging trial. [ABSTRACT FROM AUTHOR]

Strategic religious engagement in relief & development efforts requires: a careful country assessment, establishing appropriate principles of engagement, and defining priority sectors and institutions (possibly including multireligious platforms equipped to serve as intermediaries). Important factors to take into account include: (a) a risk assessment; (b) review of information sources and gaps; (c) understanding religion-state relationships; (d) religious roles in civil society and with both formal and informal institutions; (e) involvement in humanitarian activities including prevention and response; and (f) possible sensitivities and conflicts involving religious actors including potential for engagement with a peacebuilding focus. [ABSTRACT FROM AUTHOR]

Religious involvement in humanitarian aid and development takes countless forms, varying by country, traditions, and sector. Research and operational evaluations have expanded in recent years, with some sectors far better documented than others, notably health and peacebuilding. There are, however, substantial gaps in evidence, most significantly regarding local and non-formal involvement. Pandemic preparedness and response are critical issues ready for further development. Family planning, a USAID priority, exemplifies sensitivities but also positive examples and potential. Experience of religious engagement on women's empowerment including specific issues like gender-based violence (GBV) and child marriage, can be complex, but their importance warrants particular attention. Child protection poses similar issues. [ABSTRACT FROM AUTHOR]

Strategic religious engagement (SRE) is important for five main reasons: (a) the direct and significant contributions of religious actors to humanitarian assistance and development, not least their high levels of trust and access, and their distinctive contributions to spiritual care; (b) The local presence and knowledge of faith-based organizations (FBOs) and religious communities that are critical to self-reliance; (c) the significant if often complex relationships that FBOs and religious communities have with governments and other civil society actors; (d) the dual capacity of religious communities to amplify/ameliorate suffering and conflict; and, (e) the central roles of religions in shaping humanitarian norms and law. [ABSTRACT FROM AUTHOR]

Dengue is a vector-borne viral disease caused by the flavivirus dengue virus (DENV). Approximately 400 million cases and 22 000 deaths occur due to dengue worldwide each year. It has been reported in more than 100 countries in tropical and subtropical regions. A positive-stranded enveloped RNA virus (DENV) is principally transmitted by Aedes mosquitoes. It has four antigenically distinct serotypes, DENV-1 to DENV-4, with different genotypes and three structural proteins and seven non-structural proteins. Clinical symptoms of dengue range from mild fever to severe dengue hemorrhagic fever (DHF) or dengue shock syndrome (DSS), with thrombocytopenia, leucopenia, and increased vascular permeability. Although primary infection causes activation of immune responses against DENV serotypes, the severity of the disease is enhanced via heterotypic infection by various serotypes as well as antibody-dependent enhancement (ADE). The first licensed DENV vaccine was tetravalent CYD Denvaxia, but it has not been approved in all countries. The lack of a suitable animal model, a proper mechanistic study in pathogenesis, and ADE are the main hindrances in vaccine development. This review summarizes the current knowledge on DENV epidemiology, biology, and disease aetiology in the context of prevention and protection from dengue virus disease. [ABSTRACT FROM AUTHOR]

Background: Ayurveda emphasizes that different parts of plants (both organized and unorganized) should be collected on a certain season to get their better yield and therapeutic value. In general, Kshira (latex) should be collected in Sharada rutu (autumn season). However, the latex of Snuhi has been stated to be collected at Shishiranta (end of winter). The latex of Snuhi has an important place in different therapeutic formulations. One of the important mentions is for the preparation of Ksharasutra, one of the widely used paramedical procedures in Ayurveda. Objectives: The objective of this study was to evaluate the impact of seasonal variation on the quantity of euphadienol content (one of the major active constituents) in latex sample of Euphorbia antiquorum L. (EA) and Euphorbia tirucalli L. (ET). Materials and Methods: The latex was collected individually during six different seasons in a calendar year from two species i.e. EA and ET. Then, after suitable sample preparation, it was subjected to high-performance thin-layer chromatography study using euphadienol as a standard biomarker and scanned at 210 nm. Results: The euphadienol content was found to be present in all the six seasons across the calendar year. The content was found maximum in Hemanta rutu and Sharada rutu samples in case of EA and ET, respectively. Conclusion: The study proves that changes of seasons do have a certain effect on the phytoconstituents in the plants. [ABSTRACT FROM AUTHOR]

Dissociative chemisorption is one of the most significant steps in heterogeneous catalysis. The rate-limiting step for industrially important processes such as water gas-shift reaction and steam reforming of methane involves the dissociative chemisorption of water and methane, respectively. These reactions exhibit interesting mode-specificity and show a strong dependence on the surface temperature of the catalyst. The metals commonly used in industry as catalysts for these two processes have their own limitations. Certain bimetallic surfaces and subsurface alloys are suggested, which could be regarded as potential catalysts for these two industrial processes. How transition states are modified by the motion of the lattice atom during the reactions are shown using electronic structure calculations. In the present review, we have focused on the lattice atom distortion in the transition state, semi-classical tunnelling probability, and the influence of surface temperature on reactivity. Quantum dynamics study for H 2 O dissociation on metal surface is explored using three-dimensional London-Eyring-Polanyi-Sato potential energy surface. A full quantum mechanical approach following reaction path Hamiltonian is also studied by including the effects of lattice motion and site averaging. The effects of initial vibrational mode on reactivity are reported. Vibrational efficacy is examined in terms of vibrational non-adiabatic couplings. [ABSTRACT FROM AUTHOR]

Background: Ayurveda emphasizes that different parts of plants (both organized and unorganized) should be collected on a certain season to get their better yield and therapeutic value. In general, Kshira (latex) should be collected in Sharada rutu (autumn season). However, the latex of Snuhi has been stated to be collected at Shishiranta (end of winter). The latex of Snuhi has an important place in different therapeutic formulations. One of the important mentions is for the preparation of Ksharasutra, one of the widely used paramedical procedures in Ayurveda. Objectives: The objective of this study was to evaluate the impact of seasonal variation on the quantity of euphadienol content (one of the major active constituents) in latex sample of Euphorbia antiquorum L. (EA) and Euphorbia tirucalli L. (ET). Materials and Methods: The latex was collected individually during six different seasons in a calendar year from two species i.e. EA and ET. Then, after suitable sample preparation, it was subjected to high-performance thin-layer chromatography study using euphadienol as a standard biomarker and scanned at 210 nm. Results: The euphadienol content was found to be present in all the six seasons across the calendar year. The content was found maximum in Hemanta rutu and Sharada rutu samples in case of EA and ET, respectively. Conclusion: The study proves that changes of seasons do have a certain effect on the phytoconstituents in the plants. [ABSTRACT FROM AUTHOR]

Copy-move forgery is one of the most popular tampering artefacts in digital images. However, tampering effect in digital images makes the authentication of the processing as untrustworthy. In this paper, a combination of Fourier-Mellin and Zernike moments (FMZM) Transform is proposed which detects the copy-move region with high-speed and low-computational complexity. Here, initially an image is segmented into various blocks using marker controlled watershed management and from that proposed FMZM feature extraction is used which detects duplication. The detected regions are matched with the Dense Depth Reconstruction based lexicographically sorting. Finally, tampered outliers presented at the data are removed through RANSAC (RANdom Sample Consensus) algorithm, in which removed false matches are verified with the morphological operators. The efficiency of proposed method is measured by various performance metrics and this method earned up to 97.56%, 99.98%, and 97.12% for precision, recall, and F1-score performance, respectively. [ABSTRACT FROM AUTHOR]

Summary: The natural experiment proposed in this article extracts three stories from boxes of "100 paper clips". The activity requires students to apply three lessons from inferential statistics, starting with a hypothesis test and including confidence intervals as well as tolerance intervals. [ABSTRACT FROM AUTHOR]

We have developed an approach for the construction of naphthofuran‐2‐carboxaldehyde derivatives utilizing the synergy of electrochemical oxidation and organo‐selenium catalysis at room temperature. The compatibility of various functional groups and scalability of this protocol demonstrate the practicality of the electrochemical strategy. The synthetic utility of this strategy is furthermore demonstrated by synthesizing diversified molecules through downstream transformations. [ABSTRACT FROM AUTHOR]

This paper presents a technique of motion planning of robot using Fuzzy Method and Genetic Algorithm along with Three Path concept in a dynamic environment which contains both static and dynamic obstacles. The algorithm is divided into two phases. In the first phase, a path or two is generated by using Three Path Method or Fuzzy-GA while considering static obstacles only. The information about the distances and angles of obstacles from the robot is acquired by using the concept of Three Path. A collision free path is selected by using Three Path concept. When all the three paths are blocked by static obstacles Fuzzy Method is used for obstacles avoidance. Genetic Algorithm is used to find optimal range of the linguistic values of the variables for the membership functions. In the second phase, the moving obstacles are avoided along the path/paths generated in the first phase by considering the velocities of the moving obstacles and the velocity of the robot. Results show that the technique of motion planning of mobile robots using Fuzzy-GA along with Three Path concept is computationally efficient as compared to other hybrid methods for motion planning in dynamic environment. [ABSTRACT FROM AUTHOR]

Introduction: The incidence of Human Immunodeficiency Virus (HIV), Hepatitis B Virus (HBV) and Hepatitis C Virus (HCV) in India has increased over the past two decades. These infections cause significant mortality and morbidity. This increasing trend is alarming and is emerging as a global health problem. India has one of the largest reservoirs of HIV, HBV and HCV and many of its cases remain undetected. Due to the large sero-prevalence in India, serological tests for HBsAg, anti-HCV and anti-HIV are done for diagnosing the respective diseases, and screening of antenatal, preoperative cases and of blood donors. Aim: To find out the efficacy of Rapid Diagnostic Test (RDT) and Enzyme Chemiluminescence Immunoassay (ECLIA) in comparison to Enzyme Linked Immunosorbent Assay (ELISA) for diagnosis of HBV, HCV and HIV infections in patients. Materials and Methods: This cross-sectional study presented a comparative analysis of test results of HBsAg, anti-HCV and anti-HIV antibodies by different methods namely RDT and ECLIA taking ELISA as reference standard. A total of 198 serum samples were taken from patients and tests were done for HBsAg, anti-HCV and anti-HIV by three different methods i.e. ECLIA, RDT and ELISA and sensitivity, specificity, Positive Predictive Value (PPV), Negative Predictive Value (NPV) and accuracy were calculated. The agreement between the results was computed using Kappa coefficient. Results: The findings demonstrated that for HBsAg, the results of RDT and ECLIA were same. For anti-HIV 1 and 2, sensitivity of RDT and ECLIA was similar. For anti-HCV, ECLIA showed better sensitivity than RDT and RDT showed better specificity than ECLIA. Strength of agreement was almost perfect for HBsAg and anti-HIV, where as for anti-HCV it was substantial. Conclusion: There were some variations in certain results by different methods. It was observed that RDT and ECLIA are good screening tests for HIV and HBV infections. On the other hand, we inferred that for HCV, ECLIA is a better screening test than RDT. [ABSTRACT FROM AUTHOR]

This work examines the effect of pulse deposition using a “lean” electrolyte, i.e., an acid-free bath with low cupric ion and additive concentrations using direct and pulse current. To this end, 25 μm copper films have been plated on stainless steel substrates from electrolytes containing only cupric ions, chloride and commercial additives. Films have been deposited from electrolytes containing different concentrations of additives ranging from 17% to 200% of the levels recommended by the supplier. The morphology of deposits was characterised using scanning electron microscopy and grain size has been determined using electron backscattered diffraction (EBSD). The crystalline structure has been examined using x-ray diffraction (XRD). It was found that although pulse currents or increasing amounts of chemical additive can reduce the grain size, the mechanisms for size reduction may be different. Whilst current pulsing helps the generation of new nuclei, using additives suppresses grain growth. Mechanical and electrical measurements of these films showed that pulsing currents provide deposits with better mechanical and electrical properties. This has been attributed to lower number of defects when pulse currents are used. Our results also show that by using pulse currents, electrolytes containing low levels of additives and metal ions can be used to obtain copper deposits attaining industry specifications. Combining pulse currents with lean electrolytes may be therefore beneficial to the environment. [ABSTRACT FROM AUTHOR]

This work describes the design and testing of an ultrasonic reactor suitable for processes which require agitation within a narrow gap in a tank geometry. A maskless microfabrication process was used to validate the ultrasonic reactor design. This mask-less electrodeposition method requires the inter-electrode distance between the anode tool and the cathode substrate to be maintained at 300 μm, and sufficient stirring of the electrolyte by ultrasound agitation. A design was proposed allowing 74 mm × 105 mm size substrates to be mounted into an electrode holder and loaded into an 18 L ultrasonic reactor. Experiments were carried out to test the uniformity of the mass transfer within the narrow electrode gap at different locations on the substrate, and to validate the feasibility of a mask-less metal plating technique by depositing features of μm-scale. When increasing ultrasonic powers from 30 to 60 W L −1 , increasing agitation was observed at the centre of the substrate, but not at its edges. A Sherwood number correlation showed developing turbulence within the narrow gap, even in the centre of the plate. Micron scale features were plated onto A7 substrates, but the deposited features were 2.5 times the original width. The work showed that sonic streaming can produce sufficient agitation in long sub millimetre channels which can be employed to overcome mass transfer limitations. [ABSTRACT FROM AUTHOR]

Background and objectives Retinal fundus images are extensively used in manually or without human intervention to identify and analyze various diseases. Due to the comprehensive imaging arrangement, there is a large radiance, reflectance and contrast inconsistency within and across images. Method A novel method is proposed based on the cataract physical model to reduce the generated blurriness of the fundus image at the time of image acquisition through the thin layer of cataract by the fundus camera. After the blurriness reduction the method is proposed the enhancement procedure of the images with an objective on contrast perfection with no preamble of artifacts. Due to the uneven distribution of thickness of the cataract, the cataract surroundings are first predicted in the domain of frequency. Second, the resultant image of first step enhanced by the intensity histogram equalization in the adapted Hue Saturation Intensity (HSI) color image space such as the gamut problem can be avoided. The concluding image with suitable color and disparity is acquired by using the proposed max–min color correction approach. Results The result indicates that not only the proposed method can more effectively enhanced the non-uniform image of retina obtain through thin layer of cataract, but also the resulting image show appropriate brightness and saturation and maintain complete color space information. The projected enhancement method has been tested on the openly available datasets and the result evaluated with the standard used image enhancement algorithms and the cataract removal method. Results show noticeable development over existing methods. Conclusions Cataract often prevents the clinician from objectively evaluating fundus feature. Cataract also affect subjective test. Enhancement and restoration of non-uniform illuminated Fundus Image of Retina obtained through thin layer of Cataract has shown here to be potentially beneficial. [ABSTRACT FROM AUTHOR]

A neutral octa‐nuclear AuI‐cluster (2) with molecular formula [(Cy‐cAACPAu)4(AuCl)4] [Cy‐cAAC=:C(N‐2,6‐iPr2C6H3)(C6H10)(CMe2)(CH2)] has been isolated, and structurally characterized by single‐crystal X‐ray diffraction. 2 has been further studied by NMR and ESI‐MS. The μ3‐P bridged AuI‐cluster 2 possesses a C2 axis that passes through the two Au atoms positioned oppositely of the central AuI4P4 core, and two carbene‐P chromophores. The emission spectrum of 2 exhibited a broad band with λem at 720 nm, and an average lifetime of 3.36 ns when excited at 388 nm in solid state at room temperature. Cyclic voltammetry (CV) studies revealed that 2 can undergo reversible one‐electron oxidation at 0.76 V. The electronic transition in 2 has been further studied by computational methods. [ABSTRACT FROM AUTHOR]

The stability and reactivity studies of heavier di‐atomic group‐15 congeners of alkynes, e. g. the di‐phosphorus (P≡P) compounds have been the topic of huge interest because of their contrasting transient properties and lower stability compared to those of the stable molecular di‐nitrogen (N≡N). Herein, we depict the reactivity studies of the bis‐cAAC‐stabilized di‐phosphorus (P2) having an inversely polarized phosphaalkene nature featuring the C=P double bonds with Au(I)Cl. Both the mono‐, and the di‐aurated phosphaalkenes with the formulae [(Me2‐cAAC=P)2(AuCl)] (2), and [(Me2‐cAAC=P)2(AuCl)2] (3), respectively have been isolated in the solid state. Moreover, for the first time, we have been able to isolate the cAAC‐stabilized tetra‐aurated elusive di‐phosphorus‐monoxide (P2O) with the formula [(Cy‐cAAC=P)−O−(P=cAAC−Cy)(AuCl)4] (5) in presence of oxygen. Complexes 2–3, 5 have been structurally characterized by single crystal X‐ray diffraction, and further studied by NMR spectroscopy. Our findings reveal significant elongation of the CcAAC−P bonds in 2–3, 5, and the presence of aurophilic interaction in 5. Quantum chemical calculations, including density functional theory (DFT), and energy decomposition analysis coupled with natural orbitals for chemical valence (EDA‐NOCV) have been performed to study the electron densities distribution and nature of bonding in 2–3, 5. [ABSTRACT FROM AUTHOR]

In this paper, an iterative implement of level set methodology has been proposed for the precise segmentation of normal and abnormal tissues in magnetic resonance imaging (MRI) brain images. In this segmentation, the normal tissues such as WM (white matter), GM (grey matter), and CSF (cerebrospinal fluid) with other regions of human head such as skull, marrow, and muscles skin are segmented and abnormal tissues such as haemorrhage, oedema, and tumour can be segmented if any. The segmentation is done by using iterative three region level set method based on the condition sharp peak greater than three. The iterative segmented component generates a hierarchical structure for correct segmentation. The performance of the segmentation method is estimated by different metrics such as accuracy, similarity index, and relative error. The performance of segmentation method is examined using a defined set of MRI brain. [ABSTRACT FROM AUTHOR]

The cyclic alkyl(amino) carbene (cAAC) bonded chlorophosphinidene (cAAC)P−Cl ( 2/ 2') was isolated from the direct reaction between cAAC and phosphorus trichloride (PCl3). Compound 2/ 2' has been characterized by NMR spectroscopy and mass spectrometry. 31P NMR investigations [ δ≈160 ppm (major) and δ≈130 ppm (minor)] reveal that there are two different P environments of the P−Cl unit. X-ray single-crystal determination suggests a co-crystallization of two conformational isomers of (cAAC)P−Cl ( 2/ 2'); the major compound possessing a cAAC−PCl unit with CcAAC−P 1.75 Å. This C−P bond length is very close to that of (NHC)2P2 [NHC= N-heterocyclic carbene]. The residual density can be interpreted as a conformational isomer with a shorter CcAAC−P bond similar to a non-conjugated phosphaalkene [R−P=CR2]. Our study shows an unprecedented example of two conformational isomers with different Ccarbene−element bonds. Additionally, Br ( 3c/ 3c'), I ( 4c/ 4c'), and H ( 5c/ 5c') analogues [(Me2-cAAC)P−X; X=Br ( 3), I ( 4), H ( 5)] of 2c/ 2c'[(Me2-cAAC)P−Cl] were also synthesized and characterized by NMR spectroscopy suggesting similar equilibrium in solution. The unique property of cAAC and the required electronegativity of the X (X=Cl, Br, I, and H) atom play a crucial role for the existence of the two isomers which were further studied by theoretical calculations. [ABSTRACT FROM AUTHOR]

Background and objectives Multiple sclerosis is one of the major diseases and the progressive MS lesion formation often leads to cognitive decline and physical disability. A quick and perfect method for estimating the number and size of MS lesions in the brain is very important in estimating the progress of the disease and effectiveness of treatments. But, the accurate identification, characterization and quantification of MS lesions in brain magnetic resonance imaging (MRI) is extremely difficult due to the frequent change in location, size, morphology variation, intensity similarity with normal brain tissues, and inter-subject anatomical variation of brain images. Methods This paper presents a method where adaptive background generation and binarization using global threshold are the key steps for MS lesions detection and segmentation. After performing three phase level set, we add third phase segmented region with contour of brain to connect the normal tissues near the boundary. Then remove all lesions except maximum connected area and corpus callosum of the brain to generate adaptive background. The binarization method is used to select threshold based on entropy and standard deviation preceded by non-gamut image enhancement. The background image is then subtracted from binarized image to find out segmented MS lesions. Results The step of subtraction of background from binarized image does not generate spurious lesions. Binarization steps correctly identify the MS lesions and reduce over or under segmentation. The average Kappa index is 94.88%, Jacard index is 90.43%, correct detection ration is 92.60284%, false detection ratio is 2.55% and relative area error is 5.97% for proposed method. Existing recent methods does not have such accuracy and low value of error rate both mathematically as well as visually due to many spurious lesions generation and over segmentation problems. Conclusions Proposed method accurately identifies the size and number of lesions as well as location of lesions detection as a radiologist performs. The adaptability of the proposed method creates a number of potential opportunities for use in clinical practice for the detection of MS lesions in MRI. Proposed method gives an improved accuracy and low error compare to existing recent methods. [ABSTRACT FROM AUTHOR]

Platinum dichalcogenides have been known to exhibit two-dimensional layered structures. Herein, we describe the syntheses, isolation, and characterization of air-stable crystalline cyclic alkyl(amino) carbene (cAAC)-supported monomeric platinum disulfide three-membered ring complex [(cAAC)2Pt(S2)] ( 2). The highly reactive platinum(0) [(cAAC)2Pt] complex ( 1) with two-coordinate platinum activates elemental sulfur to give 2. The brown crystals of bis-carbene platinum(II)monosulfate [(cAAC)2Pt(SO4) x(S2)1− x] ( 4) have been isolated when the reaction was performed in air. The dioxygen analogue of 2 was formed upon exposing the THF solution of 1 to aerial oxygen (O2). The binding of oxygen at the Pt0 center was found to be reversible. Additionally, DFT study has been performed to elucidate the electronic structure and bonding scenario of 2, 3, and 4. Quantum chemical calculations showed donor-acceptor-type interaction for the Pt−S bonds in 2 and Pt−O bonds in 3 and 4. [ABSTRACT FROM AUTHOR]

In the digital era ontology is considered as one of the powerful tools for knowledge representation and efficient information retrieval. Ontology alignment is a process that discovers mapping between source and target ontologies, where each mapping is a relationship based on some similarity measure. This paper, has presented a new context aware alignment approach that needs little human intervention and it can map multiple ontologies to generate user interest dynamically. The objective is to design and develop an ontology alignment model that provides more benefits to its stakeholders in sharing resources and searching across digital libraries based on priorities of users. The experimental results evidently indicate significant improvement in search results when user profile and navigational pattern ontologies are aligned with digital library ontology. [ABSTRACT FROM AUTHOR]

N-Heterocyclic carbenes (NHCs) are known to stabilize some metal atoms in different oxidation states mostly by their strong σ-donation. After the successful syntheses of cyclic alkyl(amino) carbenes (cAACs), they have been proven to be much more effective in stabilizing electron rich species. In cAAC, one of the σ-withdrawing and π-donating nitrogen atoms of NHC is replaced by a σ-donating quaternary carbon atom leading to a lower lying LUMO. This makes the acceptance of π-back-donation from the element bound to the carbene carbon atom of cAAC energetically more advantageous. Further evidence suggests that the carbene carbon of cAAC can use the lone pair of electrons present on the adjacent nitrogen in a more controlled way depending on the accumulation of electron density on the bound metal. It has been found that cAAC can be utilized as excellent ligand for the stabilization of a complex with three coordinate metal center [(cAAC)2MI-Cl; M = Fe, Co, Cr]. Complex (cAAC)2MIICl2 [M = Fe, Co, Cr] was prepared by reacting anhydrous M(II)Cl2 with two equiv of cAAC followed by treatment with one equiv of KC8 (reducing agent) to obtain (cAAC)2MI-Cl. The corresponding cation (cAAC)2M+ was isolated when (cAAC)2MI-Cl was reacted with sodium-tetraarylborate (lithium) in toluene or fluorobenzene. The CV of cation (cAAC)2M+ [M = Co, Fe] suggests that it can reversibly undergo one electron reduction. The cations of Co and Fe were reduced with Na(Hg) or KC8, respectively. (cAAC)2CoICl can be directly reduced to (cAAC)2Co0 when reacted with one equiv of KC8. Analogous (cAAC.)2ZnII and (cAAC)2Mn complexes are prepared by reduction of (cAAC)MCl2 [M = Zn, Mn] with two equiv of KC8 in the presence of one equiv of cAAC. The square planar (cAAC)2NiCl2 complex was directly reduced by two equiv of LiN(iPr2) (KC8) to (cAAC)2Ni0. The (cAAC)2Pd0 and (cAAC)2Pt0 complexes are prepared by substituting all four triphenylphosphines of (Ph3P)4M0 [M = Pd, Pt] by two cAACs. Cation (cAAC)2M+ [M = Cu, Au] was reduced with sodium/potassium to obtain the neutral analogue [(cAAC)2Cu, (cAAC)2Au]. Two coordinate Zn/Mn/Cu/Au are stabilized by two neutral carbene ligands possessing radical electrons on the carbene carbon atoms, while analogous complexes of Co/Fe/Ni/Pd/Pt contain metals in the zero oxidation state. The ground electronic structure of (cAAC)2M was thoroughly studied by theoretical calculations. In this Account, we summarize our developments in stabilizing metal complexes with low coordinate metal atoms in two, one, and most significantly in their zero oxidation states by utilizing cAACs as ligands. [ABSTRACT FROM AUTHOR]

Because of the advantages of flexibility and ease of deployment, wireless mesh network (WMN) has become a promising technology for providing internet access to the users. For implementation of WMN, IEEE 802.11s standard has been developed. To route the packets from source to destination, IEEE 802.11s uses a routing algorithm named hybrid wireless mesh protocol (HWMP). But IEEE 802.11s does not support mobility of external stations. For solving this problem, many mobility management schemes such as: MEsh networks with MObility management, mesh mobility management ( M), iMesh, Smesh and WMM have been proposed. But, none of the schemes are integrated with HWMP. In this paper, an enhanced form of HWMP named forward pointer-based routing (FPBR) has been introduced. Numerical analysis of both HWMP and FPBR has been carried out. HWMP and FPBR have been simulated in NS2, and their performances have been compared. Simulation results show that by varying number of external stations, on average FPBR outperforms HWMP by 93.9, 49, 86.5 and 16.4 % in terms of normalized routing overhead, throughput, handoff cost and end-to-end delay, respectively. With variation in data transmission rate of external stations, on average FPBR outperforms HWMP by 96, 10, 87 and 12 % in terms of normalized routing overhead, throughput, handoff cost and end-to-end delay, respectively. With variation in maximum movement speed of the external stations, FPBR outperforms HWMP by 94 and 97 % in terms of handoff cost and normalized routing overhead. Finally, the number of route management packets per handoff, obtained from both numerical analysis and simulation results has been compared. [ABSTRACT FROM AUTHOR]

Reduction of the neutral carbene tetrachlorosilane adduct (cAAC)SiCl4 (cAAC=cyclic alkyl(amino) carbene :C(CMe2)2(CH2)N(2,6-iPr2C6H3) with potassium graphite produces stable (cAAC)3Si3, a carbene-stabilized triatomic silicon(0) molecule. The Si−Si bond lengths in (cAAC)3Si3 are 2.399(8), 2.369(8) and 2.398(8) Å, which are in the range of Si−Si single bonds. Each trigonal pyramidal silicon atom of the triangular molecule (cAAC)3Si3 possesses a lone pair of electrons. Its bonding, stability, and electron density distributions were studied by quantum chemical calculations. [ABSTRACT FROM AUTHOR]

Reduction of the neutral carbene tetrachlorosilane adduct (cAAC)SiCl4 (cAAC=cyclic alkyl(amino) carbene :C(CMe2)2(CH2)N(2,6-iPr2C6H3) with potassium graphite produces stable (cAAC)3Si3, a carbene-stabilized triatomic silicon(0) molecule. The Si−Si bond lengths in (cAAC)3Si3 are 2.399(8), 2.369(8) and 2.398(8) Å, which are in the range of Si−Si single bonds. Each trigonal pyramidal silicon atom of the triangular molecule (cAAC)3Si3 possesses a lone pair of electrons. Its bonding, stability, and electron density distributions were studied by quantum chemical calculations. [ABSTRACT FROM AUTHOR]

Radicals are an important class of species which act as intermediates in numerous chemical and biological processes. Most of the radicals have short lifetimes. However, radicals with longer lifetimes can be isolated and stored in a pure form. They are called stable radicals. Over the last five decades, the syntheses of several stable radicals have been reported. Recently, highly unstable radicals have been successfully stabilized via strong σ-donation of singlet carbenes. Cyclic aklyl(amino) carbene (cAAC) is regarded as a stronger σ-donor and a better π-acceptor when compared with that of an N-heterocyclic carbene (NHC). In this article we review preferentially the results of our group to generate stable radical centers on the carbene carbon atoms by employing the so far hidden and unique ability of the cAACs. We focus on the development of new synthetic routes to stable and isolable radicals containing silicon atoms. All the compounds have been well characterized by single crystal X-ray analysis; the mono-radicals have been distinguished by EPR spectroscpy and the ground state of the diradicals has been studied by magnetic susceptibility measurements and theoretical calculations. Many of these compounds are studied by cyclic voltammetry and are often converted to their corresponding radical cations or radical anions via electron abstraction or addition processes. Some of them are stable, having long lifetimes and hence are isolated and characterized thoroughly. Not much information has been obtained on the short lived persistent radical species. Herein, we discuss some of the examples of such a type of species and focus on what kind of chemical reactions are initiated by these short-lived radical species in solution. We also briefly mention the syntheses and charaterization of the so far reported stable silicon centered radicals. [ABSTRACT FROM AUTHOR]

An ecofriendly approach for the synthesis of highly substituted tetrahydropyridines by an 'on-water' multicomponent reaction has been demonstrated. The use of water as the reaction medium is essential under the catalytic influence of a surfactant. The use of a variety of anionic, cationic, and non-ionic surfactants in water was examined and the reaction was successfully catalyzed by anionic surfactants sodium dioctyl sulfosuccinate (SDOSS) and sodium dodecyl sulfate (SDS), with the former being superior. The use of an organic solvent together with a catalytic amount of sodium dioctyl sulfosuccinate to form homogeneous conditions afforded inferior yields and highlighted the specific role of water through the creation of microreactors at the water surfactant interface. A mechanistic insight for the five-component reaction leading to the formation of tetrahydropyridines is provided invoking a tandem inter- and intramolecular Mannich reaction pathway. [ABSTRACT FROM AUTHOR]

A novel synthetic strategy for phenazine formation is reported following self-coupling of anilines by Pd–Ag binary nanocluster-catalysed synchronous double C–N bond formation via non-radical mode of ortho-aryl C–H activation. [ABSTRACT FROM AUTHOR]

Herein, we present a general method for a reliable estimation of the extent of π-backdonation (CcAAC←-E) of the bonded element (E) to the carbene carbon atom and CcAAC→-E σ-donation. The CcAAC←-E π-backdonation has a significant effect on the electronic environments of the 15N nucleus. The estimation of the π-backdonation has been achieved by recording the chemical shift values of the 15N nuclei via two-dimensional heteronuclear multiple-bond correlation spectroscopy. The chemical shift values of the 15N nuclei of several cAAC-containing compounds and/or complexes were recorded. The 15N nuclear magnetic resonance chemical shift values are in the range from -130 to -315 ppm. When the cAAC forms a coordinate σ-bond (CcAAC→-E), the chemical shift values of the 15N nuclei are around -160 ppm. In case the cAAC is bound to a cationic species, the numerical chemical shift value of the 15N nucleus is downfield-shifted (-130 to -148 ppm). The numerical values of the 15N nuclei fall in the range from -170 to -200 ppm when σ-donation (CcAAC→-E) of cAAC is stronger than CcAAC←-E π-backacceptance. The π-backacceptance of cAAC is stronger than σ-donation, when the chemical shift values of the 15N nuclei are observed below -220 ppm. Electron density and charge transfer between CcAAC and E are quantified using natural bonding orbital analysis and charge decomposition analysis techniques. The experimental results have been correlated with the theoretical calculations. They are in good agreement. [ABSTRACT FROM AUTHOR]

This study was conducted to isolate endophytic bacteria possessing anti-infective property from Kalmegh (Andrographis paniculata Nees.), a well-known medicinal plant. A total of 23 strains were isolated from this plant among which the strain KL1, isolated from surface-sterilized leaf of this medicinal herb, showed broad-spectrum antagonism against an array of Gram-positive and -negative bacterial pathogens. Ethyl acetate extract of KL1-fermented media yielded a greenish amorphous substance retaining anti-infective property. Solvent-extracted crude material was separated by thin-layer chromatography, and the active ingredient was located by autobiogram analysis. The purified anti-infective compound was found as anthracene derivative as analyzed by ultraviolet and Fourier transform infrared spectroscopy. The strain was identified as Bacillus thuringiensis KL1 from cultural, physiochemical, and molecular aspects. The above results indicate the pharmaceutical potential of the candidate isolate. [ABSTRACT FROM AUTHOR]

Thiophosgene (CSCl2), a chemical reagent used in numerous organic syntheses, exists in the monomeric form while its heavier silicon analogue [siliconthiodichloride (SiSCl2)] has been isolated so far as a dimer at room temperature and as a tetramer at 180 °C. Herein, we report on the first synthesis, isolation, and characterization of cyclic alkyl(amino) carbene (cAAC) stabilized siliconthiodichloride (cAAC)SiSCl2 (3) in the neutral monomeric form. 3 is synthesized via reaction of (cAACṖ)2Si2Cl4 (1) or (cAAC)2Si2Cl2 (2) with S8 in the temperature range of −78 to 20 °C. An NHC [NHC = N-heterocyclic carbene] analogue of 3 is not isolated when (NHC)SiCl2 is reacted with S8. The bright yellow colored compound 3 is soluble in polar organic solvents. It is stable at room temperature for a month under an inert atmosphere. 3 decomposes above 160 °C. The monomeric molecular structure of 3 has been unambiguously confirmed by X-ray single crystal diffraction. 3 is also characterized by NMR, UV-vis, and IR spectroscopy. The bonding and electron density distributions of 3 have been further studied by theoretical calculations. [ABSTRACT FROM AUTHOR]

Copper and tin have been co-deposited from choline chloride ethylene glycol based deep eutectic solvent (DES) containing CuCl 2 .2H 2 O and SnCl 2 .2H 2 O. Initially, electrolyte formulation experiments were carried out containing different amounts of copper and tin at a brass cathode in a rotating cylinder Hull cell. It was found that metallic deposits containing copper and tin could be deposited from a DES containing 0.02 M CuCl 2 .2H 2 O and 0.1 M SnCl 2 .2H 2 O. Polarization scans were carried out to determine the reduction potentials for individual metals and alloys. Anodic stripping voltammetry showed that Sn co-deposits with Cu at -0.36 V, at a lower over-potential than the tin reduction potential. Smooth and bright deposits of thicknesses up to 10 μm were obtained at a potential of -0.36 V or by using a current density of −0.87 × 10 −3 A cm −2 . XRD analysis showed the formation of mainly Cu 3 Sn and some Cu 5 Sn 6 . Our results suggest that Sn is co-discharged with Cu at potentials which is noble compared to the reduction potential of the individual metal. [ABSTRACT FROM AUTHOR]

An elegant general synthesis route for the preparation of two coordinate palladium(0) and platinum(0) complexes was developed by reacting commercially available tetrakis(triphenylphosphine)palladium/platinum with π-accepting cyclic alkyl(amino) carbenes (cAACs). The complexes are characterized by NMR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. The palladium complexes exhibit sharp color changes (crystallochromism) from dark maroon to bright green if the C-Pd-C bond angle is sharpened by approximately 6°, which is chemically feasible by elimination of one lattice THF solvent molecule. The analogous dark orange-colored platinum complexes are more rigid and thus do not show this phenomenon. Additionally, [(cAAC)2Pd/Pt] complexes can be quasi-reversibly oxidized to their corresponding [(cAAC)2Pd/Pt]+ cations, as evidenced by cyclic voltammetry measurements. The bonding and stability are studied by theoretical calculations. [ABSTRACT FROM AUTHOR]

A cyclic alkyl(amino) carbene (cAAC) stabilized dimer [(cAAC)Si(P-Tip)]2 (2) (Tip = 2,4,6-triisopropylphenyl) is reported. 2 can be considered as a dimer of the heavier ketenimine (R2C═C═N-R) analogue. The dark-red rod-shaped crystals of 2 were synthesized by reduction of the precursor, cAAC-dichlorosilylene-stabilized phosphinidene (cAAC)SiCl2→P-Tip with sodium napthalenide. The crystals of 2 are storable at room temperature for several months and stable up to 215 °C under an inert atmosphere. X-ray single-crystal diffraction revealed that 2 contains a cyclic nonplanar four-membered SiPSiP ring. Magnetic susceptibility measurements confirmed the singlet spin ground state of 2. Cyclic voltammetry of 2 showed a quasi-reversible one-electron reduction indicating the formation of the corresponding radical anion 2•-, which was further characterized by EPR measurements in solution. The electronic structure and bonding of 2 and 2•- were studied by theoretical calculations. The experimentally obtained data are in good agreement with the calculated values. [ABSTRACT FROM AUTHOR]

Intermediate species dichlorosilylene was generated in situ from trichlorosilane and inserted into the P-Cl bond of diphenylchlorophosphine (Ph2P-Cl) to obtain Ph2P-SiCl3 (1). Monodechlorination of 1 by cyclic alkyl(amino) carbenes (cAACs)/KC8 in THF at low temperature led to the formation of stable radicals Ph2P-Si(cAAC⋅)Cl2 (2a,b). Compounds 2a,b were characterized by X-ray single crystal diffraction, mass spectrometry and studied by cyclic voltammetry and theoretical calculations. Radical properties of 2 are confirmed by EPR measurements that suggest the radical electron in 2 couples with 14N (I = 1), 35/37Cl (I = 3/2), and 31P (I = 1/2) nuclei leading to multiple hyperfine lines. Hyperfine coupling parameters computed from DFT calculations are in good agreement with those of experimental values. Electronic distributions obtained from the theoretical calculations suggest that the radical electron mostly resides on the carbene C of 2. [ABSTRACT FROM AUTHOR]

The unstable species dichlorosilylene was previously stabilized by carbene. The lone pair of electrons on the silicon atom of (carbene)SiCl2 can form a coordinate bond with metal--carbonyls. Herein we report that (carbene)SiCl2 can stabilize a phosphinidene (Ar--P, a carbone analogue) with the general formula carbene→SiCl2→P--Ar (carbene = cyclic alkyl(amino) carbene (cAAC; 2) and N-heterocyclic carbene (NHC; 3)). Compounds 2 and 3 are stable, isolable, and storable at 0 °C (2) to room temperature (3) under an inert atmosphere. The crystals of 2 and 3 are dark blue and red, respectively. The intense blue color of 2 arises due to the strong intramolecular charge transfer (ICT) transition from πSi=P→π*cAAC. The electronic structure and bonding of 2, 3 were studied by theoretical calculations. The HOMO of the molecule is located on the πSi=P bond, while the LUMO is located at the carbene moiety (cAAC or NHC). The dramatic change in color of these compounds from red (3, NHC) to blue (2, cAAC) is ascribed to the difference in energy of the LUMO within the carbenes (cAAC/NHC) due to a lower lying LUMO of cAAC. [ABSTRACT FROM AUTHOR]

Mounting clinical and experimental evidence implicates various cytokines in stress-related affective brain disorders. Here, we analyze behavioral phenotypes in C57BL/6J male mice following the chronic social defeat stress paradigm, and examine their serum cytokines and corticosterone levels. Loser mice experiencing 20 days of daily 15-min social confrontations demonstrate elevated levels of pro-inflammatory cytokines interleukin IL-7 and vascular endothelial growth factor (VEGF), as well as a trend to increase IL-6 and IL-15. We also found higher levels of an anti-inflammatory cytokine IL-10 in the winner mice, with unaltered serum IL-2, IL-4, IL-1a, MCP-1 and corticosterone levels between the groups. Overall, our results suggest that animal affective-like states correlate with specific cytokine profiles, including some cytokines (e.g., VEGF, IL-7 or IL-15) whose role in neuropsychiatric disorders is only beginning to emerge. This study emphasizes the importance of integrative analyses of neural and immune phenotypes in stress and stress-related neurobehavioral disorders. These findings may also help foster the search for new therapeutic and preventative strategies that target selected cytokines and their signaling pathways. [ABSTRACT FROM AUTHOR]