Current-Density Calculations on Zn-Porphyrin40 Nanorings.

Two porphyrinoid nanorings have been studied computationally. They were built by linking 40 Zn-porphyrin units with butadiyne bridges. The molecular structures belonging to the D40h point group were fully optimized with the Turbomole program at the density functional theory (DFT) level using the B3LYP functional and the def2-SVP basis sets. The aromatic character was studied at the DFT level by calculating the magnetically induced current-density (MICD) susceptibility using the GIMIC program. The neutral molecules are globally non-aromatic with aromatic Zn-porphyrin units. Charged nanorings could not be studied because almost degenerate frontier orbitals led to vanishing optical gaps for the cations. Since DFT calculations of the MICD are computationally expensive, we also calculated the MICD using three pseudo-π models. Appropriate pseudo-π models were constructed by removing the outer hydrogen atoms and replacing all carbon and nitrogen atoms with hydrogen atoms. The central Zn atom was either replaced with a beryllium atom or with two inner hydrogen atoms. Calculations with the computationally inexpensive pseudo-π models yielded qualitatively the same magnetic response as obtained in the all-electron calculations.

Risk Loci For Chronic Obstructive Disease Reside On Chromosome 14: A Case-Control Study On The Pakistani Population.

BACKGROUND: Chronic Obstructive Pulmonary Disease (COPD), the third leading cause of death worldwide, is characterized by airflow limitation that can be due to abnormalities in the airway and/or alveoli. Genetic diagnosis at an early stage can be a key factor in the provision of accurate and timely treatment. Single Nucleotide polymorphisms (SNPs) are an important tool to study genetic association/ predisposition of the disease and have great potential to be diagnostic markers for early diagnosis of disease. METHODS: This case-control COPD association study was designed for the five SNPs residing on potential candidate genes (SERPINA1, SERPINA3, RIN3), to check whether these genes are involved in the genetic predisposition for COPD in the Pakistani population or not. The SNAPshot method was used to find out the risk alleles and haplotypes using ABI Genetic analyzer 3130. GeneMapper, Haploview and PLINK 1.9 software were used for analyzing the genotypes and haplotypes taking smoking exposure and gender as covariates. RESULTS: Two of the SNPs, rs4934 and rs17473 were found to be independently and significantly associated with COPD in our studied population whereas haplotype H1 for two SNPs, rs754388 and rs17473 (that are in high linkage disequilibrium), was found to be a significant risk factor for developing COPD symptoms. CONCLUSIONS: SNP variants of SERPINA1 and SERPINA3 are significantly and independently associated with COPD in the local population of Pakistan.

Magnetically Induced Current Densities in π-Conjugated Porphyrin Nanoballs.

Magnetically induced current densities (MICDs) of Zn-porphyrinoid nanostructures have been studied at the density functional theory level using the B3LYP functional and the def2-SVP basis set. Six of the studied Zn-porphyrinoid nanostructures consist of two crossing porphyrinoid belts, and one is a porphyrinoid nanoball belonging to the octahedral (O) point group. The Zn-porphyrin units are connected to each other via butadiyne linkers as in a recently synthesized porphyrinoid structure resembling two crossed belts. The MICDs are calculated using the gauge-including magnetically induced current method. Current-density pathways and their strengths were determined by numerically integrating the MICD passing through selected planes that cross chemical bonds or molecular rings. The current-density calculations show that the studied neutral molecules are globally nonaromatic but locally aromatic sustaining ring currents only in the individual porphyrin rings or around two neighboring porphyrins. The ring-current strengths of the individual porphyrin rings are 20% weaker than in Zn-porphyrin, whereas oxidation leads to globally aromatic cations sustaining ring currents that are somewhat stronger than for Zn-porphyrin.

Magnetically Induced Current Densities in Zinc Porphyrin Nanoshells.

The molecular structures of porphyrinoid cages were obtained by constructing small polyhedral graphs whose vertices have degree-4. The initial structures were then fully optimized at the density functional theory (DFT) level using the generalized gradient approximation. Some of polyhedral vertices were replaced with Zn-porphyrin units and their edges were replaced with ethyne or butadiyne bridges or connected by fusing two neighboring Zn-porphyrin units. Molecule 1 is an ethyne-bridge porphyrinoid nanotube, whose ends are sealed with a Zn-porphyrin. Molecule 2 is the corresponding open porphyrinoid nanotube. Molecule 3 is a clam-like porphyrinoid cage, whose shells consist of fused Zn-porphyrins, and the two halves are connected via butadiyne bridges. Molecule 4 is a cross-belt of fused Zn-porphyrins, and molecule 5 is a cross-belt of Zn-porphyrins connected with butadiyne bridges. The magnetically induced current density of the optimized porphyrinoid cages was calculated for determining the aromatic character, the degree of aromaticity and the current-density pathways. The current-density calculations were performed at the DFT level with the gauge─including magnetically induced currents (GIMIC) method using the B3LYP hybrid functional and def2-SVP basis sets. Calculations of the current densities show that molecule 2 sustains a paratropic ring current around the nanotube, whereas sealing the ends as in molecule 1 leads to an almost nonaromatic nanotube. Fusing porphyrinoids as in molecules 3 and 4 results in complicated current-density pathways that differ from the ones usually appearing in porphyrinoids. The aromatic character of molecules 4 and 5 changes upon oxidation. The neutral molecule 4 is antiaromatic, whereas the dication is nonaromatic. Molecule 5 is nonaromatic, and its dication is aromatic.

Design of a computationally efficient observer-based distributed fault detection and isolation scheme in second-order networked control systems.

This paper presents a novel directional observer-based fault detection and isolation scheme for second-order networked control systems (NCS). The directional unknown input observer (UIO) tool is exploited to study the problem of distributed fault detection and isolation (FDI). Two design schemes with global and partial/local network models are proposed to solve the distributed FDI problem. Thresholds are computed for the application of the proposed schemes in a noisy environment. In addition, the salient features of the proposed schemes are that both fault detection and fault isolation are achieved in a single step using a single observer. The schemes are applied to power system models to validate their results. A detailed comparison with existing FDI schemes is also provided, which clearly shows the effectiveness of the proposed scheme in terms of computational requirements.

Genetic polymorphism of the prostasin gene in hypertensive pregnant Pakistani females.

OBJECTIVE: The study was performed to investigate the association of hypertension in pregnancy with prostasin gene polymorphism in Pakistani females. METHODS: This case-control study was performed at University of Karachi, Pakistan from April 2018 to May 2019. A total of 160 females, including 90 hypertensives and 70 healthy pregnant females, were recruited by purposive sampling after obtaining informed written consent. Genotyping was performed by polymerase chain reaction (PCR) and restriction fragment length polymorphism (RFLP). RESULTS: The frequencies of the TC and CC genotypes were higher in hypertensive pregnant females compared to healthy controls. A significant difference was evident for CC (P=0.012) genotype; however, no significant difference was observed for TC (P=0.49) and TT genotypes (P=0.06) between control and hypertensive groups. The adjusted odds ratio for CC genotype was 6.2 (P=0.025) and 1.48 (P=0.44) for TC genotype compared to the TT genotype. There was a significantly higher prevalence of the C allele of the prostasin gene at rs12597511 in the hypertensive group, suggesting that this allele is a risk factor for hypertension and cardiovascular diseases. CONCLUSION: C allele at rs12597511 of prostasin gene demonstrate as a risk factor for having hypertension in pregnancy.

Sustainable Development of Innovative Green Construction Materials: A Study for Economical Eco-Friendly Recycled Aggregate Based Geopolymer Concrete.

Green revolution and high carbon footprint concepts have attracted the development of a green and sustainable environment. This work endeavors to investigate the behavior of recycled aggregate geopolymer concrete (RAGC) developed with four different types of effluents to develop sustainability in the construction industry and to produce an eco-friendly environment. Each of the types of effluents was used by completely replacing the freshwater in RAGC to examine its influence on compressive strength (CS), chloride ion migration (CIM), split tensile strength (STS), and resistance to the sulfuric acid attack of RAGC at various testing ages. The test outputs portray that the effluent obtained from the textile mill performed well for the CS (25% higher than the control mix) and STS (17% higher than the control mix) of RAGC. Similarly, the highest mass loss of RAGC due to the acid attack (41% higher than control mix) and the highest CIM (29% higher than control mix) were represented by the RAGC mix made with effluent obtained from fertilizer mill. The statistical analysis indicated no significant influence of using textile mill effluent (TE), fertilizer mill effluent (FE), and sugar mill effluent (SE) on the STS, CIM, and mass loss due to acid attack while it presented a significant influence on the CS of various mixes. Therefore, this investigation solidly substantiates the acceptability of studied types of effluents for the fabrication of eco-friendly green materials.

Association between preeclampsia and prostasin polymorphism in Pakistani females.

OBJECTIVES: To investigate the relationship between a prostasin gene variations and the development of preeclampsia in a Pakistani female population. Methods: This was a case-control study carried out at University of Karachi, Karachi, Pakistan between May 2018 and 2019. A single nucleotide polymorphism (SNP) at rs12597511 locus was examined with polymerase chain reaction (PCR) and restriction fragment length polymorphism (RFLP) analyses in 76 preeclamptic and 74 normotensive expecting mothers. RESULTS: We observed significantly increased risk of preeclampsia associated with the CC genotype of rs12597511 polymorphism as compared to TT (p less than 0.001, OR=8.08, 95% CI: 1.28-31.19) and TT/TC (p less than 0.001, OR=14.66 and 95% CI: 3.31-65.07) genotypes carriers. Calculation of the allelic distribution revealed a higher frequency of the T allele (82%) among controls; however, the C allele was more prevalent in the preeclamptic group (36%) significantly. CONCLUSION: The significantly higher C allele frequency in the prostasin gene at the rs12597511 locus in the preeclamptic group indicates that the distribution of the C allele of the prostasin gene is a potential risk factor contributing to the development of preeclampsia.

Distributed fault detection and isolation in second order networked systems in a cyber-physical environment.

Modern industrial processes and cyber-physical systems (CPS) are prone to anomalies both due to cyber and physical perturbations. Cyber disturbances or attacks being more hazardous may give birth to a series of multiple coordinated faults. In order to detect and isolate such faults, this paper proposes a novel distributed fault detection and isolation scheme for second-order networked systems. The system is assumed to be working in a cyber-physical environment where it is likely to face multiple simultaneous faults. Each node has access to measurements of states of its neighboring nodes. A distributed fault detection and isolation filter (DFDIF) is designed such that fault detection and fault isolation can be obtained in a single step. Using the proposed filter, each node can detect and isolate multiple simultaneous faults in its neighboring nodes. The detection and isolation of faults with a single filter at each node reduces the overall computational burden of distributed fault detection and isolation (DFDI) scheme. The proposed framework is tested for power network and robotic formations. Finally, a comparison with existing techniques is provided to prove the effectiveness of the proposed method.

Arthroscopic Evaluation of Impingement and Osteochondral Lesions in Chronic Lateral Ankle Instability.

BACKGROUND: Anterolateral impingement associated with intra-articular synovitis, scarring, and fibrosis is a less recognized feature in patients with chronic lateral ankle instability. The aim of our study was to ascertain the incidence of intra-articular synovitis, osteochondral lesions (OCLs), impingement lesions (both intra- and extra-articular), and other associated pathologies in patients undergoing modified Broström-Gould ankle ligament reconstruction. METHODS: We performed a retrospective review of all patients who underwent arthroscopically assisted modified Broström-Gould ankle ligament reconstruction for symptomatic recurrent ankle instability. Patients who had previous ankle surgery or inflammatory arthropathy were excluded. Ankle arthroscopy was performed prior to reconstruction in all patients. Data were obtained from clinical and radiological records including magnetic resonance imaging scans. Arthroscopic findings were recorded in detail intraoperatively. A total of 100 patients (53 females and 47 males) with an average age of 37 years (range, 15-65 years) were reviewed over a 10-year period. RESULTS: Sixty-three patients (63%) had intra-articular synovitis mostly in the anterior and/or anterolateral compartment, which required arthroscopic debridement. Seventeen patients (17%) were found to have OCLs, and 12 (12%) patients had anterior bony impingement lesions. CONCLUSION: This study found a high incidence of anterior/anterolateral synovitis in patients with chronic lateral ankle instability. However, there was a relatively low incidence of anterior bony impingement lesions or OCLs in our series. LEVEL OF EVIDENCE: Level IV, retrospective case series.