Six-membered ring systems: with O and/or S atoms

A large variety of publications have emerged in 2012 involving O- and S-6- membered ring systems. The increasing number of reviews and other communica- tions dedicated to natural and synthetic derivatives and their biological significance highlights the importance of these heterocycles. Reviews on natural products involve biosynthesis and isolation of enantiomeric derivatives h12AGE4802i, biosynthesis, isolation, synthesis, and biological studies on the pederin family h12NPR980i and xanthones obtained from fungi, lichens, and bacteria h12CR3717i and on the potential chemotherapeutic value of phyto- chemical products and plant extracts as antidiabetic h12NPR580i, antimicrobial, and resistance-modifying agents h12NPR1007i. A more specific review covers a structure–activity relationship of endoperoxides from marine origin and their antitry- panosomal activity h12OBC7197i. New synthetic routes to naturally occurring, biologically active pyran derivatives have been the object of several papers. Different approaches have been discussed for the total synthesis of tetrahydropyran-containing natural products (")-zampanolide h12CEJ16868, 12EJO4130, 12OL3408i, (")-aspergillides A and B h12H(85)587, 12H(85)1255, 12TA252i, (þ)-neopeltolide h12JOC2225, 12JOC9840, 12H(85) 1255i, or their macrolactone core h12OBC3689, 12OL2346i. The total synthesis of bistramide A h12CEJ7452i and (þ)-kalihinol A h12CC901i and the stereoselec- tive synthesis of a fragment of bryostatin h12S3077, 12TL6163i have also been sur- veyed. Other papers relate the total synthesis of naturally occurring carbocyclic and heterocyclic-fused pyran compounds, such as (")-dysiherbaine h12CC6295i, penos- tatin B h12OL244i, Greek tobacco lactonic products, and analogues h12TL4293i and on the structurally intriguing limonoids andhraxylocarpins A–E h12CEJ14342i. The stereocontrolled synthesis of fused tetrahydropyrans was used in the preparation of blepharocalyxin D h12AGE3901i. Polyphenolic heterocyclic compounds have also received great attention in 2012. The biological activities and the chemistry of prenylated caged xanthones h12PCB78i, the occurrence of sesquiterpene coumarins h12PR77i, and the medicinal properties of the xanthone mangiferin h12MRME412i have been reviewed. An overview on the asymmetric syntheses of flavanones and chromanones h12EJO449i, on the synthesis and reactivity of flavones h12T8523i and xanthones h12COC2818i, on the synthesis and biosynthesis of biocoumarins h12T2553i, and on the synthesis and applications of flavylium compounds h12CSR869i has been discussed. The most recent developments in the synthesis and applications of sultones, a very important class of sulfur compounds, were reported h12CR5339i. A review on xanthene-based fluorescent probes for sensing cations, anions, bio- logical species, and enzyme activity has described the spiro-ring-opening approach with a focus on the major mechanisms controlling their luminescence behavior h12CR1910i. The design and synthesis of other derivatives to be used as sensors of gold species h12CC11229i and other specific metal cations h12PC823i have also been described. Recent advances related to coumarin-derived fluorescent chemosen- sors for metal ions h12COC2690i and to monitoring in vitro analysis and cellular imaging of monoamine oxidase activity h12CC6833i have been discussed. The study of various organic chromophores allowed the synthesis of novel dica- tionic phloroglucinol-type bisflavylium pigments h12SL2053i, and the optical and spectroscopic properties of several synthetic 6-aryldibenzo[b,d]pyrylium salts were explored h12TL6433i. Discussion of specific reactions leading to O- and S-membered heterocyclic compounds covers intramolecular radical cyclization h12S2475i and asymmetric enamine and dienamine catalysis h12EJO865i, oxa-Michael h12CSR988i and dom- ino Knoevenagel–hetero-Diels–Alder (hDA) reactions h12T5693i, and the versatility in cycloadditions as well as nucleophilic reactions using o-quinones h12CSR1050i. The use of specific reagents relevant to this chapter includes molecular iodine h12CEJ5460, 12COS561i, samarium diiodide–water for selective reductive transfor- mations h12CC330i, o-quinone methides as versatile intermediates h12CEJ9160i, InCl3 as catalyst h12T8683i, and gold and platinum p-acid mediated insertion of alkynes into carbon–heteroatom s-bonds h12S3401i. The remainder of this chapter discusses the most studied transformations on O- and S-6-membered heterocycles

Articulation Defects in Cleft Palate Cases

The present study was conducted on 56 cases of cleft palate and/or lip attending the Rehabilitation Unit in Audiology and Speech Pethology, All India Institute of Medical Sciences, New Delhi. Cleft palate was found to be more prevalent in males than females. 75% of the cases were below the age of 14 years, Only a few parents could give relevant history. It was, therefore, difficult to establish and generalise the causative factors. 29% of the cleft palate cases had mild to moderate degree of hearing loss. About 42% of the cases had undergone palate surgery and 35% both the lip and palate surgery. Many cases reported late for surgical treatment. Velar sounds among all the consonants were found to be substituted most and fricatives were distorted. Distortion was the most common defective articulatory pattern in the cleft palate cases while omissions were least affected. There has been numerous investigations designed to describe the speech articulation on cleft palate. The studies vary in terms of subjects used and the methods of assessment. Yet there is a general agreement on this problem. Plosives, fricatives and consonants which require building up of maximum oral pressure are the most affected sounds in cleft palate speech

Platform-independent Robust Query Processing

To address the classical selectivity estimation problem in databases, a radically different approach called PlanBouquet was recently proposed in 3], wherein the estimation process is completely abandoned and replaced with a calibrated discovery mechanism. The beneficial outcome of this new construction is that, for the first time, provable guarantees are obtained on worst-case performance, thereby facilitating robust query processing. The PlanBouquet formulation suffers, however, from a systemic drawback - the performance bound is a function of not only the query, but also the optimizer's behavioral profile over the underlying database platform. As a result, there are adverse consequences: (i) the bound value becomes highly variable, depending on the specifics of the current operating environment, and (ii) it becomes infeasible to compute the value without substantial investments in preprocessing overheads. In this paper, we present SpillBound, a new query processing algorithm that retains the core strength of the PlanBouquet discovery process, but reduces the bound dependency to only the query. Specifically, SpillBound delivers a worst-case multiplicative bound of D-2 + 3D, where D is simply the number of error-prone predicates in the user query. Consequently, the bound value becomes independent of the optimizer and the database platform, and the guarantee can be issued just by inspecting the query, without incurring any additional computational effort. We go on to prove that SpillBound is within an O(D) factor of the best possible deterministic selectivity discovery algorithm in its class. Further, a detailed empirical evaluation over the standard TPC-H and TPC-DS benchmarks indicates that SpillBound provides markedly superior worst-case performance as compared to PlanBouquet in practice. Therefore, in an overall sense, SpillBound offers a substantive step forward in the quest for robust query processing

Impact of bandgap tuning on ZnS for degradation of environmental pollutants and disinfection

The materials showing multiple applications are appealing for their practical use and industrial production. To realize the suitable property for various applications, we have produced ZnS (sf-ZnS) and metal-doped ZnS nanoflakes (sf-m-ZnS; where m = Cu, Ni, Cd, Bi, or Mn) and correlated their activity with bandgap variation. We obtained all these materials via hexamethyldisilazane (HMDS)-assisted synthetic method without using any surfactants, polymers, or template molecules and characterized them thoroughly using various techniques. Photocatalytic, as well as antibacterial, activities of these materials showed their bifunctional utility. We have demonstrated the effect of doping and consequent extension of absorption band to the visible region and resultant improved photocatalytic activity under sunlight. Thus, the change in bandgap influenced their performance as photocatalysts. Among all materials produced, sf-Cd-ZnS provided superior results as a photocatalyst while degrading two organic pollutants—rhodamine B (RhB) and methylene blue (MB) in water. The antibacterial activity of sf-ZnS and sf-m-ZnS against Gram-positive bacteria, i.e., Staphylococcus aureus (S. aureus), was examined by the zone of inhibition method, wherein sf-Ni-ZnS showed maximum activity. The enhanced activity of these ZnS materials can be attributed to the free surface of nanoparticles without any capping by organic molecules, which provided an intimate interaction of inorganic semiconductor material with organic and biomolecules. Thus, we have demonstrated modification of properties both by bandgap tuning of materials and providing the opportunity for intimate interaction of materials with substrates. The photocatalytic activity and antibacterial action of metal-doped ZnS produced by our method exhibited their potential for environmental remediation, specifically water purification. © 2022, The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature

An Affordable Insole-Sensor-Based Trans-Femoral Prosthesis for Normal Gait

This paper proposes a novel and an affordable lower limb prosthesis to enable normal gait kinematics for trans-femoral amputees. The paper details the design of a passive prosthesis with magneto-rheological (MR) damping system and electronic control. A new control approach based on plantar insole feedback was employed here. Strategically placed sensors on the plantar insole provide required information about gait cycle to a finite state controller for suitable action. A proportional integral (PI) based current controller controls the required current for necessary damping during gait. The prosthesis was designed and developed locally in India keeping in view the cost, functionality, socio-economic, and aesthetic requirements. The prototype was experimentally tested on a trans-femoral amputee and the results are presented in this work. The implementation of the proposed design and control scheme in the prototype successfully realizes the notion that normal gait kinematics can be achieved at a low cost comparable to passive prostheses. The incurring cost and power expenditure of the proposed prosthesis are evaluated against passive and active prostheses, respectively. The commercial implications for the prosthesis were explored on the basis of recommendations of ISPO Consensus Conference on Appropriate Prosthetic Technology in Developing Countries. The key objective of this work is to enable lucid design for development of an affordable prosthesis in a low-resource setting