Indian Association for the Cultivation of Science

This Colloquium gives an overview of recent theoretical and experimental progress in the area of nonequilibrium dynamics of isolated quantum systems. There is particularly a focus on quantum quenches: the temporal evolution following a sudden or slow change of the coupling constants of the system Hamiltonian. Several aspects of the slow dynamics in driven systems are discussed and the universality of such dynamics in gapless systems with specific focus on dynamics near continuous quantum phase transitions is emphasized. Recent progress on understanding thermalization in closed systems through the eigenstate thermalization hypothesis is also reviewed and relaxation in integrable systems is discussed. Finally key experiments probing quantum dynamics in cold atom systems are overviewed and put into the context of our current theoretical understanding.

Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.

Access to hierarchically porous carbons from polymers and biopolymers<italic>via</italic>a non-templating route has emerged as a promising strategy for a range of energy applications.

The paper presents some general relations obtaining in relativistic cosmology. It appears from these that a simple change over to anisotropy without the introduction of spin does not solve any of the outstanding difficulties of isotropic cosmological models.

Fluorescent carbon nanoparticles (CNPs) 2−6 nm in size with a quantum yield of about ∼3% were synthesized via nitric acid oxidation of carbon soot, and this approach can be used for milligram-scale synthesis of these water-soluble particles. These CNPs are nanocrystalline with a predominantly graphitic structure and show green fluorescence under UV exposure. Nitric acid oxidation induces nitrogen and oxygen incorporation into soot particles, which afforded water solubility and a light-emitting property; the isolation of small particles from a mixture of different sized particles improved the fluorescence quantum yield. These CNPs show encouraging cell-imaging applications. They enter into cells without any further functionalization, and the fluorescence property of these particles can be used for fluorescence-based cell imaging applications.

Faradaic and non-faradaic energy storage mechanisms, impact of the nano-structuring of electrode materials and state-of-art applications in robotics,<italic>etc.</italic>of hybrid supercapacitors, and their coupling with batteries and solar cells are elucidated.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDielectric Relaxation and Solvation Dynamics of Water in Complex Chemical and Biological SystemsNilashis Nandi, Kankan Bhattacharyya, and Biman BagchiView Author Information Department of Chemistry, Faculty of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-01, Japan Department of Physical Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Calcutta, 700032, India Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, 560012, India Cite this: Chem. Rev. 2000, 100, 6, 2013–2046Publication Date (Web):May 12, 2000Publication History Received23 February 1999Revised11 April 2000Published online12 May 2000Published inissue 1 June 2000https://pubs.acs.org/doi/10.1021/cr980127vhttps://doi.org/10.1021/cr980127vresearch-articleACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views7064Altmetric-Citations821LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Insulators,Molecules,Solution chemistry,Solvation dynamics,Solvents Get e-Alerts

The last two decades have witnessed an upsurge of research activities in the area of supramolecular gelators, especially low molecular mass organic gelators (LMOGs), not only for academic interests but also for their potential applications in materials science. However, most of the gelators are serendipitously obtained; their rational design and synthesis is still a major challenge. Wide structural diversities of the molecules known to act as LMOGs and a dearth of molecular level understanding of gelation mechanisms make it difficult to pin-point a particular strategy to achieve rational design of gelators. Nevertheless, some efforts are being made to achieve this goal. Once a gelling agent is serendipitously obtained, new gelling agents with novel properties may be prepared by modifying the parent gelator molecule following a molecular engineering rationale; however, such approach is limited to the same class of gelling agent generated from the parent gelating scaffold. A crystal engineering approach wherein the single-crystal structure of a molecule is correlated with its gelling/nongelling behaviour (structure-property correlation) allows molecular level understandings of the self-assembly of the gelator and nongelator molecules and therefore, provides new insights into the design aspects of supramolecular gelling agents. This tutorial review aims at highlighting some of the developments covering both molecular and crystal engineering approaches in designing LMOGs.

Fluorescent nanoparticle-based imaging probes have advanced current labelling technology and are expected to generate new medical diagnostic tools based on their superior brightness and photostability compared with conventional molecular probes. Although significant progress has been made in fluorescent semiconductor nanocrystal-based biological labelling and imaging, the presence of heavy metals and the toxicity issues associated with heavy metals have severely limited the application potential of these nanocrystals. Here, we report a fluorescent carbon nanoparticle-based, alternative, nontoxic imaging probe that is suitable for biological staining and diagnostics. We have developed a chemical method to synthesise highly fluorescent carbon nanoparticles 1-10 nm in size; these particles exhibit size-dependent, tunable visible emission. These carbon nanoparticles have been transformed into various functionalised nanoprobes with hydrodynamic diameters of 5-15 nm and have been used as cell imaging probes.

Recent advances and the current status of challenging light-harvesting nanomaterials, such as semiconducting quantum dots (QDs), metal nanoparticles, semiconductor-metal heterostructures, π-conjugated semiconductor nanoparticles, organic-inorganic heterostructures, and porphyrin-based nanostructures, have been highlighted in this review. The significance of size-, shape-, and composition-dependent exciton decay dynamics and photoinduced energy transfer of QDs is addressed. A fundamental knowledge of these photophysical processes is crucial for the development of efficient light-harvesting systems, like photocatalytic and photovoltaic ones. Again, we have pointed out the impact of the metal-nanoparticle-based surface energy transfer process for developing light-harvesting systems. On the other hand, metal-semiconductor hybrid nanostructures are found to be very promising for photonic applications due to their exciton-plasmon interactions. Potential light-harvesting systems based on dye-doped π-conjugated semiconductor polymer nanoparticles and self-assembled structures of π-conjugated polymer are highlighted. We also discuss the significance of porphyrin-based nanostructures for potential light-harvesting systems. Finally, the future perspective of this research field is given.

When a closed quantum system is driven periodically with period T, it approaches a periodic state synchronized with the drive in which any local observable measured stroboscopically approaches a steady value. For integrable systems, the resulting behavior is captured by a periodic version of a generalized Gibbs ensemble. By contrast, here we show that for generic nonintegrable interacting systems, local observables become independent of the initial state entirely. Essentially, this happens because Floquet eigenstates of the driven system at quasienergy ω(α) consist of a mixture of the exponentially many eigenstates of the undriven Hamiltonian, which are thus drawn from the entire extensive undriven spectrum. This is a form of equilibration which depends only on the Hilbert space of the undriven system and not on any details of its Hamiltonian.

This review highlights the functionalization chemistry of graphene with polymers by both covalent and non-covalent approaches. Due to the strong cohesive interactions graphene platelets agglomerate, causing difficulty to attain its optimum properties. The covalent functionalization is illuminated both from ‘grafting to’ and ‘grafting from’ techniques discussing the merits and demerits of the processes. The controlled free radical polymerization techniques used for this purpose e.g. ATRP, SET–LRP and RAFT etc. are discussed along with the conventional free radical polymerization. We have also noted the various approaches used in non-covalent functionalization e.g. π–π, H-bonding and hydrophobic interactions. These functionalized graphenes show good and stable dispersion facilitating composite formation with commodity plastics enhancing it's mechanical, thermal and conductivity properties. The optoelectronic properties of these functionalized graphene are interesting to fabricate sensors, photovoltaics, supercapacitors etc. A short account of the properties of these modified graphenes is also embodied with an emphasis on different area where future developments are expected.

We have collated various supramolecular designs that utilize organic donor-acceptor CT complexation to generate noncovalently co-assembled structures including fibrillar gels, micelles, vesicles, nanotubes, foldamers, conformationally restricted macromolecules, and liquid crystalline phases. Possibly inspired by nature, chemists have extensively used hydrogen bonding as a tool for supramolecular assemblies of a diverse range of abiotic building blocks. As a structural motif, CT complexes can be compared to hydrogen-bonded complexes in its directional nature and complementarities. Additional advantages of CT interactions include wider solvent tolerance and easy spectroscopic probing. Nevertheless the major limitation is their low association constant. This article shows different strategies have evolved over the years to overcome this drawback by reinforcing the CT interactions with auxiliary noncovalent forces without hampering the alternate stacking mode. Emerging reports on promising CT complexes in organic electronics are intimately related to various supramolecular designs that one can postulate based on donor-acceptor CT interactions.

[reaction: see text] A task-specific ionic liquid, [bmIm]OH, has been introduced as a catalyst and as a reaction medium in Michael addition. Very interestingly, although the addition to alpha,beta-unsaturated ketones proceeds in the usual way, giving the monoaddition products, this ionic liquid always drives the reaction of open-chain 1,3-dicarbonyl compounds with alpha,beta-unsaturated esters and nitriles toward bis-addition to produce exclusively bis-adducts in one stroke.

ADVERTISEMENT RETURN TO ISSUEPREVNoteNEXTIndium(III) Chloride-Catalyzed One-Pot Synthesis of Dihydropyrimidinones by a Three-Component Coupling of 1,3-Dicarbonyl Compounds, Aldehydes, and Urea: An Improved Procedure for the Biginelli ReactionBrindaban C. Ranu, Alakananda Hajra, and Umasish JanaView Author Information Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Calcutta 700 032, India [email protected]Cite this: J. Org. Chem. 2000, 65, 19, 6270–6272Publication Date (Web):August 24, 2000Publication History Received9 May 2000Published online24 August 2000Published inissue 1 September 2000https://pubs.acs.org/doi/10.1021/jo000711fhttps://doi.org/10.1021/jo000711fbrief-reportACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views4197Altmetric-Citations417LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Aldehydes,Anions,Chemical reactions,Condensation,Urea Get e-Alerts

The effect of substrate-induced strain in polycrystalline ZnO thin films on different substrate, e.g., GaN epilayer, sapphire (0001), quartz glass, Si(111)∕SiO2, and glass deposited by sol-gel process, has been investigated by x-ray diffraction, scanning electron microscope, electrical resistivity, and photoluminescence measurements. A strong dependence of orientation, crystallite size, and electrical resistivity upon the substrate-induced strain along the c axis has been found. The results of structural and morphological studies indicate that relatively larger tensile strain exists in ZnO deposited on sapphire and glass, while a smaller compressive strain appears in film deposited on GaN and the strain is relaxed in larger crystallite size. The electrical resistivity of the films increases exponentially with increasing strain. The excitonic peak positions are found to shift slightly towards lower energy side with increasing strain. The analysis shows that GaN being a closely lattice-matched substrate produces ZnO films of better crystallinity with a lower resistivity.

Water molecules confined in a supramolecular assembly control reactivity and dynamics of biological systems in a unique way. In a confined system, water molecules display an ultraslow component of solvation which is slower than that in bulk water by 2-4 orders of magnitude. The ultraslow component arises mainly from the disruption of the hydrogen-bond network of water and the binding of water molecules to a macromolecule. The ultraslow component of solvation markedly retards polar reactions. Many examples of slow dynamics in complex systems, and their implications in biological and natural processes are discussed.

ConspectusThe electrocatalytic CO2 reduction reaction (CO2RR) to generate fixed forms of carbons that have commercial value is a lucrative avenue to ameliorate the growing concerns about the detrimental effect of CO2 emissions as well as to generate carbon-based feed chemicals, which are generally obtained from the petrochemical industry. The area of electrochemical CO2RR has seen substantial activity in the past decade, and several good catalysts have been reported. While the focus was initially on the rate and overpotential of electrocatalysis, it is gradually shifting toward the more chemically challenging issue of selectivity. CO2 can be partially reduced to produce several C1 products like CO, HCOOH, CH3OH, etc. before its complete 8e–/8H+ reduction to CH4. In addition to that, the low-valent electron-rich metal centers deployed to activate CO2, a Lewis acid, are prone to reduce protons, which are a substrate for CO2RR, leading to competing hydrogen evolution reaction (HER). Similarly, the low-valent metal is prone to oxidation by atmospheric O2 (i.e., it can catalyze the oxygen reduction reaction, ORR), necessitating strictly anaerobic conditions for CO2RR. Not only is the requirement of O2-free reaction conditions impractical, but it also leads to the release of partially reduced O2 species such as O2–, H2O2, etc., which are reactive and result in oxidative degradation of the catalyst.In this Account, mechanistic investigations of CO2RR by detecting and, often, chemically trapping and characterizing reaction intermediates are used to understand the factors that determine the selectivity in CO2RR. The spectroscopic data obtained from different intermediates have been identified in different CO2RR catalysts to develop an electronic structure selectivity relationship that is deemed to be important for deciding the selectivity of 2e–/2H+ CO2RR. The roles played by the spin state, hydrogen bonding, and heterogenization in determining the rate and selectivity of CO2RR (producing only CO, only HCOOH, or only CH4) are discussed using examples of both iron porphyrin and non-heme bioinspired artificial mimics. In addition, strategies are demonstrated where the competition between CO2RR and HER as well as CO2RR and ORR could be skewed overwhelmingly in favor of CO2RR in both cases.

The first measurements are reported for the frequency-dependent (ac) conductivity (real as well as imaginary parts) for various compositions of the bismuth-vanadate glassy semiconductors in the frequency range ${10}^{2}$--${10}^{5}$ Hz and in the temperature range 77--420 K. The behavior of the ac conductivity is broadly similar to what has been observed previously in many other types of amorphous semiconductors, namely, nearly linear frequency dependence and weak temperature dependence. The experimental results are analyzed with reference to various theoretical models based on quantum-mechanical tunneling and classical hopping over barriers. The analysis shows that the temperature dependence of the ac conductivity is consistent with the simple quantum-mechanical tunneling model at low temperatures; however, this model completely fails to predict the observed temperature dependence of the frequency exponent. The overlapping-large-polaron tunneling model can explain the temperature dependence of the frequency exponent at low temperatures. Fitting of this model to the low-temperature data yields a reasonable value of the wave-function decay constant. However, this model predicts the temperature dependence of the ac conductivity much higher than what actual data showed. The correlated barrier hopping model is consistent with the temperature dependence of both the ac conductivity and its frequency exponent. This model provides reasonable values of the maximum barrier heights but higher values of characteristic relaxation times.

Circular RNAs are new players in regulation of post transcriptional gene expression. Animal genomes express many circular RNAs from diverse genomic locations. A recent study has validated a fairly large number of circular RNAs in human, mouse, and nematode. Circular RNAs play a crucial role in fine tuning the level of miRNA mediated regulation of gene expression by sequestering the miRNAs. Their interaction with disease associated miRNAs indicates that circular RNAs are important for disease regulation. In this paper we studied the potential association of circular RNAs (circRNA) with human diseases in two different ways. Firstly, the interactions of circRNAs with disease associated miRNAs were identified, following which the likelihood of a circRNA being associated with a disease was calculated. For the miRNAs associated with individual diseases, we constructed a network of predicted interactions between the miRNAs and protein coding, long non-coding and circular RNA genes. We carried out gene ontology (GO) enrichment analysis on the set of protein coding genes in the miRNA- circRNA interactome of individual diseases to check the enrichment of genes associated with particular biological processes. Secondly, disease associated SNPs were mapped on circRNA loci, and Argonaute (Ago) interaction sites on circular RNAs were identified. We compiled a database of disease-circRNA association in Circ2Traits (http://gyanxet-beta.com/circdb/), the first comprehensive knowledgebase of potential association of circular RNAs with diseases in human.