COR Groups Research Articles

Comprehensive approach to the multigram, heavy-metal-free synthesis of 4-EWG-substituted quinoline derivatives

2-Nitrotoluenes activated by CN, SO2Tol, CO2R or COR groups condense under particular conditions with acetaldehyde in moderate to excellent yields. The unsaturated products are starting materials for cyclization furnishing quinoline oxides substituted with the above electron-withdrawing groups. Under relevant reaction conditions they can be reduced to the corresponding substituted quinolines. The protocol is suitable for multigram scale and extends the scope of the condensation step on non–CN–substituted 2-nitroarenes.

Posterior Inferior Comminution Significantly Influences Torque to Failure in Vertically Oriented Femoral Neck Fractures: A Biomechanical Study.

To evaluate axial fracture obliquity and posterior inferior comminution in vertically oriented femoral neck fractures (FNFs) in the physiologically young patient. A biomechanical investigation was designed to evaluate the impact of these fracture elements on torque to failure using cannulated screw (CS) and sliding hip screw fixation. Four Pauwels III FNF models were established in synthetic femurs: (1) vertically oriented in the coronal plane (COR), (2) coronal plane with axial obliquity (AX), (3) coronal plane with posterior inferior comminution (CCOM), and (4) coronal plane with axial obliquity and posterior inferior comminution (ACOM). In each group (n = 10), specimens were fixed using either 3 CSs or a sliding hip screw with supplemental antirotation screw (SHS). Quasistatic cyclic ramp-loading to failure was performed using a custom testing jig combining axial preloading and torsional ramp-loading. The primary outcome was torque to failure, defined as angular displacement ≥5 degrees. In the CS group, torque to failure was 40.2 ± 2.6 Nm, 35.0 ± 1.4 Nm, 29.8 ± 1.5 Nm, and 31.8 ± 2.2 Nm for the COR, AX, CCOM, and ACOM fracture groups, respectively (P < 0.05). In the SHS group, torque to failure was 28.6 ± 1.3 Nm, 24.2 ± 1.4 Nm, 21.4 ± 1.2 Nm, and 21.0 ± 0.9 Nm for the COR, AX, CCOM, and ACOM fracture groups, respectively (P < 0.05). In both constructs, groups with posterior inferior comminution demonstrated significantly lower torque to failure compared to the COR group (P < 0.05). The CS construct demonstrated higher torque to failure in all groups when compared to the SHS construct (P < 0.01). Posterior inferior comminution significantly affects torque to failure in vertically oriented FNFs. Three peripherally placed CSs may resist combined axial and torsional loading better than a sliding hip screw construct.

Effects of a short-term molt using cassava meal, broken rice, or corn meal on plasma thyroxin concentrations, organ weights and intestinal histopathology in older (95 wk) laying hens

The effects of a nonfasting induced molt were determined on the thyroxin concentration, organ weight and intestinal histopathology in 95-wk-old hens. Hens (60 birds each treatment) were randomly assigned to four treatments for 14 d: 1) molted by feeding broken rice (BRO), 2) fed corn (COR), 3) fed cassava (CAS), or 4) a non-molt control (NON). During the molt period, the BRO, COR and CAS groups were exposed to an 8 h light: 16 h dark photoperiod, whereas the control hens were fed a layer ration and provided with 16 h of light per day. The body weight loss in the CAS hens was 21.90% which was significantly higher than those of the BRO (6.01%) or COR hens (9.30%). The CAS hens completely stopped laying on d 7, whereas the BRO and COR birds exhibited reductions but continued laying. The egg weight of the COR treatment was significantly lower than those of the BRO and CAS treatments. At the end of the molt period, the hematocrit values of the BRO and CAS hens were significantly higher than those of the COR hens. The plasma thyroxin concentrations of the CAS treatment were significantly higher than those of the COR treatment, whereas the BRO hens had a value intermediate between the two groups. The CAS and COR hens had reduced liver weights compared with the BRO hens. However, the thyroid weights of the CAS and COR hens were significantly greater than those of the BRO hens. No inflammatory evidence was observed in any treatment from the examination of intestinal histopathology.

Characterization of a collection of local varieties of tomato (Solanum lycopersicum L.) using conventional descriptors and the high-throughput phenomics tool Tomato Analyzer

Conventional tomato (Solanum lycopersicum L.) descriptors are of great utility for gross morphological characterization but may not be practical for the precise fruit description required for distinguishing closely related cultivar groups. Tomato Analyzer is a new phenomics tool that provides multiple fruit morphology data from scanned images of fruit sections. We characterized 69 accessions of local tomato varieties from the region of València (Spain) corresponding to eight cultivar groups (Borseta, Cherry, Cor, Penjar, Plana, Pruna, Redona, and Valenciana) with 64 conventional and 38 Tomato Analyzer descriptors. Significant differences were found among accessions for all traits except for five monomorphic conventional descriptors, revealing a large diversity in the collection. Significant differences were also found among cultivar groups for 36 conventional and 37 Tomato Analyzer descriptors. The groups Borseta, Cherry, Penjar, Plana, and Pruna were clearly distinct and each of them presented many significant differences with the rest of groups. Conventional descriptors did not differentiate well the Cor, Redona, and Valenciana cultivar groups, but Tomato Analyzer descriptors clearly distinguish Valenciana from Cor and Redona groups. A multivariate principal components analysis (PCA) showed that with the exception of six (8.7 %) accessions, the different cultivar groups (including the very similar Cor and Redona) plotted in separate areas of the PCA graph. The results have shown that combined conventional and Tomato Analyzer descriptors in conjunction with PCA analysis are a powerful tool for characterization and classification of local tomato varieties, as well as for distinguishing between related cultivar groups. This has important implications for the enhancement and protection of local tomato varieties.

NBS-mediated sequential one-pot synthesis of multifunctionalized thiazoles and thiophenes from 1,3-dicarbonyl compounds and mercaptonitrile salts

A NBS-mediated sequential one-pot synthesis of multifunctionalized thiazoles and thiophenes from 1,3-dicarbonyl compounds and mercaptonitrile salts has been developed under mild conditions. This transformation involves sequential bromination/SN2 alkylation/Thorpe–Ziegler cyclization/regio-selective elimination of a –COR group, affording the desired products in moderate to good yields. The sequence of the leaving reactivity of –COR groups was determined and a possible mechanism was proposed.

Understanding how sexual offenders compare across psychiatric and correctional settings: examination of Canadian mentally ill sexual offenders

Much of what is known about sexual offenders is based on correctional samples and then applied across settings based on the assumption that this group is homogeneous. In this study, 149 files were compared, including 108 cases from the forensic mental health system (FMH) and 41 cases from the correctional system (COR). Although many similarities were observed between the FMH and COR groups, the results also revealed important differences. The FMH group was characterised by more frequent hospitalisations, higher rates of major mental illness and single status. The COR group was characterised by a history of physical and sexual abuse, family history of addictions, more intrusive sexual offences and higher rates of offending. These results highlight different profiles for sexual offenders in forensic mental health and correctional settings and challenge us to consider the implications for assessment, treatment and risk management of this unique group of sexual offenders.

Intermolecular Alkyl Radical Additions to Enantiopure N-tert-Butanesulfinyl Aldimines

The sulfinyl group in (R)-N-tert-butanesulfinyl aldimines provides efficient control of the stereoselectivity in the intermolecular reactions with alkyl radicals. The methodology is applicable to aryl, heteroaryl, benzyl, and alkynyl imines, even those containing CN, CO2Me, COR, and OH groups. The best results are attained with hindered radicals (tertiary and secondary ones) without C═N bond reduction. This reaction complements the well-established organometallic additions to N-sulfinyl aldimines to obtain enantiomerically pure functionalized α-branched primary amines.

Beneficial effects of hydrocortisone or spironolactone coating on foreign body response to mesh biomaterial in a mouse model

Prosthetic reinforcements markedly reduce the risk of hernia recurrence. However, the implantation of meshes is related to an inflammatory foreign body reaction (FBR) with serious complications (i.e., persistent seroma, wound infection, mesh migration, entrapment, chronic pain). Adrenal hormones profoundly modify inflammatory response. Their effects on FBR however, remain ill defined. We therefore studied the FBR to polyvinylidenfluoride (PVDF) mesh material that was coated with four different substances: hydrocortisone (COR) or mifepristone (MIF), which respectively stimulate and block the glucocorticoid receptor, and aldosterone (ALD) or spironolactone (SPI), which respectively stimulate and block the mineralocorticoid receptor. The coated substances were released from the meshes within 24 h. Seven, 21, and 90 days after implantation, the specimen was evaluated for collagen formation, granuloma size, inflammatory activity, and angiogenesis. COR and SPI coating protected from inflammatory response, while ALD and MIF coating showed little difference to the control group. The COR and SPI groups showed smaller granuloma sizes at all time points, as well as a reduced number of inflammatory cells (p < 0.001) at day 90, and decreased collagen formation starting after 21 days (p < 0.05). There was a negative correlation for angiogenesis with inflammation around foreign body structures. In summary, these results suggest that early and temporary stimulation of the glucocorticoid receptor or blockade of the mineralocorticoid receptor have beneficial effects on FBR in the long term.

19 Treatment of multivessel coronary artery disease in primary PCI for ST elevation myocardial infarction: culprit only revascularisation is associated with higher mace rates

Background Multi-vessel disease occurs in 40%–65% of patients undergoing Primary PCI for STEMI and is associated with adverse prognosis. Contemporary guidelines recommend treating the infarct related artery alone (culprit) during the urgent procedure. There is limited data comparing outcomes of complete with infarct-related artery (IRA)-only revascularisation in primary PCI for STEMI with few studies including the option of later date elective procedures for the other lesions (staged revascularisation). We therefore sought to clarify the outcome of patients with multi-vessel disease undergoing primary PCI dependent on management strategy. Methods Clinical information was analysed from a prospective data base on 2131 STEMI patients who underwent Primary PCI between January 2004 and May 2010 at a London centre. Patients with previous CABG were excluded. Information was entered at the time of procedure and outcome assessed by all-cause mortality information provided by the Office of National Statistics via the BCIS/CCAD national audit. Patients were split into three different treatment groups: culprit vessel angioplasty-only (COR group); staged revascularisation (SR group) and simultaneous treatment of non-IRA (CR group). The primary end point used was major adverse cardiac events (MACE), defined as death, myocardial infarction (MI), stroke and target vessel revascularisation (TVR). Results There were 963 (45%) consecutive patients with STEMI and multivessel CAD undergoing primary angioplasty. There were similar baseline characteristics between the 3 groups, aside from cardiogenic shock, which was significantly higher in the complete revascularisation group. See Abstract 19 table 1. At 30-days of follow-up, 23/263 (9%) patients in the CR group experienced at least one major adverse cardiac event (MACE), 1 (1%) in the SR group and 35 (5%) in the COR group, p=0.01. This trend continued up to 1-year of follow-up with the lowest rates of events in the SR group. However after 3 years MACE rates are significantly increased in the COR group (24%) but were similar in the CR (18%) and SR (17%) groups. See Abstract figure 1. MACE rates were driven mainly by death in the CR with high rates of TVR in the COR and SR groups. See Abstract figure 2. Conclusions Culprit vessel-only angioplasty was associated with the highest rate of long-term MACE compared with multivessel treatment. Patients scheduled for staged revascularisation experienced a similar rate of MACE to patients undergoing complete simultaneous treatment of non-IRA.

ChemInform Abstract: NMR Study of the Conformational Distribution in Methyl Esters and N,N- Dimethylamides of Diastereoisomeric 4-Cyano-3,4-diphenyl- and 4-Cyano- 3-phenyl-4-(1-naphthyl)-butyric Acids. Relation to the Configurations

Abstract The conformational behaviour of Ar 2 CH(CN)CH(Ar 1 )CH 2 COR (R  OCH 3 ; N(CH 3 ) 2 ; Ar 1  Ph; Ar 2  Ph or 1-naphthyl) has been investigated by 1 H and 13 C NMR spectroscopy. The vicinal proton-proton coupling constants were used together with those of carbon-proton couplings to provide information on the conformational preference in the compounds studied. The conformational distribution with respect to the C(2)C(3) bond is shifted to the conformation having trans Ph and COR groups. Coupling constants involving the cyano carbon atom and the methine proton are J g CN,H = 2.0 Hz and J t CN,H = 14.1 Hz. The conformation with the cyano group and the methine proton trans to each other, with gauche-oriented protons around the C(3)C(4) bond is the preferred one for both isomers in the compounds investigated. The results obtained support the assumption that electrostatic (non-bonded attractive) interactions rather than steric demands operate as dominant factors in controlling the conformational equilibrium.

Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT)4S6], [(RSn)3S4]2−, [(RT)2(CuPPh3)6S6], and [(RSn)6(OMe)6Cu2S6]4− (R=C2H4COOH, CMe2CH2COMe; T=Ge, Sn)

A series of compounds comprising functionalized thiometallate cages [(RT)4S6] (R terminated by COO(H) or COR groups), based on adamantane (T=Ge) or double-decker (T=Sn) type structures or [(RSn)3S4]2- anionic defect heterocubanes were synthesized and their reactions with 1) transition-metal compounds and 2) hydrazine derivatives were explored. Hence it was possible to generate functionalized ternary CuSnS or CuGeS clusters and to transfer COR ligands into CR(N-NH2) or CR(N-NHPh) terminal groups, respectively. The report provides the proof-of-principle for a directed functionalization and derivatization of chalcogenidometallate cages with respect to the formation of chalcogenidometallate-organic hybrid compounds containing M/E semiconductor nodes, as an alternative to the so far most prominent M/O combination in metal-organic frameworks. DFT investigations deliver further insight in the peculiarities of Ge/S versus Sn/S precursors and their products.

Structural Modification Induced in Heparin by a Fenton-Type Depolymerization Process

A low molecular weight heparin (LMWH) obtained by a depolymerization process induced by a Fenton-type reagent was characterized in depth by nuclear magnetic resonance (NMR) spectroscopy. The depolymerization involves the cleavage of glycosidic bonds, leading to natural terminal reducing end residues, mainly represented by N-sulfated glucosamine (A (NS)). Natural uronic acids, especially the 2- O-sulfate iduronic acid (I (2S)), are also present as reducing residues. A peculiar reaction results, such as the disappearance of the nonsulfated iduronic acid residues when followed by 6-O-nonsulfated glucosamine, and the decrease of the glucuronic acid when followed by the N-acetylglucosamine, were observed. Iduronic acid residues, followed by 6- O-sulfate glucosamine (A (Nx,6S)), and the glucuronic acid residues, followed by A (NS) residues, were not modified. A few minor internal chain modifications occur, possibly arising from oxidative breaking of the bond between C2-C3 of glucosamine and uronic acids, suggested by evidence of formation of new -COR groups. Finally, no change was observed in the content of the N-sulfated, 6-O-sulfated glucosamine bearing an extra sulfate on 3-O, which is considered the marker of the active site for antithrombin. With respect to the original heparin, this LMWH is characterized by a lower number of nonsulfated uronic acid residues, and as a consequence, by a lower degree of structural heterogeneity than LMWHs prepared with other procedures.

Optimization of Xe adsorption kinetics in single walled carbon nanotubes

Closed end (10, 10) single walled carbon nanotubes (SWNTs) have been opened by oxidation at their ends and at wall defect sites, using ozone. Oxidation with ozone, followed by heating to 973 K to liberate CO and CO2, causes etching of the nanotube surface at carbon atom vacancy defect sites. The rate of adsorption of Xe has been carefully measured as a function of the degree of nanotube etching by ozone. It is found that a level of etching corresponding to wall openings of about 5–7 Å radius is optimal for maximizing the rate of Xe adsorption. Beyond this level of etching, the rate of Xe adsorption decreases as the surface area of the SWNTs decreases due to further carbon atom removal. Both experiment and modeling show that the presence of polar oxidized groups, such as –COOH or –COR groups, with dipole moments in the range 1.5–3.0 D at the perimeter of the defect sites, causes a retardation of the rate of Xe adsorption due to dipole-induced dipole interactions. This effect is larger for smaller radius defect sites and decreases as the defect sites increase in size beyond about 7 Å radius. At large defect radii, the energetic profile of the adsorption pathway controls the physisorption rate. Modeling shows that after Xe adsorption has been completed inside the nanotubes, then Xe clusters begin to form on the outer surface of the nanotubes at the defect sites where polar groups are present. The Xe clustering effect also occurs to a smaller degree when the defect sites are not decorated by polar groups. The experiments and modeling demonstrate how one may optimize the rate of adsorption of a gas into nanotubes by the adjustment of the size and polar character of the vacancy-site entry ports in the walls of the nanotubes.

Chemical ionization mass spectrometry of some nitro‐containing bifunctional aromatic compounds. Location of protonation site

AbstractIt is found that the nitro substituent of some aromatic bifunctional compounds shows unusual reactivity towards protonation. In the chemical ionization mass spectra of nitrobenzoic acids and their esters and amides, and of nitrophenols and their ethers, protonations on the carboxyl, ester, amide, hydroxyl or alkoxyl groups are highly suppressed by that on the nitro group. As a result, fragmentations based on protonation on these groups unexpectedly become negligible. Ortho effects were observed for all the ortho isomers where the initial protonation on the nitro group is followed by an intramolecular proton transfer reaction, which leads to the expected ‘normal’ fragmentations. Protonation on the nitro substituent is much more favourable in energy than on any of the other substituents. The interaction of the two substituents through the conjugating benzene ring is found to be responsible for this ‘unfair’ competitive protonation. The electron‐attracting nitro group strongly destabilizes the MH+ ions formed through protonation on the other substituent; although the COR (R  OH, OMe, OEt, NH2) groups are also electron‐withdrawing, their effects are weaker than that of NO2; thus protonation on the latter group produces more‐stable MH+ ions. On the other hand, an electron‐releasing group OR (R  H, Me, Et) stabilizes the nitro‐protonated species; the stronger the electron‐donating effect of this group the more stable the nitro‐protonated ions.

NMR study of the conformational distribution in methyl esters and N,N-dimethylamides of diastereoisomeric 4-cyano-3,4-diphenyl- and 4-cyano-3-phenyl-4-(1-naphthyl)-butyric acids. Relation to the configurations

The conformational behaviour of Ar 2CH(CN)CH(Ar 1)CH 2COR (R  OCH 3; N(CH 3) 2; Ar 1  Ph; Ar 2  Ph or 1-naphthyl) has been investigated by 1H and 13C NMR spectroscopy. The vicinal proton-proton coupling constants were used together with those of carbon-proton couplings to provide information on the conformational preference in the compounds studied. The conformational distribution with respect to the C(2)C(3) bond is shifted to the conformation having trans Ph and COR groups. Coupling constants involving the cyano carbon atom and the methine proton are J g CN,H = 2.0 Hz and J t CN,H = 14.1 Hz. The conformation with the cyano group and the methine proton trans to each other, with gauche-oriented protons around the C(3)C(4) bond is the preferred one for both isomers in the compounds investigated. The results obtained support the assumption that electrostatic (non-bonded attractive) interactions rather than steric demands operate as dominant factors in controlling the conformational equilibrium.

Pseudohalogen chemistry. VIII—Substituent constants (Z) for the thiocyanato group in the estimation of the chemical shifts of vinyl protons in α,β‐unsaturated thiocyanates

AbstractSubstituent constants for the thiocyanato group (Z = 0.94, Z = 0.45 and Z= 0.41) have been derived by an additivity procedure, and shown to reproduce the chemical shifts of vinyl protons in a wide variety of α,β‐unsaturated thiocyanates with an accuracy of ±0.30 ppm in 94% of the cases studied. Deviations due to tBu and COR groups are discussed in terms of steric and field effects.

Predictable long-delay matching-to-sample trials result in long-latency sample responding by pigeons

When a delayed matching-to-sample task does not involve short-delay trials interspersed among the long-delay trials, there is evidence that pigeons show long latencies in responding to the sample (sample observing response). They may even stop responding altogether. Two experiments were conducted to confirm the phenomenon and determine what aspect of the procedure is responsible for it. In Experiment 1 pigeons were trained on a delayed matching-to-sample task in which the delay remined constant throughout each session and was increased as each bird reached a performance criterion. The results indicated that sampleresponse latency increased in a regular fashion as delay increased. When the delay increased to 8.0 s, responding to the sample often stopped for long periods of time. In Experiment 2 pigeons were exposed to constant delay sessions (LONG), or mixed delay sessions with the delay length signaled (COR) or unsignaled (UNC). Sample-response latencies increased with increasing delay on long-delay trials for the LONG and the COR groups but not for the UNC group. Results supported the hypothesis that predictability of the long delay and not the loss of association between sample responses and reinforcement was responsible for the increased sample-response latency.

Etude par resonance magnetique nucleaire de derives anthraceniques—I : Effet “peri” et conformations

The predominant conformation of anthracene derivatives bearing OCH 3, NR 1R 2, COR groups at the 1 or 9 positions has been ascertained using NOE data and lanthanide shift reagents. Whenever a lone pair in OCH 3 or NR 1R 2 group is directed toward a peri proton this proton is deshielded. The magnitude of the peri effect induced by various substituents is given. The downfield peri shifts parallel those previously observed in naphthalenic and phenanthrenic compounds.