Reaction Of Bis Research Articles

Synthesis and structural characterization of a novel large type double-layered cyclophanes based on the reaction of bis(N-alkylene benzothiazolium) dibromide and triethylamine

The synthesis of a novel large type double-layered cyclophanes has been successfully accomplished by free radical coupling reaction with the bis(N-alkylene benzothiazolium) dibromide salts as their important synthetic intermediates. The structures of the two-layered cyclophanes and the synthetic intermediates have been elucidated based on the NMR data and X-ray structural analysis, respectively. The two-layered cyclophanes consist of two different geometries, anti-two cyclic lactam amide rings inside and two bridges of disulfide bonds outside, which are unique and novel structures. Their physical properties were investigated by UV–Vis and redox potential, too.

Differential cross-section measurement for 10B(p, αγ1)7Be, 10B(p, p’γ1)10B and 11B(p, p’γ1) 11B reactions

Differential cross-sections of the 10B(p, αγ1)7Be (Eγ = 429 keV), 10B(p, p’γ1)10B (Eγ = 718 keV) and 11B(p, p’γ1) 11B (Eγ = 2124 keV) reactions have been measured at proton laboratory energies of 912–2776 keV at 90°. The proton beam impinged on a thin natB2O3 film evaporated onto a self-supporting thin carbon layer. The incident energies were increased by 10 (20) keV steps in the resonance (off-resonance) regions. Our data are compared with the existing ones from literature. A benchmark procedure was performed by comparing the calculated thick-target yields from the current differential cross-sections with the existing measured thick target gamma-ray yields. The overall systematic uncertainty of the cross-sections was estimated to be about 10 %, mainly related to the target thickness determination.

Boron Neutron Capture Therapy-Derived Extracellular Vesicles via DNA Accumulation Boost Antitumor Dendritic Cell Vaccine Efficacy.

Radiated tumor cell-derived extracellular vesicles (RT-EVs) encapsulate abundant DNA fragments from irradiated tumor cells, in addition to acting as integrators of multiple tumor antigens. Accumulating evidence indicates these DNA fragments from damaged cells are involved in downstream immune responses, but most of them are degraded in cells before incorporation into derived RT-EVs, thus the low abundance of DNA fragments limits immune responses of RT-EVs. Here, this study found that different radiations affected fates of DNA fragments in RT-EVs. Boron neutron capture therapy (BNCT) induced DNA accumulation in RT-EVs (BEVs) by causing more DNA breaks and DNA oxidation resisting nuclease degradation. This is attributed to the high-linear energy transfer (LET) properties of alpha particles from the neutron capture reaction of 10B. When being internalized by dendritic cells (DCs), BEVs activated the DNA sensing pathway, resulting in functional enhancements including antigen presentation, migration capacity, and cytokine secretion. After vaccination of the BEVs-educated DCs (BEV@BMDCs), the effector T cells significantly expanded and infiltrated into tumors, suggesting robust anti-tumor immune activation. BEV@BMDCs not only effectively inhibited the primary tumor growth and metastasis formation but also elicited long-term immune memory. In conclusion, a successful DC vaccine is provided as a promising candidate for tumor vaccine.

Interplay of single-particle and collective modes in the 12C(p,2p) reaction near 100 MeV

The 12C(p,2p)11B reaction at Ep=98.7 MeV proton beam energy is analyzed using a rigorous three-particle scattering formalism extended to include the internal excitation of the nuclear core or residual nucleus. The excitation proceeds via the core interaction with any of the external nucleons. We assume the 11B ground and low-lying excited states [32− (0.0 MeV), 52− (4.45 MeV), 72− (6.74 MeV)] and the excited states [12− (2.12 MeV), 32− (5.02 MeV)] to be members of K=32− and K=12− rotational bands, respectively. The dynamical core excitation results in a significant cross section for the reaction leading to the 52− (4.45 MeV) excited state of 11B that cannot be populated through the single-particle excitation mechanism. The detailed agreement between the theoretical calculations and data depends on the used optical model parametrizations and the kinematical configuration of the detected nucleons.

Chemical Reaction Modulated Low-Dimensional Phase Toward Highly Efficient Sky-Blue Perovskite Light-Emitting Diodes.

Blue perovskite light-emitting diodes (PeLEDs) are crucial avenues for achieving full-color displays and lighting based on perovskite materials. However, the relatively low external quantum efficiency (EQE) has hindered their progression towards commercial applications. Quasi-two-dimensional (quasi-2D) perovskites stand out as promising candidates for blue PeLEDs, with optimized control over low-dimensional phases contributing to enhanced radiative properties of excitons. Herein, the impact of organic molecular dopants on the crystallization of various n-phase structures in quasi-2D perovskite films. The results reveal that the highly reactive bis(4-(trifluoromethyl)phenyl)phosphine oxide (BTF-PPO) molecule could effectively restrain the formation of organic spacer cation-ordered layered perovskite phases through chemical reactions, simultaneously passivate those uncoordinated Pb2+ defects. Consequently, the prepared PeLEDs exhibited a maximum EQE of 16.6 % (@ 490 nm). The finding provides a new route to design dopant molecules for phase modulation in quasi-2D PeLEDs.

Chemical Reaction Modulated Low‐Dimensional Phase Toward Highly Efficient Sky‐Blue Perovskite Light‐Emitting Diodes

Blue perovskite light‐emitting diodes (PeLEDs) are crucial avenues for achieving full‐color displays and lighting based on perovskite materials. However, the relatively low external quantum efficiency (EQE) has hindered their progression towards commercial applications. Quasi‐two‐dimensional (quasi‐2D) perovskites stand out as promising candidates for blue PeLEDs, with optimized control over low‐dimensional phases contributing to enhanced radiative properties of excitons. Herein, the impact of organic molecular dopants on the crystallization of various n‐phase structures in quasi‐2D perovskite films. The results reveal that the highly reactive bis(4‐(trifluoromethyl)phenyl)phosphine oxide (BTF‐PPO) molecule could effectively restrain the formation of organic spacer cation‐ordered layered perovskite phases through chemical reactions, simultaneously passivate those uncoordinated Pb2+ defects. Consequently, the prepared PeLEDs exhibited a maximum EQE of 16.6% (@ 490 nm). The finding provides a new route to design dopant molecules for phase modulation in quasi‐2D PeLEDs.

Syntheses, Characterization, and Redox Activity of Ferrocene-Containing Titanium Complexes.

The chemistry of bis(π-η5:σ-η1-pentafulvene)titanium complexes is characterized by a broad range of E-H activation and Ti-C functionalization reactions, whereas ferrocene derivatives are easily accessible and redox-active compounds. The reaction of ferrocenealdehyde and -ketones with bis(π-η5:σ-η1-pentafulvene)titanium complexes result in the formation of bimetallic complexes via insertion of the C=O double bond of the aldehyde/ketone into the Ti-Cexo bond of the pentafulvene moiety. The reaction of bis(π-η5:σ-η1-pentafulvene)titanium complexes with ferrocenyl alcohols leads to alcoholate complexes via deprotonation of the OH group by the pentafulvene ligand. Because of the one remaining pentafulvene unit, further functionalization of the complexes is possible. In this work, we proceeded with 1,1'-bifunctionalized ferrocene derivatives for intramolecular follow-up reactions. 1,1'-Ferrocenedimethanol reacts with bis(π-η5:σ-η1-pentafulvene)titanium complexes in a double O-H deprotonation reaction to yield the dialcoholate complex. 1,1'-bis(phenylphosphine)ferrocene reacts differently as the double P-H deprotonation reaction results in the formation of a P-P linked phosphine. Therefore, we studied the reactivity of 1,1'-bis(phenylphosphine)ferrocene toward Rosenthal's reagent. As Rosenthal's reagent is regarded as a masked titanocene(II) species, it undergoes redox reactions toward H-acidic substrates, forming a paramagnetic Ti(III) complex.

M(TEIM) complexes with M as Co and Fe: Analogues of classic M(TIM)

The syntheses and characterization of Fe and Co complexes supported by a new tetra-imine macrocycle, TEIM (2,3,9,10-tetraethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene), are reported. Templating with Co(OAc)2·4H2O yielded trans-[Co(TEIM)Cl2][PF6] (1a), which was converted to trans-[Co(TEIM)X2][PF6] (X = N3 (2a) and NO2 (3a)) through reactions with NaX (X = N3 or NO2). Templating with Fe generated trans-[Fe(TEIM)(NCCH3)2][PF6]2, which was oxidized to trans-[Fe(TEIM)Cl2][PF6] (1b). The reaction of 1b with NaN3 formed [Fe(TEIM)(N3)2][PF6] (2b) while the reaction with [Fe(TEIM)(NCCH3)2][PF6]2 and NaNO2 yielded trans-[Fe(TEIM)(NO2)2] (3b). Single crystal X-ray diffraction studies revealed a pseudo-octahedral geometry around the Co / Fe centers with the ethyl groups oriented above or below the plane of the TEIM ring. The absorption spectra of 1b displays weak charge transfer bands near the UV to visible region, while 2b and 3b displayed intense charge transfer bands within the visible region. Cyclic voltammograms of 1a revealed four 1 e− reductions while those of 2a and 3a display only three cathodically shifted reductions. Analogous studies of 1b and 2b revealed two 1 e- reductions while 3b displays only an oxidation event. EPR studies of ferric complexes 1b and 2b indicated a low spin d5 electronic figuration with S = ½ ground state.

Study of [formula omitted] reactions with polarized photons at energy 40-65 MeV

The photon beam asymmetry of the C12(γ→,p01)11B and C12(γ→,p2−6)11B reactions has been measured in the energy range 40–65 MeV, using a tagged, linearly-polarized photon beam at the MAX-lab facility in Sweden. The asymmetry of the C12(γ→,p01)11B reaction to ground and first excited state of B11 is Σ≈0.82 over the measured energy range. The main contribution to the C12(γ→,p2−6)11B reaction to higher excited states comes from processes in which the residual nucleus is in the 3/2−(5.02MeV) or 7/2−(6.74MeV) excited states. The asymmetry of this reaction is Σ≈0.6, close to the value for free deuteron photodisintegration.

Cryogenic solid deuterium target formation to realize highly pure deuteron acceleration by high-intensity laser

In recent years, laser-driven neutron sources have attracted attention for their applications such as nondestructive analysis and the production of medical radioisotopes. One of the efficient neutron production methods is the use of the 9Be(d, n)10B reaction on a beryllium target with deuterons accelerated by laser–plasma interactions, since this is an exothermic reaction. For efficient deuteron acceleration, we have developed a formation system for solid deuterium targets. A millimeter thick solid deuterium target can be formed with the system. Before the laser shot, the solid deuterium target in the laser chamber can be mechanically moved to the laser irradiation point. We have demonstrated deuteron acceleration by the LFEX laser, and a highly pure deuteron pulse with energies of up to 6.2 MeV was measured with a Thomson parabola ion spectrometer.

Radioisotope production using lasers: From basic science to applications

The discovery of chirped pulse amplification has led to great improvements in laser technology, enabling energetic laser beams to be compressed to pulse durations of tens of femtoseconds and focused to a few micrometers. Protons with energies of tens of MeV can be accelerated using, for instance, target normal sheath acceleration and focused on secondary targets. Under such conditions, nuclear reactions can occur, with the production of radioisotopes suitable for medical application. The use of high-repetition lasers to produce such isotopes is competitive with conventional methods mostly based on accelerators. In this paper, we study the production of 67Cu, 63Zn, 18F, and 11C, which are currently used in positron emission tomography and other applications. At the same time, we study the reactions 10B(p,α)7Be and 70Zn(p,4n)67Ga to put further constraints on the proton distributions at different angles, as well as the reaction 11B(p,α)8Be relevant for energy production. The experiment was performed at the 1 PW laser facility at Vega III in Salamanca, Spain. Angular distributions of radioisotopes in the forward (with respect to the laser direction) and backward directions were measured using a high purity germanium detector. Our results are in reasonable agreement with numerical estimates obtained following the approach of Kimura and Bonasera [Nucl. Instrum. Methods Phys. Res., Sect. A 637, 164–170 (2011)].

Cross section measurement for the 14N(n,α0,1)11B reactions in the 4.5–11.5 MeV neutron energy region

Cross section measurement for the 14N(n,α0,1)11B reactions in the 4.5–11.5 MeV neutron energy region

Zinc‐bis(imino)pyridine Complexes as Catalysts for Intermolecular Amidation of Benzylic C(sp3)−HBond

AbstractEfficient NNN‐pincer type bis(imino)pyridine ligand based zinc(II) catalyzed intermolecular amidation of benzylic hydrocarbons with sulfonamides has been developed. The zinc complexes were synthesized by the reaction of bis(imino)pyridine ligand with zinc(II) precursors such as Zn(OAc)2 ⋅ 2H2Oand ZnBr2. The structure of the bis(imino)pyridine‐Zn(OAc)2 complex was characterized by single crystal X‐ray diffraction. The zinc(II)‐bis(imino)pyridine complexes were utilized as catalysts for the intermolecular amidation of benzylic C(sp3)−H bond in the presence of N‐bromosuccinimide (NBS) as an oxidant. A broad range of substrates delivered the products in moderate to good yields. This protocol provides the synthesis of various amides viaC−H activation.

Germaborene reactivity study - addition of carbon nucleophiles, cycloaddition reactions, coordination chemistry.

MeNHC substituted germaborenium cation 2 was synthesized directly in reaction of bromo-substituted germaborene 1b with MeNHC. The adamantyl isonitrile substituted germaborenium cation 4 was obtained stepwise: substitution of the chloride atom against adamantyl isonitrile at the B-Cl unit in 1a, simultaneous migration of the chloride to the germanium atom followed by chloride abstraction using Na[BArF 4] gives the germaborenium cation 4. Substitution of the bromide atom in 1b against carbon monoxide followed by bromide abstraction using Ag[Al(OtBuF)4] leads to compound 6 exhibiting a B[double bond, length as m-dash]C double bond substituted at the boron atom by a germylium cation. Treating the germaborene [Ge[double bond, length as m-dash]B-Ph] (1c) with selenium, a cycloaddition product 7 was characterised featuring a GeBSe heterocycle. Carbon dioxide reacts with 1b to give a four membered ring molecule 8 as the product of a B-C and Ge-O bond formation. In reaction of 1b with dimethylbutadiene, a product 9 of a [2 + 4] cycloaddition was isolated. Transition metal fragments [Fe(CO)4 (10), CuBr (11), AuCl (12)] show coordination at the germaborene double bond. Molecular structures of the germaborene coordination compounds 10-12 are presented and the ligand properties are discussed. After treating the germaborene [Ge[double bond, length as m-dash]B-Br] (1b) with [Cp*Al]4, insertion of a Cp*Al moiety into the B-Br bond was found (13).

Quantifying variation in cooperative B-H bond activations using Os(ii) and Os(iii) κ2-N,S-chelated complexes: same, but different.

In an effort to investigate small molecule activation by heavier transition metal (TM) based κ2-N,S-chelated species, we have synthesised a series of bis-κ2-1,3-N,S-chelated complexes of osmium, [Os(PPh3)2(κ2-N,S-La/Lb)2], 2a-b, and [Os(PPh3)(La/Lb)(κ2-N,S-La/Lb)2], 3a-b (2a and 3a: La[double bond, length as m-dash] = C7H4NS2; 2b and 3b: Lb = C5H4NS), from the thermolysis of [Os(PPh3)3Cl2], 1, with a potassium salt of heterocyclic ligands La and Lb. The former complexes are diamagnetic in nature, while the EPR spectra, XPS study and density functional theory (DFT) calculations have substantiated the paramagnetic behaviour of 3a-b with a significant spin contribution from non-innocent ligands. These species were engaged in B-H activation of boranes utilizing the combined effect of hemilability and metal-ligand cooperativity (MLC), where 2a-b upon treatment with BH3·SMe2 yielded Os(σ-borate)hydride complexes, [Os(PPh3)2(H){κ3-H,S,S'-BH2(La/Lb)2}], 4a-b (4a: La = C7H4NS2; 4b: Lb = C5H4NS). The formation of 4a-b was emphasized on the basis of possible dual B-H activation that involved a few concerted steps, i.e., (i) cleavage of one hemilabile Os-N bond and cooperative B-H bond activation, (ii) cleavage of another hemilabile Os-N bond and formation of a B-N bond and (iii) activation of another B-H bond. In stark contrast, the paramagnetic bis-κ2-1,3-N,S-chelated species 3a-b manifested diverse activation patterns in the light of the different electronic nature of non-innocent ligands. While the reaction of 3b with borane generated dihydridoborate species, [Os(PPh3)(κ2-N,S-Lb)(κ3-H,H,S'-BH2(OH)C5H4NS)], 5, complex 3a led to the formation of an Os(σ-borate) complex, [Os(PPh3)(κ2-N,S-La)(κ3-H,S,S'-BH2L2 a)], trans-6. As the σ-borate entity shows a tendency to adapt to different spatial arrangements around the metal center, we have established a modified synthetic strategy to isolate the cis isomer of 6 that involved the reaction of [Os(PPh3)3Cl2], 1, with NaBH2La 2. In a similar fashion, the treatment of [Os(PPh3)3Cl2], 1, with NaBH2Lb 2 yielded [Os(PPh3)(κ2-N,S-Lb)(κ3-H,S,S'-BH2L2 b)], cis-7. The kinetic and thermodynamic stability of these isomeric species were investigated on the basis of extensive density functional theory (DFT) calculations. Theoretical calculations also provided insightful information on the electronic nature of the species, generated from B-H activations of boranes.

Exploring cluster structures in the high excitation energy region of Be, B, and C isotopes via 10B + 10B nuclear reactions

The unique opportunity presented by 10B + 10B reactions to study high-energy, high-spin states in the A=10 mass region is explored. Results from the measurement at 72 MeV are presented, the most important being new and rarely seen states in the 12C [1] and 13C [2], which motivate targeted future experiments. In particular, a new state of 12C at Ex = 24.4 MeV is strongly populated in the triple α-particle coincidences, while the rarely seen state at Ex = 30.3 MeV is found to be strong in the d+10B decay channel, reinforcing the previous suggestions that it has the exotic 2α+2d molecular structure [3]. Regarding the 13C nucleus, a potentially novel state at Ex = 19.0 MeV is prominently observed in α+ 9Be coincidences and demonstrates a well-defined cluster structure. Lastly, high-spin states in mirror nuclei pairs 9Be-9B, 10Be-10C and 11B-11C populated in the presented measurement are explored.

Synthesis and Reactivity of Aluminum Disilacyclopropenes. Cyclic AlSi2 Delocalized 2π Systems.

The synthesis, structures, and reactivity of the first unsaturated AlSi2 three-membered ring systems were described. Reactions of dilithiodisilene [(NHB)LiSi═SiLi(NHB)] (1, NHB = diazaborolyl) with aluminum halides AlCl3, Ar(SiMe3)NAlCl2 (Ar = 2,6-iPr2C6H3), Cp*AlBr2 (Cp* = C5Me5), and TipAlBr2·Et2O (Tip = 2,4,6-iPr3C6H2) led to the formation of AlSi2 three-membered ring species, solvated (NHBSi)2AlCl(OEt2) (2) and solvent-free (NHBSi)2AlN(SiMe3) Ar (3), (NHBSi)2AlCp* (4), and (NHBSi)2AlTip (5), in good yields. X-ray diffraction studies and DFT calculations disclosed delocalized AlSi2 2π electron systems. Methanolysis of 4a resulted in cleavage of the Al-Si σ and Si-Si π bonds, giving trihydrodisilane (NHB)H(MeO)SiSiH2 (NHB) (6). Reaction of 4b with 4 equiv of N2O and H2C═CH2 resulted in the insertion of four oxygen atoms and four H2C═CH2 π bonds into all of the Al-Si and Si-Si bonds, yielding the O- and CH2CH2-bridged polycyclic species 7 and 8, demonstrating the synergistic reactivity of the Al-Si and Si-Si bonds in the AlSi2 ring system.

Synthesis and Characterization of Polyazothiazole and Polyacetyltetrazine from Novel Bis-Ketohydrazonoyl Dichlorides

The present work describes the preparation and characterization of new polyazothiazole and polyacetyltrazine polymers in good yields from new bis-(α-ketohydrazonoyl) dichlorides. Synthesis of the new polyazothiazole proceeds through the reaction of bis-(α-ketohydrazonoyl) dichlorides with 1,4-phenylene[bis(carbothioamide)] in a basic medium to afford novel polyazothiazole derivatives. Additionally, the self-polymerization reaction to synthesize polydiacetyltetrazine derivatives based on bis-(α-ketohydrazonoyl) dichlorides is described. The new polyazothiazole and polyacetyltetrazine derivatives were characterized using spectral and thermal techniques.

Lewis Acid-Base Adducts of α-Amino Acid-Derived Silaheterocycles and N-Methylimidazole

In chloroform solution, the reaction of bis(tert-butylamino)dimethylsilane ((tBuNH)2SiMe2) and an α-amino acid (α-amino isobutyric acid, H2Aib; D-phenylglycine, H2Phg; L-valine, H2Val) in the presence of N-methylimidazole (NMI) gave rise to the formation of the pentacoordinate silicon complexes (Aib)SiMe2-NMI, (Phg)SiMe2-NMI and (Val)SiMe2-NMI, respectively. Therein, the amino acid building block was a di-anionic bidentate chelator at the silicon atom. In solution, the complexes were involved in rapid coordination–dissociation equilibria between the pentacoordinate Si complex (e.g., (Aib)SiMe2-NMI) and its constituents NMI and a five-membered silaheterocycle (e.g., (Aib)SiMe2), as shown by 29Si NMR spectroscopy. The energetics of the Lewis acid-base adduct formation and the competing solvation of the NMI molecule by chloroform were assessed with the aid of computational methods. In CDCl3 solution, deuteration of the silaheterocycle NH group proceeded rapidly, with more than 50% conversion within two days. Upon cooling to −44 °C, the chloroform solvates of the adducts (Aib)SiMe2-NMI and (Phg)SiMe2-NMI crystallized from their parent solutions and allowed for their single-crystal X-ray diffraction analyses. In both cases, the Si atom was situated in a distorted trigonal bipyramidal coordination sphere with equatorial Si–C bonds and an equatorial Si–N bond (the one of the silaheterocycle). The axial positions were occupied by a carboxylate O atom of the silaheterocycle and the NMI ligand’s donor-N-atom.

Synthesis of Two Isomers of pyrido/benzo[b][1,4]selenazines: A Selective Catalyst‐Dependent Formation of C−N and C‐Se Bonds

AbstractThis work describes the selective synthesis of a series of pyrido/benzo‐fused 1,4‐selenazines, through the reaction of bis(3‐amino‐2‐pyridyl) or bis(2‐aminophenyl) diselenides with different β‐dicarbonyl compounds. When molecular I2 was used as catalyst, a series of (Z)‐1‐(1H‐pyrido[2,3‐b][1,4]selenazin‐2(3H)‐ylidene)propan‐2‐ones were obtained. On the other hand, in the absence of catalyst, 1‐(2‐methyl‐1H‐pyrido[2,3‐b][1,4]selenazin‐3‐yl)ethan‐1‐ones could be prepared selectively. The structure of the prepared compounds was elucidated by NMR and HRMS analysis and confirmed by single crystal X‐ray diffraction. The versatility of the protocol was demonstrated not only by the access to a variety of 1,4‐selenazine derivatives, but also by the structural diversity in the 1,3‐dicarbonyl precursors, incorporating multifunctionalities in the synthesized heterocycles.