Diminutive Effect Research Articles

Ligand and Substituent Effect on Regium-π Bonding in Cu and Ag π-Conjugated Complexes: A Density Functional Study.

Density functional theory investigation of regium (Rg)-π bonding using the RgL-X model system, where Rg = Cu and Ag; L = CN, NO2, and OH; X = π-conjugated system (benzene, cyanobenzene, benzoic acid, pyridine, 2-methoxy aniline, 1,4-dimethoxy benzene, and cyclophane), has been performed. Conclusive evidence of the Rg-π bond has been provided by analysis of molecular electrostatic potential surfaces, Rg-π bond length, interaction energy (ΔE), second-order perturbation energy (E2), charge transfer (Δq), quantum theory of atom in molecules, and noncovalent interaction plots for 42 structural arrangements with varying ligands and the substituted aromatic ring. The Rg-π bond length in the optimized model systems varies from 2.03 to 2.12 Å in Cu complexes (1-21) and from 2.26 to 2.38 Å in Ag complexes (22-42) at the PBE0-D3 functional. While the ligand (L) attached to the Rg metal has a bargaining effect on the strength of the Rg-π bond (in the order of -OH > -CN = -NO2), the π-conjugated systems have a diminutive effect. Two X-ray crystal structures (CUCSOI and AHIDQU) having the Rg-π bond, accessed from Cambridge Crystallographic Data Centre (CCDC), are discussed here to signify the influence of Rg-π bonding on the crystal structure.

CONNOTATIVE PROPER NAMES AS AFFECTONYMS IN THE SPEECH OF FRANCOPHONES

The article is devoted to connotative proper names-affectonyms, which are proper names of people / characters of artistic reality, used in a figurative sense as synonyms for the name of the addressee of the speech (rarely the third person). The research was implemented on the basis of questionnaires and analysis of social media texts. The purpose of the research is to analyze the semantics of connotative proper names used as affectonyms, to demonstrate their (in)dependence on the cultural preferences of generations, to find out the motivation of such naming. In the course of the study, it was found that proper names-affectonyms, regardless of the origin of the primary signified (a real proper name or a literary proper name), are metaphors: mostly positive features of the primary signified are transferred to the addressee of speech. Despite the fact that a certain part of proper names-affectonyms remains unchanged over time (usually we are talking about well-known connotative proper names such as Roméo, Juliette, Don Juan), this is a rather dynamic group of names that reflects the interests and cultural demands of society. However, there are general models of metaphorical transfer, the semantics of such names, which are meant to refer to the ideas of strength, beauty, intelligence, power, and the romanticism of fictitious or real personalities. So, instead of mon Alain Delon, mon petit Timothée Chalamet is used, instead of Einstein — mon Steve Jobs — both in an approving and ironic sense. In certain cases, affectonyms of this kind are formed through metonymy — according to the sphere of interests of the addressee of the speech. Sometimes the phonic structure of the affective names plays a role. Through reduplication or the use of diminutive suffixes in the name, diminutive effect is created. In the context of the use of proper names-affectonyms, we note the presence of a language play, which is manifested both in the modification of the primary proper name and in playing with logical connections between concepts.

What Do Reference Librarians Do Now?

Objective - The primary purpose of this study was to better understand the nature of “reference” and reference transactions. Methods - This study looked at four years’ of reference transaction (RT) data recorded at a small, state-owned university. Results - The data clearly indicates that the overall number of RT continues to decline. It also reveals that, despite the use of student mentors, librarians are still involved with a majority of RT, regardless of whether or not they require the expertise of a librarian to resolve. Conclusion - Continuing to be involved with RT which do not require the knowledge or training of a librarian (e.g., directional) can have a diminutive effect on the perceived role, work, and value of librarians. As such, it is suggested that these sorts of questions be addressed by student mentors or staff members. In turn, this will allow librarians to focus on those questions and activities which do require their unique knowledge and skills. Along similar lines, it is also suggested that librarians explore and identify new, non-traditional ways of applying their expertise to student success initiatives and the overall academic life of the institution. With the merger of three libraries, data from this study has been and continues to be used to make informed decisions about the provision of reference services in a new, integrated library environment.

Oxidation of cystatin imparted by riboflavin generated free radicals: Spectral analysis

Thiol Protease inhibitors (cystatins) are endogenous natural inhibitors of cysteine proteases. They are present in all mammalians cells and body fluids. Cystatin are allocated into three major families. Family –I stefins, family –II cystatins and family –III kininogens, according to their amino acid sequence, molecular weight, carbohydrate content and disulphide bonds. It has been investigated that thiol proteases (cathepsin) and their endogenous inhibitor, cystatins have been closely associated with diseases like Alzheimer's, Prions, neurodegenerative diseases, cancer and diabetes. Photodynamic effect of various sensitizers' have long been applied to delineate structural and functional properties of biologically active proteins. Flavins are well known to photo oxidize amino acids which effects conformation of proteins. Riboflavin (Vit B2) with a recommended daily requirement of approximately 2–3 mg is a yellow pigment, It is widely distributed in human tissues and blood, in both free and conjugated forms.In the present Study it has been shown that cystatin purified from buffalo brain (BC) is susceptible to reactive oxygen species generated by photo activation of riboflavin. It was observed that Photo activated riboflavin leads to inactivation of BC. Major Loss of tryptophan intensity was observed in the presence of purified thiol protease inhibitor upon incubation with 50 μM of riboflavin.In order to inspect the type of reactive oxygen species involved in inactivation of the inhibitor, different scavenger's were used namely glucose, potassium Iodide, sodium azide, manitol, thiourea, sodium benzoate, curcumin, quercetin, ascorbic acid and uric acid. It was found that Glucose, Potassium Iodide and sodium azide, have preventive effect on photo inactivation of the purified cystatin whilst other scavengers illustrated diminutive defensive effect.

Selective conversion of aromatics into cis-isomers of naphthenes using Ru catalysts based on the supports of different nature

A series of Ru-contained catalysts based on mesoporous and micro-mesoporous supports synthesized for the selective hydrogenation of naphthalene and tetralin in n-hexadecane solution. The influence of the support – HMS, SBA-15 and ZSM-5/MCM-41, namely porous structure and acidity on the catalysts activity were thoroughly investigated. It was found that the supports acidity has a diminutive effect on the cis-decalin formation due to increased isomerization activity of cis-decalin to trans-decalin. It was shown that the amount of unconverted tetralin influenced the final cis/trans decalines ratio considerably. The effect of parameters such as temperature, hydrogen pressure and reaction time on conversion and selectivity to partially or fully hydrogenated products was investigated under 3–7 MPa H2, 220–320 °C and 0.5–3 h. It provides a practically fully naphthalene conversion and a high cis-decalin selectivity.

The B3 triangle faces of B6H62− as the preferred electron donor sites for successive interactions with HF in B6H6(HF)n2– complexes (n = 1–8)

The ab initio calculations were done at MP2/aug-cc-pvdz computational level to analyze interactions of 1–8 HF molecules with B6H62− in B6H6(HF)n2– clusters (n = 1–8). In the B6H6(HF)n2– clusters the HF molecules as hydrogen bond donors were interacting with B3 triangle faces of B6H62− as hydrogen bond acceptor. Distances of HF molecules from center of B3 triangles are in the range of 2.03–2.13 Å. Interaction of B6H62− with HF molecules leads to contraction along with blue shift of B–H bonds. Stabilities, structural properties and spectral characteristics of B6H6(HF)n2– adducts have been determined. The energetic, structural and spectral results are dealing with diminutive effect in these clusters. The Bader’s Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Orbital (NBO) calculations were used to analyze the optimized complexes. Good correlations were found between different methods which were applied for analyzing these clusters.

Plio-Pleistocene sedimentary record from the Northwind Ridge: new insights into paleoclimatic evolution of the western Arctic Ocean for the last 5 Ma

Sediment core HLY0503-03JPC from the top of the Northwind Ridge provides the first confirmed Plio-Pleistocene record from the western Arctic Ocean, with calcareous microfossils uniquely preserved to ca. 5 Ma. Results are compared to nearby core P1-93AR-P23 from the ridge slope, which was previously used to reconstruct early Quaternary sea-ice conditions in the region (Polyak et al. in Quat Sci Rev 79:145–156, 2013), and is now re-dated to at least the late Pliocene. Ages were estimated primarily from strontium isotope stratigraphy on benthic foraminifers. Based on multiple physical, paleomagnetic, elemental geochemical, and paleobiological (foraminifers) proxies, we identify three major stratigraphic divisions (Units 1, 2a, and 2b) roughly representing upper to middle (“glacial”) Quaternary, lower Quaternary to Pliocene, and lower Pliocene to possibly upper Miocene (undated). Benthic foraminiferal assemblages were utilized to evaluate paleo-sea-ice conditions, while other proxies were used to interpret paleocirculation and sediment transport processes. Early Quaternary and older sediments indicate diminutive effect from glaciations, reduced sea-ice conditions, and a periodic strong current impact on the ridge top, possibly due to an enhanced Atlantic water flow. Ages derived from the first foraminiferal tests appearing at ca. 5 Ma likely indicate a redeposition pulse that we attribute to the onset of Pacific water throughflow via the Bering Strait. A large hiatus above this level in JPC3 spans most of the Pliocene. The Unit 2a/1 boundary, estimated to ca. 0.8 Ma, is marked by an abrupt faunal and sedimentary change, which is consistent with the major climatic shift that occurred during this time (Mid-Pleistocene Transition). Unit 1 exhibits a strong control from glacial cyclicity, with a progressive expansion of the Laurentide Ice Sheet primarily affecting the study region, and mostly perennial sea-ice conditions. Overall results suggest that the Pliocene and early Pleistocene may provide relevant paleoclimatic analogs for the rapidly changing Arctic environments of today.

Consequence on long term storage on phytochemical attributes of cumin (Cuminum cyminum, L.) from districts of north Gujarat, India

Among spices, cumin (Cuminum cyminum L.) is a most traditional spice which possesses culinary as well as medicinal uses. Cumin stored for years together become a common practice by the farmers, traders and processors during superfluous production as well as lower market price, in order to be fetch high price in future. Impact of long time storage of cumin seed under ambient condition were ascertain quality attribute for oil, oleoresin and phytochemicals. Cumin variety Gujarat cumin-4 (GC4) has been preferred for large scale sowing in India particularly in Gujarat and Rajasthan state due to high yield, potent to first wilt resistance with superior grain quality and high aromatic effect. The aim of present study was to assess the long time storage consequence on volatile oil, oleoresin and phytochemical constituents of cumin seed stored for 1, 12, 24, 36, 48, and 60 months at ambient condition under standard storage practice. The study shows that volatile oil estimated by with hydro distillation method, yield reduced from 4.1% to 3.25% and 2.10%, whereas the oleoresin by soxhlet extraction with solvent petroleum ether, content reduced from 16.11% to 15.95% and 14.32% in cumin seed upon storage for 1–36 and 60 months, respectively. Total phenolic content (TPC) estimated by Folin-Ciocalteau (FC) reagent method from 80% methanolic extract, was reduced from 12.60±0.934 to 10.08±0.32mg Gallic acid equivalent (GAE)/g cumin seed upon 48 months of storage whereas total flavonoid content was reduced from 7.53±0.07 to 6.92±0.31mg Quercetin equivalent (QE)/g cumin seed upon 60 months of storage. Antioxidant capacity of the methanolic extract were measured as 1,1-diphenyl-2-picryl-hydrazyl (DPPH) free radical scavenging potential and ferric reducing antioxidant power (FRAP) assay. DPPH scavenging potential was reduced from 743.26±74 to 588.62±38 milimolar Ascorbic acid equivalent (mM AAE)/g cumin seed and FRAP value was reduced from 720.54±33 to 474.88±31 milimolar Ferrous sulfate equivalent (mM FE)/g cumin seed during long term storage upto 60 months with respect to fresh harvest. The storage upto 36 months had diminutive reduction effect on oleoresin, volatile oils and phytochemical constituents whereas further storage till to 60 months showed marginal reduction in both oils and phytochemical constituents in cumin seed which may lead to some extent decreases in its flavor and aroma characteristics as well as medicinal values.

Theoretical study of intermolecular interactions in FH⋯C4B2H6⋯X clusters (X = H2O, CH3OH, NH3, O2, N2, HCN, CO, NO and CO2)

Asa result of HF and X molecules’ (X=H2O, CH3OH, NH3, O2, CO, NO, HCN, CO2 and N2) interactions with nido-C4B2H6, FH⋯C4B2H6⋯X clusters were obtained. Ab initio calculations were applied to analyze the interactions at MP2/6-311++G(2d,2p) computational level. The FH⋯C4B2H6⋯X clusters were obtained from the interactions of HF on the apex and X molecules from the pentagonal base with nido-C4B2H6 pyramid. Energetic, structural and spectral properties of FH⋯C4B2H6, C4B2H6⋯X as well as FH⋯C4B2H6⋯X adducts were examined. The interaction energies, structural parameters and spectral properties of FH⋯C4B2H6⋯X clusters, with respect to their components (FH⋯C4B2H6 and C4B2H6⋯X), indicated a weak diminutive effect. The Bader’s Quantum Theory of Atoms in Molecules (QTAIM) was used to analyze the optimized complexes.

Comparison of hydrogen and halogen bonds between dimethyl sulfoxide and hypohalous acid: competition and cooperativity

ABSTRACTA theoretical study of the complexes formed between dimethyl sulfoxide (DMSO) and hypohalous acid (HOX, X = Cl, Br, and I) has been carried out at the MP2/aug-cc-pVTZ level. For each HOX, four minima binary complexes were found, two mainly with an OH•••O hydrogen bond and the other two with an OX•••O halogen bond. The hydrogen-bonded complexes are more stable than the halogen-bonded analogues for HOCl and HOBr, while both types of complexes have similar stability in the iodine case. A red shift was found for the associated H–O and X–O bond stretch vibrations and a small blue shift for the distant bonds. As the oxygen of DMSO simultaneously binds with two HOCl molecules, the corresponding interactions are weakened with diminutive effect. This diminutive effect is the largest in the complexes with two OH•••O hydrogen bonds but the smallest in those with two OCl•••O halogen bonds.

Interplay between the σ-tetrel bond and σ-halogen bond in PhSiF3⋯4-iodopyridine⋯N-base

The ternary complexes of PhSiF3⋯4-iodopyridine⋯N-base (N-base = HCN, NH3, NHNH2, and NH2CH3), PhTF3⋯4-iodopyridine⋯NH3 (T = C and Ge), PhSiY3⋯4-iodopyridine⋯NH3 (Y = H and Cl), PhSiF3⋯4-bromopyridine⋯NH3 and the respective binary complexes have been investigated. 4-Halopyridine in these ternary complexes plays a dual role of both a Lewis acid with the σ-hole on the halogen atom in the halogen bond and a Lewis base with the nitrogen atom in the tetrel bond. The interplay between both interactions in the ternary complexes has been analyzed in terms of the binding distance, binding energy, charge transfer, electron density and electrostatic potentials. A synergistic effect is found for the tetrel and halogen bonds in most of the ternary complexes, while a diminutive effect is present for the hydrogen and halogen bonds in PhCF3⋯4-iodopyridine⋯NH3. The magnitude of cooperative energy depends on the strength of both interactions. Interestingly, PhSiCl3⋯4-iodopyridine has a stronger tetrel bond than PhSiH3⋯4-iodopyridine, inconsistent with the size of the σ-hole on the Si atom. In addition, the tetrel bond exhibits a partially covalent interaction nature.

Synthesis of α-santonin derivatives for diminutive effect on T and B-cell proliferation and their structure activity relationships

A new library of 20 compounds from α-santonin was synthesized and tested against Con-A induced T-cell proliferation and LPS-induced B-cell proliferation via MTT assay. The study resulted in the identification of potent immunosuppressant molecules, which were further screened along with α-santonin for Tumor Necrosis Factor Alpha (TNF-α) inhibitory activity. One of the molecules (7) at 10 μM showed equipotency to that of dexamethasone (1 μM conc.) used as a standard. Structure activity relationships of the synthesized compounds along with our earlier reported α-santonin derivatives have been studied. Inferences from the modifications carried out at all the three sites of α-santonin have been elaborated. Computational study of the active compounds shows TNF-α protein as its preferable target rather than Inosine Monophosphate Dehydrogenase (IMPDH).

Tuning of chalcogen bonds by cation-π interactions: cooperative and diminutive effects.

The tunability of Y···N chalcogen bond via formation of a cation-π interaction in ternary complexes M(+)-PhYH-NH3, M(+)-PhYH-NCH, and M(+)-PhCCCN-YHF (M = Li, Na; Y = Se, Te) is investigated at MP2/aug-cc-pVDZ computational level. Our results indicate that the strength of Y···N and cation-π interactions in the ternary complexes depends on the role of the aromatic molecule. That is, a cooperative effect is evident if aromatic molecule acts as the Lewis acid and Lewis base, simultaneously, while a diminutive effect is observed when the aromatic molecule acts only as the Lewis base in both Y···N and cation-π interactions. For a given aromatic system, the shortening or lengthening of Y···N distances is more important for Li(+) complexes than Na(+) counterparts. The mechanism of cooperative/diminutive effects in the ternary complexes is studied by molecular electrostatic potential (MEP) and topological analysis of the electron density.

Influence of substituents on the nature of metal⋯π interaction and its cooperativity with halogen bond.

High-level quantum chemical calculations have been performed to investigate the influence of substituents on the metal-π interaction and its cooperative effect with halogen bond in C2X4⋯MCN⋯ClF (X = H, CN, CH3; M = Cu, Ag, Au). The strong electron-withdrawing group CN weakens the metal-π covalent interaction, while the weak electron-withdrawing group CH3 strengthens it. The metal-π covalent interaction is dominated by electrostatic energy although the AuCN complex has approximately equal electrostatic and polarization contributions. However, the metal-π covalent interaction is governed by polarization energy due to the CN substitution. A cooperative effect is found for the halogen bond and metal-π interactions in C2H4⋯MCN⋯ClF, while a diminutive effect occurs in the triads by the CN substituent. Orbital interaction analysis indicates that the strong electron-withdrawing group CN causes the C=C group vary from a stronger donor orbital to a stronger acceptor orbital.

Effects of Emulsifiers, Precooking and Washing Treatments on the Quality of Retorted Ginseng Chicken Soup

To improve the quality of retorted ginseng chicken soup (samgyetang), the effects of three different treatments, including emulsifier addition (T1), emulsifier addition/precooking (T2) and emulsifier addition/precooking/washing (T3), were investigated. T2 and T3 treatments showed a better quality with significant diminutive effect (P < 0.05) on the fat content of breast meat (11.29 and 19.35%, respectively) as well as broth (29.69 and 45.31%, respectively) compared with that of the control. The CIE L* values of the breast meat significantly increased, whereas CIE a* and b* values of porridge and broth decreased compared with those of the control (P < 0.05). Furthermore, all treatments significantly resulted in smaller fat droplet particles on the broth and increased the pH values of all breast meat, porridge and broth samples (P < 0.05). Based on the overall acceptability results from the sensory evaluation, T2 was identified as the best method to improve the quality of samgyetang. Practical Applications This research would have practical applications in the reduction of fat content in meat and broth of retorted soups like samgyetang. The results indicate that combination of emulsifiers and precooking could improve the quality of samgyetang without sacrificing its flavor. In addition, emulsifier addition on this experiment produced smaller fat droplets compared with the control group. From this point of view, it is recommended to use emulsifiers and precooking combination treatment to decrease the fat content of the final product, increasing flavor and imparting small fat droplets of broth, which is favored by the consumers.

Compound Specific Extraction of Camptothecin fromNothapodytes nimmonianaand Piperine fromPiper nigrumUsing Accelerated Solvent Extractor

Effects of varying temperatures with constant pressure of solvent on extraction efficiency of two chemically different alkaloids were studied. Camptothecin (CPT) from stem of Nothapodytes nimmoniana (Grah.) Mabb. and piperine from the fruits of Piper nigrum L. were extracted using Accelerated Solvent Extractor (ASE). Three cycles of extraction for a particular sample cell at a given temperature assured complete extraction. CPT and piperine were determined and quantified by using a simple and efficient UFLC-PDA (245 and 343 nm) method. Temperature increased efficiency of extraction to yield higher amount of CPT, whereas temperature had diminutive effect on yield of piperine. Maximum yield for CPT was achieved at 80°C and for piperine at 40°C. Thus, the study determines compound specific extraction of CPT from N. nimmoniana and piperine from P. nigrum using ASE method. The present study indicates the use of this method for simple, fast, and accurate extraction of the compound of interest.

Comparison of melting and crystallization behaviors of polylactide under high-pressure CO2, N2, and He

This study investigated the melting and crystallization behaviors of polylactide (PLA) under high-pressure CO2, N2, and helium (He) using a high-pressure differential scanning calorimeter and a wide-angle X-ray diffractometer. The results showed that the PLA's melting temperature was depressed only when contacted with pressurized CO2 where at high CO2 pressures the lubricating gas molecules induced more imperfect melt and cold crystals during the cooling and heating cycle. PLA's melt crystallization was analyzed during both isothermal and nonisothermal processes. In contrast to the effect of dissolved CO2 that expedited the PLA's crystallization rate, N2 showed almost a neutral impact on the PLA's crystallization kinetics. Because of the lower solubility, N2 gas dissolved in the PLA had a diminutive plasticization effect, and thereby it could only counterbalance its negative hydraulic pressure effect. Moreover, as the helium pressure increased, the PLA's final crystallinity was reduced due to the dominant effect of helium's hydraulic pressure.

Diminutive effect on T and B-cell proliferation of non-cytotoxic α-santonin derived 1,2,3-triazoles: A report

α-Santonin derived new series of 1,2,3-triazoles synthesized through Azide–Alkyne Huisgen 1,3-dipolar cycloaddition reaction between substituted aryl azide and a propargylated α-desmotrosantonin were bio-evaluated for their diminutive effect on ConA induced T-cell and LPS induced B-cell proliferation. Interestingly, most of the synthesized compounds showed better immunosuppressant activity than α-santonin. Triazole derivatives 9, 10, 17, 18, 29, and 30 displayed significant diminutive effect on cell proliferation. Compounds 12 and 13 were found selective against ConA T-cell proliferation exhibiting >90% inhibition at 1 × 10−6 M concentration. The present study resulted in identification of several triazole derivatives as effective immunosuppressive agents.

Surface Modification of Sisal Fibers Using Cellulase and Microwave-Assisted Grafting: A Study of Morphology, Crystallinity, and Thermal Stability

Surface modification of sisal fibers (Agave sisalana) using microwave-radiation-induced grafting and cellulase has been carried out in this paper. The modified fibers were characterized by various techniques to determine their morphology, crystallinity, and thermal stability. It has also been found that microwave-radiation-assisted graft copolymerization results in enhanced thermal stability and has a diminutive effect on the crystalline structure of sisal fibers. Cellulase enzyme treatment also results in enhanced thermal stability with negligible change in percentage crystallinity.

Theoretical study of the triangular bonding complex formed by carbon tetrabromide, a halide, and a solvent molecule in the gas phase

MP2(full)/aug-cc-pVDZ(-PP) computations predict that new triangular bonding complexes CBr4...X-...H-C (where X- is a halide and H-C refers to a protic solvent molecule) consist of one halogen bond and two hydrogen bonds in the gas phase. Carbon tetrabromide acts as the donor in the halogen bond, while it acts as an acceptor in the hydrogen bond. The halide (which commonly acts as an acceptor) can interact with both carbon tetrabromide and solvent molecule (CH3CN, CH2Cl2, CHCl3) to form a halogen bond and a hydrogen bond, respectively. The strength of the halogen bond obeys the order CBr4...Cl->CBr4...Br->CBr4...I-. For the hydrogen bonds formed between various halides and the same solvent molecule, the strength of the hydrogen bond obeys the order C-H...Cl->C-H...Br->C-H...I-. For the hydrogen bonds formed between the same halide and various solvent molecules, the interaction strength is proportional to the acidity of the hydrogen in the solvent molecule. The diminutive effect is present between the hydrogen bonds and the halogen bond in chlorine and bromine triangular bonding complexes. Complexes containing iodide ion show weak cooperative effects.