Plasmon-Enhanced Raman and Resonance Raman Scattering and Single Molecule Detection in Langmuir-Blodgett Monolayers

The present work explores vibrational Raman spectroscopy. Vibrational Raman and vibrational infrared are the most commonly used spectroscopies for detection and identification of molecules with their vibrational fingerprint. Under certain conditions, molecules display unique florescence and Raman scattering behavior when they are close to metal nanostructures sustaining localized surface plasmon resonances (LSPR), giving rise to surface-enhanced Raman scattering (SERS) and surface-enhanced resonance Raman scattering (SERRS). The utilization of LSPR in metallic nanoparticles, in particular silver and gold nanostructures, is a remarkable means of improving the efficiency of Raman scattering enhancing optical signals in SERS and SERRS. Correspondingly, the fabrication and characterization of silver and gold island films are first presented, and SERS signals enhancement of an organic dye on these metal nanostructured films are demonstrated. The excitations are characterized by UV-Vis absorption spectroscopy, while the morphology is revealed by atomic force microscopy (AFM). To control the surface coverage of the metal nanostructures, the Langmuir-Blodgett (LB) technique is used to coat the SERS substrate with monomolecular layers of several target systems, such as dyes and phospholipids. The most important results in this work are in the field of single molecule detection (SMD) using two spectroscopic approaches: LB-SERRS and LB-SERS. LB-SERRS improves the scattering efficiency from the electronic resonances (resonance Raman) of dye using silver island film with a plasmon absorption overlapping the molecular absorption. Several experiments are designed to the statistical average of LB-SERRS spectra, and the statistical breakdown observed in spectral characteristics when SMD is approached. The development of other SERS-substrates was attempted to control plasmonic using LSPR. A convenient method was pursued using a self-assembly of silver colloidal nanoparticles on a silanized glass surface. The SERS spectral evidence is presented to validate the substrate development. Surface-enhanced florescence (SEF) was also used for single molecule studies. Shell-isolated nanoparticles (SHINs) are used to produce SEF that named SHINEF. Using mixed LB monolayers of perylene tetracarboxylic (PTCD) derivatives, we report single molecule fluorescence and single molecule SERRS. In addition, overtones and combinations of fundamental vibrational modes are seen with atypical relative intensity in the LB-SERRS spectra of PTCDs

Use Case of Counterfactual Examples: Data Augmentation

Counterfactual explanations are gaining popularity as a way of explaining machine learning models. Counterfactual examples are generally created to interpret the decision of a model. In this case, if a model makes a certain decision for an instance, the counterfactual examples of that instance reverse the decision of the model. The counterfactual examples can be created by craftily changing particular feature values of the instance. In this work, we explore other potential application areas of utilizing counterfactual examples other than model explanation. We are particularly interested in exploring whether counterfactual examples can be a good candidate for data augmentation. At the same time, we look for ways of validating the generated counterfactual examples

Aiming to Minimize Alcohol-Impaired Road Fatalities: Utilizing Fairness-Aware and Domain Knowledge-Infused Artificial Intelligence

Approximately 30% of all traffic fatalities in the United States are attributed to alcohol-impaired driving. This means that, despite stringent laws against this offense in every state, the frequency of drunk driving accidents is alarming, resulting in approximately one person being killed every 45 minutes. The process of charging individuals with Driving Under the Influence (DUI) is intricate and can sometimes be subjective, involving multiple stages such as observing the vehicle in motion, interacting with the driver, and conducting Standardized Field Sobriety Tests (SFSTs). Biases have been observed through racial profiling, leading to some groups and geographical areas facing fewer DUI tests, resulting in many actual DUI incidents going undetected, ultimately leading to a higher number of fatalities. To tackle this issue, our research introduces an Artificial Intelligence-based predictor that is both fairness-aware and incorporates domain knowledge to analyze DUI-related fatalities in different geographic locations. Through this model, we gain intriguing insights into the interplay between various demographic groups, including age, race, and income. By utilizing the provided information to allocate policing resources in a more equitable and efficient manner, there is potential to reduce DUI-related fatalities and have a significant impact on road safety.Comment: IEEE Big Data 202

Smart Fraud Detection in Smart Metering System of AMI Networks

Advanced metering infrastructure (AMI) is a critical part of modern smart grids. It performs the delivery of sensitive power information such as smart metering data of power consumption. While smart meter data helps to improve the overall performance of the grid in terms of efficient energy management, it has also made the AMI an attractive target of cyberattackers with a goal of stealing energy. This is performed through the physical or cyber tampering of the meters, as well as by manipulating the network infrastructure to alter collected data. Proper technology is required for the identification of energy fraud. We propose a Machine Learning based technique to detect fraudulent data from smart meters based on energy consumption patterns of the consumers by utilizing both supervised and unsupervised techniques. We analyze the performance of our proposed technique and show the correctness of the models in identifying the suspicious smart meter data

PERFORMANCE OF SOME MAINLAND TREES AND PALM SPECIES PLANTED IN THE COASTAL ISLANDS OF BANGLADESH

Abstract Considering the sustainability of coastal forests, a trial with 13 mainland tree species was conducted at Rangabali island of Patuakhali district and Char Kukri-Mukri island of Bhola district to observe the site-suitability and growth performance of the species. Another experiment of 4 palm species was conducted in a foreshore area at Char KukriMukri island. On the basis of survival, height and diameter growth, Samanea saman (Jacq.) Merr

The assessment of musculoskeletal disorders, quality of life, and comorbidities in older people in Bangladesh

Musculoskeletal disorders are debilitating conditions that significantly impact the state of health, especially in older people. The study, which employed a cross-sectional design and practical sampling, included 206 participants among them 124 (62.2%) were men and 82 (39.8%) were women, from all over Bangladesh with musculoskeletal issues of varying severity and impact. The mean age of the participants was 64.9 (SD 4.3). The study was carried out between January and June of 2022. The majority of participants experienced musculoskeletal pain. Back pain was the most commonly complained of symptom among the participants (74.9%). It was also common to have limited mobility as a result of arthritic change, which eventually affected daily activities like taking care of oneself. To improve the health of the older adult population, more studies must be conducted to identify the many factors that contribute to musculoskeletal issues. The development of effective prevention and rehabilitation programs must then be based on this knowledge

A nickel(II)-sulfur-based radical-ligand complex as a functional model of hydrogenase

A nickel(II) dithiolene complex [Ni<SUP>II</SUP>(L<SUP>2−</SUP>)(L<SUP>−</SUP>.)][PPh<SUB>4</SUB>] (1; see figure; L=1,2-dicarbomethoxyethylene dithiolate) electrocatalyzes hydrogen evolution at the lowest achievable reduction potential (−0.69 V) in CH3CN and also in aqueous medium (−0.71 V) to date. Compound 1 shows strikingly similar EPR and reduction potential values to those observed with native Ni-containing hydrogenases

Electronic structure of monodithiolated iron&#8212;oxotungsten heterometallic complexes: integer-spin Fe&#8212;W assembly

Fe&#8212;W heterometallic complexes, in which an FeX2 (X=Cl, SPh) moiety is attached to monodithiolene oxotungsten through a sulfide bridge, that is, [Ph4P]2[Cl2Fe(S)2WOS2] (1), [Ph4P]2[Cl2Fe(S)2WOS2(DMED)] (2, DMED=dimethylethylenedicarboxylate), [Ph4P]2[Cl2Fe(S)2WO(tdt)] (3, tdt=toluenedithiolate), [Ph4P]2[(SPh)2Fe(S)2WO(tdt)] (4), and [Ph4P]2[Cl2Fe(S)2WO(edt)] (5, edt=ethanedithiolate), are reported. Mössbauer and EPR spectroscopy, magnetism, electrochemistry, and electronic structural analysis based on DFT and TD-DFT calculations show the transfer of electron from the iron center to the tungsten center, thus resulting in a ferromagnetically coupled FeIIIWV unit, along with antiferromagnetic intermolecular interactions, from the starting FeII and WVI compounds. A net spin of a S=3 ground state, which arises from ferromagnetically coupled FeIII and WV atoms, displays a rare X-band EPR in normal mode at g≈7 in the solid state

Mono(maleonitriledithiolene)molybdenum(IV) and bis(μ-sulfido)-bridged dimolybdenum(V) complexes with Mo=S moiety

Mono(maleonitriledithiolene)sulfidomolybdenum(IV) complex, [MoS(S4)(mnt)]2− (2; mnt=maleonitriledithiolene) was synthesized by the substitution reaction of a tetrasulfido ligand of the known [MoS(S4)2]2− (1) upon reaction with one or even excess equivalent of Na2(mnt) in aqueous MeCN solution in air. Surprisingly, 2 undergoes dimerization on treatment with alkyl halide such as MeI and PhCH2Br to form bis(μ-sulfido)dimolybdenum(V) species, [{MoS(mnt)}2(μ-S)2]2− (3). These complexes have been characterized by IR, UV/VIS spectroscopy, cyclic voltammetry, elemental analysis, and by X-ray crystal-structure analysis. Differences in the relative stability and electrochemical behavior of 1, 2, and 3 have been correlated with theoretical calculations at DFT level

Replica of a fishy enzyme: structure–function analogue of trimethylamine-N-oxide reductase

Three new complexes, [MoIVO(mnt)(SS)]2- (SS = dimethylethylenedicarboxylate (DMED), toluenedithiolate (tdt), benzenedithiolate (bdt); mnt = maleonitriledithiolate), each possessing two different dithiolene ligands, are synthesized as model of trimethylamine-N-oxide reductase. The asymmetric dithiolene ligands present in these complexes simulate the two different (P and Q) pterin coordinations in the family of DMSO reductase. These complexes reduce trimethylamine-N-oxide ((CH3)3N+–O– or TMANO), the biological substrate of trimethylamine-N-oxide reductase, to trimethylamine ((CH3)3N), responsible for the fishy smell of dead aquatic animals. The reaction kinetics of trimethylamine-N-oxide reduction by these complexes follow the Michaelis–Menten saturation kinetics. These experimental findings have been rationalized by DFT, TD-DFT level of calculations