545 research outputs found
NIR-VCD, vibrational circular dichroism in the near-infrared: Experiments, theory and calculations
The first well documented experiments of Near Infrared Vibrational Circular
Dichroism (NIR-VCD) were performed around 1975. We review the thirty year history
of NIR-VCD, encompassing both instrumental development and theoretical/computational
methods that allow interpretation of experimental spectra, harvesting useful structural
information therefrom. We hope to stimulate interest in this still scarcely explored
spectroscopy of chiral molecule
Harmonic and Anharmonic Features of IR and NIR Absorption and VCD Spectra of Chiral 4-X-[2.2]Paracyclophanes
The vibrational absorption spectra and vibrational circular dichroism (VCD) spectra of both enantiomers of
4-X-[2.2]paracyclophanes (X ) COOCD3, Cl, I) have been recorded for a few regions in the range of 900-
12000 cm-1. The analysis of the VCD spectra for the two IR regions, 900-1600 cm-1 and 2800-3200 cm-1,
is conducted by comparing with DFT calculations of the corresponding spectra; the latter region reveals
common motifs of vibrational modes for the three molecules for aliphatic CH stretching fundamentals, whereas
in the mid-IR region, one is able to identify specific signatures arising from the substituent groups X. In the
CH stretching region between 2900 and 2800 cm-1, we identify and interpret a group of three IR VCD bands
due to HCH bending overtone transitions in Fermi resonance with CH stretching fundamental transitions.
The analysis of the NIR region between 8000 and 9000 cm-1 for X ) COOCD3 reveals important features
of the aromatic CH stretching overtones that are of value since the aromatic CH stretching fundamentals are
almost silent. The intensifying of such overtones is attributed to electrical anharmonicity terms, which are
evaluated here by ab initio methods and compared with literature data
Lymphocyte Subsets and Inflammatory Cytokines of Monoclonal Gammopathy of Undetermined Significance and Multiple Myeloma
Almost all multiple myeloma (MM) cases have been demonstrated to be linked to earlier monoclonal gammopathy of undetermined significance (MGUS). Nevertheless, there are no identified characteristics in the diagnosis of MGUS that have been helpful in differentiating subjects whose cancer may progress to a malignant situation. Regarding malignancy, the role of lymphocyte subsets and cytokines at the beginning of neoplastic diseases is now incontestable. In this review, we have concentrated our attention on the equilibrium between the diverse lymphocyte subsets and the cytokine system and summarized the current state of knowledge, providing an overview of the condition of the entire system in MGUS and MM. In an age where the therapy of neoplastic monoclonal gammopathies largely relies on drugs capable of acting on the immune system (immunomodulants, immunological checkpoint inhibitors, CAR-T), detailed knowledge of the the differences existing in benign and neoplastic forms of gammopathy is the main foundation for the adequate and optimal use of new drugs
Generating human-computer micro-task workflows from domain ontologies
With the growing popularity of micro-task crowdsourcing platforms, a renewed interest in the resolution of complex tasks that require the coopera-tion of human and machine participants has emerged. This interest has led to workflow approaches that present new challenges at different dimensions of the human-machine computation process, namely in micro-task specification and human-computer interaction due to the unstructured nature of micro-tasks in terms of domain representation. In this sense, a semi-automatic generation envi-ronment for human-computer micro-task workflows from domain ontologies is proposed. The structure and semantics of the domain ontology provides a com-mon ground for understanding and enhances human-computer cooperation.This work is partially funded by FEDER Funds and by the
ERDF (European Regional Development Fund) through the COMPETE Programme
(operational programme for competitiveness) and by National Funds through the FCT
(Portuguese Foundation for Science and Technology) under the projects AAL4ALL (QREN13852) and FCOMP-01-0124-FEDER-028980 (PTDC/EEI-SII/1386/2012)
Chlorinative stress in age-related diseases: A literature review
Aging is an agglomerate of biological long-lasting processes that result being inevitable. Main actors in this scenario are both long-term inflammation and oxidative stress. It has been proved that oxidative stress induce alteration in proteins and this fact itself is critically important in the pathophysiological mechanisms leading to diseases typical of aging. Among reactive species, chlorine ones such as hypochlorous acid (HOCl) are cytotoxic oxidants produced by activated neutrophils during chronic inflammation processes. HOCl can also cause damages by reacting with biological molecules. HOCl is generated by myeloperoxidase (MPO) and augmented serum levels of MPO have been described in acute and chronic inflammatory conditions in cardiovascular patients and has been implicated in many inflammatory diseases such as atherosclerosis, neurodegenerative conditions, and some cancers. Due to these data, we decided to conduct an up-to-date review evaluating chlorinative stress effects on every age-related disease linked; potential anti-oxidant countermeasures were also assessed. Results obtained associated HOCl generation to the aging processes and confirmed its connection with diseases like neurodegenerative and cardiovascular pathologies, atherosclerosis and cancer; chlorination was mainly linked to diseases where molecular (protein) alteration constitute the major suspected cause: i.e. inflammation, tissue lesions, DNA damages, apoptosis and oxidative stress itself. According data collected, a healthy lifestyle together with some dietary suggestion and/or the administration of nutracetical antioxidant integrators could balance the effects of chlorinative stress and, in some cases, slow down or prevent the onset of age-releated diseases
ArCo: the Italian Cultural Heritage Knowledge Graph
ArCo is the Italian Cultural Heritage knowledge graph, consisting of a
network of seven vocabularies and 169 million triples about 820 thousand
cultural entities. It is distributed jointly with a SPARQL endpoint, a software
for converting catalogue records to RDF, and a rich suite of documentation
material (testing, evaluation, how-to, examples, etc.). ArCo is based on the
official General Catalogue of the Italian Ministry of Cultural Heritage and
Activities (MiBAC) - and its associated encoding regulations - which collects
and validates the catalogue records of (ideally) all Italian Cultural Heritage
properties (excluding libraries and archives), contributed by CH administrators
from all over Italy. We present its structure, design methods and tools, its
growing community, and delineate its importance, quality, and impact
Absorption flattening as one cause of distortion of circular dichroism spectra of Delta-RuPhen(3) . H(2)TPPS complex
To extend the model that explains why and how much absorption flattening
(AF) influences circular dichroism (CD) signals, we have investigated the interesting
case of exciton CD in the Soret region of a noncovalent complex formed by (DRuPhen3)
21 and the tetraanionic porphyrin H2TPPS. Different concentrations have been
studied by using an AF emulator and spectra simulation. The CD spectra of this compound
occasionally show distortions in the solution sampling mode with the increase of
concentration; the inhomogeneous distribution in the cell volume is due to aggregation
and is the source of the AF effect. On the basis of these results, we conclude that AF is
an important cause of distortions in CD spectra for D-RuPhen3 H2TPPS complexes and
might affect the CD bands of other aggregated systems as wel
A comparative study of overtone CH- stretching vibrational circular dichroism spectra of fenchone and camphor
Near-infrared vibrational circular dichroism (VCD) spectra in the region 1500-850 nm are recorded for both
enantiomers of camphor and fenchone using a home-built dispersive instrument. Two CH-stretching overtone
regions and two CH-stretching/HCH-bending combination regions are investigated. The near-infrared VCD
data are examined and compared with the corresponding previously published data of (3R)-(+)-methylcyclopentanone
and (3R)-(+)-methylcyclohexanone. The absorption spectra of both the fundamental and overtone
regions are also considered, and the fundamental CH-stretching VCD data are taken into account, where
possible. An empirical assignment of the spectra is first considered, with special regard to the second CHstretching
overtone region. This region is then investigated by a heuristic approach based on DFT calculations,
using the hybrid functional B3LYP at the 6-31G** basis set level. Subsequently rotational strengths have
been evaluated by use of a classical model based on the contribution of polarizable groups to the optical
activity. The same models are also used to interpret the VCD spectra between 2000 and 3000 wavenumbers
for (3R)-(+)-methylcyclopentanone-d4
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