Reductive dimerization of benzothiazolium salts.

Three different types of reaction products were obtained from the reduction of 2-substituted 3-methylbenzothiazolium salts using Na : Hg (1 wt%). Depending on the 2-substituents, two types of dimeric compounds were obtained: the 2-cyclohexyl-, 2-phenyl-, and 2-(p-tolyl)-substituted species are reduced to the corresponding 2,2'-bibenzo[d]thiazoles, while their 2-((p-OMe)C6H4)- and 2-((p-NMe2)C6H4)-substituted derivatives afford cis-[1,4]benzothiazino[3,2-b][1,4]benzothiazines. Furthermore, in the presence of molecular O2, new disulfide derivatives were obtained from the bibenzo[d]thiazoles. The products were obtained in a moderate to good yield, and the structures were confirmed using single-crystal X-ray diffraction. The electrochemistry and further reactivity towards different oxidants of the dimeric compounds were studied; the 2,2'-bibenzo[d]thiazoles show oxidation potentials similar to that of ferrocene and are converted back to the corresponding benzothiazolium cations by mild oxidants such as TCNQ. In contrast, the benzothiazino-benzothiazines show no oxidations in the solvent window of THF.

Benzoimidazolium-derived dimeric and hydride n-dopants for organic electron-transport materials: impact of substitution on structures, electrochemistry, and reactivity.

1,3-Dimethyl-2,3-dihydrobenzo[d]imidazoles, 1H, and 1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[d]imidazoles, 12, are of interest as n-dopants for organic electron-transport materials. Salts of 2-(4-(dimethylamino)phenyl)-4,7-dimethoxy-, 2-cyclohexyl-4,7-dimethoxy-, and 2-(5-(dimethylamino)thiophen-2-yl)benzo[d]imidazolium (1g-i+, respectively) have been synthesized and reduced with NaBH4 to 1gH, 1hH, and 1iH, and with Na:Hg to 1g2 and 1h2. Their electrochemistry and reactivity were compared to those derived from 2-(4-(dimethylamino)phenyl)- (1b+) and 2-cyclohexylbenzo[d]imidazolium (1e+) salts. E(1+/1•) values for 2-aryl species are less reducing than for 2-alkyl analogues, i.e., the radicals are stabilized more by aryl groups than the cations, while 4,7-dimethoxy substitution leads to more reducing E(1+/1•) values, as well as cathodic shifts in E(12•+/12) and E(1H•+/1H) values. Both the use of 3,4-dimethoxy and 2-aryl substituents accelerates the reaction of the 1H species with PC61BM. Because 2-aryl groups stabilize radicals, 1b2 and 1g2 exhibit weaker bonds than 1e2 and 1h2 and thus react with 6,13-bis(triisopropylsilylethynyl)pentacene (VII) via a "cleavage-first" pathway, while 1e2 and 1h2 react only via "electron-transfer-first". 1h2 exhibits the most cathodic E(12•+/12) value of the dimers considered here and, therefore, reacts more rapidly than any of the other dimers with VII via "electron-transfer-first". Crystal structures show rather long central C-C bonds for 1b2 (1.5899(11) and 1.6194(8) Å) and 1h2 (1.6299(13) Å).

Powerful Organic Molecular Oxidants and Reductants Enable Ambipolar Injection in a Large-Gap Organic Homojunction Diode.

Doping has proven to be a critical tool for enhancing the performance of organic semiconductors in devices like organic light-emitting diodes. However, the challenge in working with high-ionization-energy (IE) organic semiconductors is to find p-dopants with correspondingly high electron affinity (EA) that will improve the conductivity and charge carrier transport in a film. Here, we use an oxidant that has been recently recognized to be a very strong p-type dopant, hexacyano-1,2,3-trimethylene-cyclopropane (CN6-CP). The EA of CN6-CP has been previously estimated via cyclic voltammetry to be 5.87 eV, almost 300 meV higher than other known high-EA organic molecular oxidants. We measure the frontier orbitals of CN6-CP using ultraviolet and inverse photoemission spectroscopy techniques and confirm a high EA value of 5.88 eV in the condensed phase. The introduction of CN6-CP in a film of large-band-gap, large-IE phenyldi(pyren-1-yl)phosphine oxide (POPy2) leads to a significant shift of the Fermi level toward the highest occupied molecular orbital and a 2 orders of magnitude increase in conductivity. Using CN6-CP and n-dopant (pentamethylcyclopentadienyl)(1,3,5-trimethylbenzene)ruthenium (RuCp*Mes)2, we fabricate a POPy2-based rectifying p-i-n homojunction diode with a 2.9 V built-in potential. Blue light emission is achieved under forward bias. This effect demonstrates the dopant-enabled hole injection from the CN6-CP-doped layer and electron injection from the (RuCp*Mes)2-doped layer in the diode.

Organometallic and Organic Dimers: Moderately Air-Stable, Yet Highly Reducing, n-Dopants.

ConspectusElectrical doping using redox-active molecules can increase the conductivity of organic semiconductors and lower charge-carrier injection and extraction barriers; it has application in devices such as organic and perovskite light-emitting diodes, organic and perovskite photovoltaic cells, field-effect transistors, and thermoelectric devices. Simple one-electron reductants that can act as n-dopants for a wide range of useful semiconductors must necessarily have low ionization energies and are, thus, highly sensitive toward ambient conditions, leading to challenges in their storage and handling. A number of approaches to this challenge have been developed, in which the highly reducing species is generated from a precursor or in which electron transfer is coupled in some way to a chemical reaction. Many of these approaches are relatively limited in applicability because of processing constraints, limited dopant strength, or the formation of side products.This Account discusses our work to develop relatively stable, yet highly reducing, n-dopants based on the dimers formed by some 19-electron organometallic complexes and by some organic radicals. These dimers are sufficiently inert that they can be briefly handled as solids in air but react with acceptors to release two electrons and to form two equivalents of stable monomeric cations, without formation of unwanted side products. We first discuss syntheses of such dimers, both previously reported and our own. We next turn to discuss their thermodynamic redox potentials, which depend on both the oxidation potential of the highly reducing odd-electron monomers and on the free energies of dissociation of the dimers; because trends in both these quantities depend on the monomer stability, they often more-or-less cancel, resulting in effective redox potentials for a number of the organometallic dimers that are approximately -2.0 V vs ferrocenium/ferrocene. However, variations in the dimer oxidation potential and the dissociation energies determine the mechanism through which a dimer reacts with a given acceptor in solution: in all cases dimer-to-acceptor electron transfer is followed by dimer cation cleavage and a subsequent second electron transfer from the neutral monomer to the acceptor, but examples with weak central bonds can also react through endergonic cleavage of the neutral dimer, followed by electron-transfer reactions between the resulting monomers and the acceptor. We, then, discuss the use of these dimers to dope a wide range of semiconductors through both vacuum and solution processing. In particular, we highlight the role of photoactivation in extending the reach of one of these dopants, enabling successful doping of a low-electron-affinity electron-transport material in an organic light-emitting diode. Finally, we suggest future directions for research using dimeric dopants.

HSF1 and GM-CSF expression, its association with cardiac health, and assessment of organ function during heat stress in crossbred Jersey cattle.

The study aimed to evaluate the differential expression of HSF1 and GM-CSF mRNA in PBMCs and correlate it with myocardial injury in crossbred Jersey heifers during heat stress. The study also assessed the effect of heat stress on cardiac electrical activity, vascular health, liver function and kidney function. The experiment was conducted in two phases: for heat stressed animals; HS in June (THI ranged from 80.0 to 89.8) and for control group i.e. not exposed to heat stress in January (THI ranged between 70.1 and 71.4). Results of the study revealed that the relative abundance of HSF1 and GM-CSF mRNA increased significantly (P < 0.05) in HS. Serum cardiac biomarkers such as CK-MB, AST and CRP were significantly elevated (P < 0.05) in HS. cTnI was detected 'positive' in nineteen out of twenty four cases in HS. Correlation of HSF1 and GM-CSF expression with concentration of LDH, CKMB, CRP and AST in HS was negative but non-significant (P > 0.05). Significant (P < 0.05) ECG findings in HS were increased heart rate, decreased RR interval, decreased PR interval, decreased QRS amplitude and decreased amplitude of P wave. Marked reduction (P < 0.05) in serum cholesterol and triglyceride levels was observed in HS. ALP, AST, bilirubin and urea levels in serum were significantly elevated (P < 0.05) in HS. In conclusion, cardiac enzymes in serum were significantly elevated in HS indicating myocardial injury. HSF1 and GM-CSF mRNA expression alone was inadequate in conferring cytoprotection to cardiac cells in HS. Cardiac electrical activity, vascular status, liver and kidney function were significantly altered in HS.

An integrative bioinformatics analysis of caprine GNAI3 gene.

Goat is the most preferred domesticated animal in Indian subcontinent. However, the climatic change-induced heat stresscauses a formidable challenge for maintaining optimum productivity. G protein subunit alpha i3 (GNAI3) is one of the genes that may have significant role in heat tolerance mechanism in goats. The caprine GNAI3 gene was searched for homology analysis and its three dimensional protein structure was predicted followed by its validation through in silico approach. Nucleotide sequence-based phylogenetic tree analysis showed that the caprine GNAI3 gene has close evolutionary relationship with that of Ovis aries. Homology modelling of caprine GNAI3 protein was done in MODELLER 9.18 (P1), PHYRE2 (P2), GENO3D (P3) and SWISS MODEL (P4). The modelled structures were further validated after observing the Ramachandran and hydrophobicity plots. In the best of three dimensional protein structure (P4 as produced by SWISS MODEL), 330 (98.8%), three (0.9%) and one (0.3%) amino acid residues were found in favoured region, allowed region and outlier region, respectively. Degree of hydrophobicity of the generated protein structures revealed the presence of alternate hydrophobic and hydrophilic regions. The ligand receptor interaction site of the predicted 3D model was traced out using Discovery Studio 3.5. STRING database revealed protein interactions with Plcb1, Plcb2, Plcb3 and other proteins of G family such as Gnb1, Gnb2, Gnb3,Gnb4, Gng2, Gng4 and Gpsm1. KEGG pathway maps revealed interaction with eNOS, iNOS, VEGF and MAPK, which are reported to be transcribed in response to heat stress. Thus, caprine GNAI3 can be used as a possible biomarker for studying heattolerance mechanism in goats.

Electrocardiographic reference values and configuration of electrocardiogram waves recorded in Black Bengal goats of different age groups.

AIM: A study on age-related electrocardiographic (ECG) changes was conducted on 20 apparently healthy Black Bengal goats with no history of cardiac disorders during 2015-2016. MATERIALS AND METHODS: The goats selected for the study belonged to four different age groups; Group 1: Goats up to 6 months of age, Group 2: Above 6 months and below 1 year of age, Group 3: Above 1 year and below 2 years of age, and Group 4: Above 2 years of age. The ECG was recorded with the animals in standing position using a 12-lead standard ECG recorder (Model-Cardiart-108 MK VII, manufactured by BPL, India). The paper speed was set to 25 mm/s with the sensitivity of the machine was adjusted at 1 (1 cm=mV). RESULTS: The ECG parameters were compared within different age groups, and the data were analyzed statistically using SPSS 16.0 taking a significant level of 95% (p<0.05) in all cases. The lead-I ECG revealed a significant difference in amplitude of QRS complex, PR interval, QT interval, RR interval, PQ segment, ST segment, TP segment, and heart rate among some age groups. In bipolar limb lead-II, the amplitude of T-wave, RR interval, ST segment, TP segment, and heart rate was a significant difference among some age groups. Lead-III presented significant difference among age groups in different parameters such as QRS complex duration, T-wave duration, RR interval, ST segment, TP segment, and heart rate. CONCLUSION: The study concluded that there is a significant variation in the ECG parameters both in terms of values and configuration of ECG waves when age is taken into consideration. The results of the study might be used as a reference value for field veterinarians.

Loop mediated isothermal amplification: An innovative gene amplification technique for animal diseases.

India being a developing country mainly depends on livestock sector for its economy. However, nowadays, there is emergence and reemergence of more transboundary animal diseases. The existing diagnostic techniques are not so quick and with less specificity. To reduce the economy loss, there should be a development of rapid, reliable, robust diagnostic technique, which can work with high degree of sensitivity and specificity. Loop mediated isothermal amplification assay is a rapid gene amplification technique that amplifies nucleic acid under an isothermal condition with a set of designed primers spanning eight distinct sequences of the target. This assay can be used as an emerging powerful, innovative gene amplification diagnostic tool against various pathogens of livestock diseases. This review is to highlight the basic concept and methodology of this assay in livestock disease.

Dimers of nineteen-electron sandwich compounds: crystal and electronic structures, and comparison of reducing strengths.

The dimers of some Group 8 metal cyclopentadienyl/arene complexes and Group 9 metallocenes can be handled in air, yet are strongly reducing, making them useful n-dopants in organic electronics. In this work, the X-ray molecular structures are shown to resemble those of Group 8 metal cyclopentadienyl/pentadienyl or Group 9 metal cyclopentadienyl/diene model compounds. Compared to those of the model compounds, the DFT HOMOs of the dimers are significantly destabilized by interactions between the metal and the central CC σ-bonding orbital, accounting for the facile oxidation of the dimers. The lengths of these CC bonds (X-ray or DFT) do not correlate with DFT dissociation energies, the latter depending strongly on the monomer stabilities. Ru and Ir monomers are more reducing than their Fe and Rh analogues, but the corresponding dimers also exhibit much higher dissociation energies, so the estimated monomer cation/neutral dimer potentials are, with the exception of that of [RhCp2 ]2 , rather similar (-1.97 to -2.15 V vs. FeCp2 (+/0) in THF). The consequences of the variations in bond strength and redox potentials for the reactivity of the dimers are discussed.

Synthesis and electrochemical characterization of hexanuclear platinum bis-pseudohalides.

The hexanuclear phosphido-bridged dication [Pt6(µ-PBu(t)2)4(CO)6](2+), (1)(2+), reacts under mild conditions with pseudo-halide anions (CN(-), NCO(-), NCS(-)) to afford the corresponding neutral bis-substituted clusters Pt6(µ-PBu(t)2)4(CO)4X2 (2, X = CN; 3, X = SCN; 4, X = NCO). The reaction with sodium azide affords 4, which may arise from the formation of the intermediate bis-azido derivative Pt6(µ-PBu(t)2)4(CO)4(N3)2, 5, and CO. These react rapidly with each other affording 4 and N2. Cluster 5 was alternatively prepared as a stable compound by reacting with NaN3 the neutral cluster Pt6(µ-PBu(t)2)4(CO)4(OTf)2, 14, which contains two weakly bonded triflate anions. As expected, 5 reacts with carbon monoxide (1 atm) affording cluster 4 instantaneously and quantitatively. The new pseudo-halide clusters 2-5, which are interesting potential precursors of cluster-containing molecular frameworks, have been characterized by IR and multinuclear NMR spectroscopy. The solid state structures of clusters 2-4 have also been studied by single-crystal X-ray diffractometry. The main features of the molecular structures remain similar to those of many related congeners described previously; in addition, an interesting reversible phase transition was observed in the crystal structure of cluster 3. As their known congeners, the clusters undergo two reversible one-electron reductions and an irreversible oxidation. An excellent linear correlation was found between the redox potentials of the cathodic processes and Lever's ligand parameter E(L).

Ultralow doping in organic semiconductors: evidence of trap filling.

Tail states in organic semiconductors have a significant influence on device performances by acting as traps in charge transport. We present a study of the controlled passivation of acceptor tail states in fullerene C(60) by the addition of electrons introduced by molecular n doping. Using ultralow doping, we are able to successively fill the traps with charges and examine the changes in conductivity, activation energy, mobility, and Fermi-level position. Passivation of the traps leads to an increase of the electron mobility in C(60) by more than 3 orders of magnitude, to reach 0.21 cm(2)/(V s).

n-Doping of organic electronic materials using air-stable organometallics: a mechanistic study of reduction by dimeric sandwich compounds.

Several 19-electron sandwich compounds are known to exist as "2×18-electron" dimers. Recently it has been shown that, despite their air stability in the solid state, some of these dimers act as powerful reductants when co-deposited from either the gas phase or from solution and that this behavior can be useful in n-doping materials for organic electronics, including compounds with moderate electron affinities, such as 6,13-bis[tri(isopropyl)silylethynyl]pentacene (3). This paper addresses the mechanisms by which the dimers of 1,2,3,4,5-pentamethylrhodocene (1 b(2)), (pentamethylcyclopentadienyl)(1,3,5-trialkylbenzene)ruthenium (alkyl=Me, 2 a(2); alkyl=Et, 2 b(2)), and (pentamethylcyclopentadienyl)(benzene)iron (2 c(2)) react with 3 in solution. Vis/NIR and NMR spectroscopy, and X-ray crystallography indicate that the products of these solution reactions are 3(·-) salts of the monomeric sandwich cations. Vis/NIR kinetic studies for the Group 8 dimers are consistent with a mechanism whereby an endergonic electron transfer from the dimer to 3 is followed by rapid cleavage of the dimer cation. NMR crossover experiments with partially deuterated derivatives suggest that the C-C bond in the 1 b(2) dimer is much more readily broken than that in 2 a(2); consistent with this observation, Vis/NIR kinetic measurements suggest that the solution reduction of 3 by 1 b(2) can occur by both the mechanism established for the Group 8 species and by a mechanism in which an endergonic dissociation of the dimer is followed by rapid electron transfer from monomeric 1 b to 3.

n-Doping of organic electronic materials using air-stable organometallics.

Air-stable dimers of sandwich compounds including rhodocene and (pentamethylcyclopentadienyl)(arene)ruthenium and iron derivatives can be used for n-doping electron-transport materials with electron affinities as small as 2.8 eV. A p-i-n homojunction diode based on copper phthalocyanine and using rhodocene dimer as n-dopant shows a rectification ratio of greater than 10(6) at 4 V.

Synthesis and reactivity of boron-, silicon-, and tin-bridged ansa-cyclopentadienyl-cycloheptatrienyl titanium complexes (troticenophanes).

A novel one-pot method was developed for the preparation of [Ti(η(5)-C(5)H(5))(η(7)-C(7)H(7))] (troticene, 1) by reaction of sodium cyclopentadienide (NaCp) with [TiCl(4)(thf)(2)], followed by reduction of the intermediate [(η(5)-C(5)H(5))(2)TiCl(2)] with magnesium in the presence of cycloheptatriene (C(7)H(8)). The [n]troticenophanes 3 (n=1), 4, 8, 10 (n=2), and 11 (n=3) were synthesized by salt elimination reactions between dilithiated troticene, [Ti(η(5)-C(5)H(4)Li)(η(7)-C(7)H(6)Li)]⋅pmdta (2) (pmdta = N,N',N',N'',N''-pentamethyldiethylenetriamine), and the appropriate organoelement dichlorides Cl(2)Sn(Mes)(2) (Mes = 2,4,6-trimethylphenyl), Cl(2)Sn(2)(tBu)(4), Cl(2)B(2)(NMe(2))(2), Cl(2)Si(2)Me(4), and (ClSiMe(2))(2)CH(2), respectively. Their structural characterization was carried out by single-crystal X-ray diffraction and multinuclear NMR spectroscopy. The stanna[1]- and stanna[2]troticenophanes 3 and 4 represent the first heteroleptic sandwich complexes bearing Sn atoms in the ansa bridge. The reaction of 3 with [Pt(PEt(3))(3)] resulted in regioselective insertion of the [Pt(PEt(3))(2)] fragment into the Sn-C(ipso) bond between the tin atom and the seven-membered ring, which afforded the platinastanna[2]troticenophane 5. Oxidative addition was also observed upon treatment of 4 with elemental sulfur or selenium, to produce the [3]troticenophanes [Ti(η(5)-C(5)H(4)SntBu(2))(η(7)-C(7)H(6)SntBu(2))E] (6: E=S; 7: E=Se). The B-B bond of the bora[2]troticenophane 8 was readily cleaved by reaction with [Pt(PEt(3))(3)] to form the corresponding oxidative addition product [Ti(η(5)-C(5)H(4)BNMe(2))(η(7)-C(7)H(6)BNMe(2))Pt(PEt(3))(2)] (9). The solid-state structures of compounds 5, 6, and 9 were also determined by single-crystal X-ray diffraction.

Proton-transfer reactions on hexanuclear platinum clusters: reversible heterolytic cleavage of H2 and C-H activation affording a linear, cluster-containing polymer.

The hexanuclear cluster {Pt(6)}H(2) (2) contains a sterically hindered and chemically stable {Pt(6)} = Pt(6)(mu-PtBu(2))(4)(CO)(4) core, with the six metals forming an edge-bridged tetrahedron. The two hydrides are the reactive sites of the cluster and lie on opposite sides of the cluster, terminally bonded to the two "apical" edge-bridging platinum centres. Indeed, cluster 2 reacts with acids of different acidity (HA = CF(3)SO(3)H, HBF(4), p-CH(3)-C(6)H(4)-SO(3)H, CF(3)COOH, PhCOOH and CH(3)COOH), affording, after evolution of two equivalents of dihydrogen, the corresponding anion-substituted clusters {Pt(6)}A(2) (4). We suggest that the reaction proceeds through a mechanism similar to the one generally accepted for the analogous protonation of mononuclear hydrides, with some of the intermediates partially characterised at low temperature. Interestingly, the reverse reaction, the heterolytic splitting of H(2) by clusters 4, occurs readily under mild conditions. The anions in clusters 4a and 4b (4a: A = CF(3)SO(3), 4b: A = BF(4)) are bonded in the solid state but very easily dissociate in solution and may be substituted under mild conditions by weak ligands, such as CH(2)Cl(2) or CH(3)CN. With dialkyl ethers, the reaction proceeds further with the heterolytic splitting of a C-H bond of the ethereal ligand. This process allowed us to isolate the polymer [{Pt(6)}(CH(2)OCH(2)CH(2)OCH(2))](x) (8), in which the {Pt(6)} cluster units are connected by insulating spacers arising from dimethoxyethane. The results of single-crystal X-ray diffraction studies on 4a and 8 are also reported.

Selective lithiation and phosphane-functionalization of [(eta(7)-C7H7)Ti(eta(5)-C5H5)] (troticene) and its use for the preparation of early-late heterobimetallic complexes.

The cycloheptatrienyl-cyclopentadienyl sandwich complex [(eta(7)-C(7)H(7))Ti(eta(5)-C(5)H(5))] (troticene) can be dilithiated (once at each ring) or selectively monolithiated, either at the seven- or five-membered ring, depending on the reaction conditions. Treatment of the resulting lithiotroticenes with ClPPh(2) afforded the corresponding troticenyl-phosphanes [(eta(7)-C(7)H(6)PPh(2))Ti(eta(5)-C(5)H(4)PPh(2))] (1), [(eta(7)-C(7)H(6)PPh(2))Ti(eta(5)-C(5)H(5))] (2), or [(eta(7)-C(7)H(7))Ti(eta(5)-C(5)H(4)PPh(2))] (3). The use of nBuLi/N,N',N',N'',N"-pentamethyldiethylenetriamine (pmdta) allowed us to isolate the lithium complexes [(eta(7)-C(7)H(6)Li)Ti(eta(5)-C(5)H(4)Li)] x pmdta (4) and [(eta(7)-C(7)H(7))Ti(eta(5)-C(5)H(4)Li)] x pmdta (5), which were structurally characterized by X-ray diffraction analyses. Reaction of the monophosphane 3 with Mo(CO)(6) and [(tht)AuCl] (tht = tetrahydrothiophene) afforded the heterobimetallic complexes [(3)Mo(CO)(5)] (6) and [(3)AuCl] (7) and also the trimetallic species [(3)(2)AuCl] (8). The reaction of trans-[PtCl(2)(SEt(2))(2)] with the diphosphane 1 led to the formation of cis-[(1)PtCl(2)] (9), whereas the complexes trans-[(2)(2)PtCl(2)] (10) and trans-[(3)(2)PtCl(2)] (11) were isolated by reaction of two equivalents of the monophosphanes 2 and 3 with trans-[PtCl(2)(SEt(2))(2)]. The X-ray crystal structures of 6-11 are also reported.