Heideenemark4120

031) and a smaller extent of resection (p=0.0086) were associated with a shorter MT-free survival.

In our series, less extensive resections were associated with a shorter time to MT. Our data support an adoption of techniques enabling extensive G2G resections, such as intraoperative imaging and awake resections, into everyday routine (Tab. 1, Fig. 2, Ref. 40).

In our series, less extensive resections were associated with a shorter time to MT. Our data support an adoption of techniques enabling extensive G2G resections, such as intraoperative imaging and awake resections, into everyday routine (Tab. 1, Fig. 2, Ref. 40).Three new lead-free organic-inorganic metal halides (OIMHs) (C7H8N3)3InX6·H2O (X = Cl, Br) and (C7H8N3)2SbBr5 were synthesized. First-principles calculations indicate that the highest occupied molecular orbitals (HOMOs) of the two In-based OIMHs are constituted of π orbitals from [C7H8N3]+ spacers. (C7H8N3)3InX6·H2O (X = Cl, Br) shows an indirect optical gap, which may result from this organic-contributed band edge. Despite the indirect-gap nature with extra phonon process during absorption, the photoluminescence of (C7H8N3)3InBr6·H2O can still be significantly enhanced through Sb doping, with the internal photoluminescence quantum yields (PLQY) increased 10-fold from 5% to 52%. A white light-emitting diode (WLED) was fabricated based on (C7H8N3)3InBr6·H2OSb3+, exhibiting a high color-rendering index of 90. Our work provides new systems to deeply understand the principles for organic spacer choice to obtain the 0D metal OIMHs with specific band structure and also the significant enhancement of luminescence performance by chemical doping.Luquilloamides A-G (1-7) were isolated from a small environmental collection of a marine cyanobacterium found growing on eelgrass (Zostera sp.) near Luquillo, Puerto Rico. Structure elucidation of the luquilloamides was accomplished via detailed NMR and MS analyses, and absolute configurations were determined using a combination of advanced Mosher's method, J-based configuration analysis, semisynthetic fragment analysis derived from ozonolysis, methylation, Baeyer-Villiger oxidation, Mosher's esterification, specific rotations, and ECD data. Except for 2, the luquilloamides share a characteristic tert-butyl-containing polyketide fragment, β-alanine, and a proposed highly modified polyketide extension. While compound 1 is a linear lipopeptide with two α-methyl branches and a vinyl chloride functionality in the polyketide portion, compounds 4, 6, and 7 possess a cyclohexanone structure with methylation on the α- or β-positions of the polyketide as well as an acetyl group. Interestingly, the absolute configuration at C-5 and C-6 on the cyclohexanone unit in 7 is opposite to that of 4-6. Compound 3 was revealed to have a tert-butyl-containing polyketide, β-alanine, and a PKS/NRPS-derived γ-isopropyl pyrrolinone. Compound 2 may be a hydrolysis product of 3. Of the seven new compounds, 1 showed the most potent cytotoxicity to human H-460 lung cancer cells.Resonantly stabilized free radicals (RSFRs) have been contemplated as fundamental molecular building blocks and reactive intermediates in molecular mass growth processes leading to polycyclic aromatic hydrocarbons (PAHs) and carbonaceous nanoparticles on Earth and in deep space. By combining molecular beams and computational fluid dynamics simulations, we provide compelling evidence on the formation of benzene via the cyclopentadienyl-methyl reaction and of naphthalene through the cyclopentadienyl self-reaction, respectively. These systems offer benchmarks for the conversion of a five-membered ring to the 6π-aromatic (benzene) and the generation of the simplest 10π-PAH (naphthalene) at elevated temperatures. These results uncover molecular mass growth processes from the "bottom up" via RSFRs in high temperature circumstellar environments and combustion systems expanding our fundamental knowledge of the organic, hydrocarbon chemistry in our universe.With 8-(methyltosylaminoethynyl)-1-naphthyl (MTAEN) glycoside as donors, a novel and efficient glycosylation protocol has been established. The MTAEN glycosylation protocol exhibits the merits of shelf-stable donors, mild catalytic promotion conditions, considerably extended substrate scope encompassing both free alcohols, silylated alcohols, nucleobases, primary amides, and C-type nucleophile acceptors, and applicability to various one-pot strategies for highly efficient synthesis of oligosaccharides, such as orthogonal one-pot, single-catalyst one-pot, and acceptor reactivity-controlled one-pot strategies.Because of their nucleophilic character and high reactivity, enols─reaction intermediates carrying a hydroxyl group connected to a carbon-carbon double bond─play a key role in the formation of complex organic molecules in astrobiology and biochemistry. Here, we report the first bottom-up preparation of 1,1-ethenediol (H2CC(OH)2)─the simplest unsaturated geminal enol of acetic acid (CH3COOH) and potential precursor for the formation of glycine─in interstellar analogue ices of carbon dioxide and methane processed by proxies of galactic cosmic rays. These enols can easily form via nonequilibrium chemistry in low temperature (10 K) interstellar ices at abundances orders of magnitude higher than thermodynamically predicted. These energetically less favorable tautomers remain stable in ice-coated interstellar nanoparticles in molecular clouds and also upon sublimation into the gas phase in star forming regions thus providing the raw material to a complex and exotic organic chemistry under extreme conditions in deep space.α-Tertiary hydroxyimines were stereoselectively synthesized from enantioenriched N-tert-butanesulfinyl ketimines using potassium tert-butoxide, molecular oxygen, and trimethyl phosphite. The stereoselective hydroxylation of acyclic ketimines bearing two sterically similar α-substituents was achieved by controlling the geometry of the metalloenamine intermediates and the facial selectivity of hydroxylation. The synthetic utility of the resulting α-tertiary hydroxyimines was demonstrated through the successful diastereoselective synthesis of highly substituted β-amino alcohols.In this study, Wadsley B phase vanadium oxide (VO2(B)) with broad-band photoabsorption ability, a large temperature coefficient of resistance (TCR), and low noise was developed for uncooled broad-band detection. By using a freestanding structure and reducing the size of active area, the VO2(B) photodetector shows stable and excellent performances in the visible to the terahertz region (405 nm to 0.88 mm), with a peak TCR of -4.77% K-1 at 40 °C, a peak specific detectivity of 6.02 × 109 Jones, and a photoresponse time of 83 ms. A terahertz imaging ability with 30 × 30 pixels was demonstrated. Scanning photocurrent imaging and real-time temperature-photocurrent measurements confirm that a photothermal-type bolometric effect is the dominating mechanism. The study shows the potential of VO2(B) in applications as a new type of uncooled broad-band photodetection material and the potential to further raise the performance of broad-band photodetectors by structural design.A novel DMF-assisted radical cyclization of o-isocyanodiaryl ethers via 1,5-aryl migration has been developed for the synthesis of a series of 2-arylbenzoxazoles by the FeCl3/TBHP/Et3N catalytic system in DMF. However, N,N-dimethylbenzo[d]thiazole-2-carboxamide and N,N-dimethylbenzo[d]selenazole-2-carboxamide were obtained from the corresponding substrate 2-isocyanophenyl p-methoxyphenyl thioether and 2-isocyanodiphenyl selenoether under the same conditions. A possible mechanism may involve aryl 1,5-migration and DMF-assisted radical cyclization of o-isocyanodiaryl ethers.Liposomes, molecular self-assemblies resembling biological membranes, are a promising scaffold to investigate the physicochemical logic behind the complexity of living cells. Despite elaborate synthetic studies constructing cell-like chemical systems using liposomes, less attention has been paid to the proactive role of the membrane emerging as dynamics of the molecular self-assembly. This study investigated the liposomes containing anionic phospholipids by exposing them to steady flow conditions using a newly constructed automatic microfluidic observation platform. We demonstrated that the liposomes accumulated even macromolecules under the microfluidic condition without pore formation. By investigating the effect of composition of liposomes and visualizing negatively charged phospholipids upon the flow, we presumed that the external flow caused a compositional asymmetry of anionic phospholipids between the inner/outer leaflets, and the asymmetry enabled a rapid accumulation of those molecules against the concentration gradient. The current study opens new research interests regarding the nature of biological membranes under steady flow conditions.Surfactant-laden sessile droplet evaporation plays a crucial role in a variety of omnipresent natural and technological applications, such as drying, coating, spray, and inkjet printing. Surfactant molecules can adsorb easily on interfaces and, hence, destructively ruin the useful gas-trapping wetting state (i.e., Cassie-Baxter, CB) of a drop on superhydrophobic (SH) surfaces. PI4KIIIbeta-IN-10 However, the influence of surfactant adsorption or concentration on evaporation modes has been rarely investigated so far. Here, we investigate the evaporation dynamics of aqueous didodecyldimethylammonium bromide (DDAB) sessile droplet on SH surfaces made of regular hydrophobic micropillars, with various dimensionless surfactant concentrations (CS), primarily using experiments. We find that all drops initially form a CB state with a pinned base radius and evaporate in a mode of constant contact radius (CCR). Water and low-CS (=0.02) drop subsequently evaporate with a constant contact angle (CCA) mode, followed by a CCR mode and, eventually, a mixed-mode. By contrast, high-CS (of 0.25-1) droplets undergo a complex mixed mode, with rapidly increasing base radius, and finally a mixed mode, with slowly decreasing base radius and contact angle. The experimental data reveal that contact-angle-dependent evaporative mass flux, ṁ, collapses onto a nearly universal curve depending on CS. For the low-CS (of 0-0.25) drops, ṁ is lower and consistent with an evaporative cooling model, whereas high-CS (of 0.5-1) droplets are consistent with a pure vapor-diffusive model. We further show that the critical CS delineating these two evaporative models correlates with saturated surfactant adsorption on both liquid-solid and liquid-vapor interfaces.A general and efficient palladium catalyzed hydroalkynylation of allenes was developed to produce synthetically versatile (E)-1,3-enyne derivatives with high regio- and stereoselectivity. This catalytic system proceeded under mild conditions and was compatible with a broad range of substrates, especially for allenes without electron-bias groups. This work further broadens the synthetic potential of these scaffolds in organic synthesis and medicinal chemistry.We have previously reported that neoechinulin B (1a), a prenylated indole diketopiperazine alkaloid, shows antiviral activities against hepatitis C virus (HCV) via the inactivation of the liver X receptors (LXRs) and the resultant disruption of double-membrane vesicles. In this study, a two-step synthesis of the diketopiperazine scaffold of 1a was achieved by the base-induced coupling of 1,4-diacetyl-3-[(tert-butyldimethylsilyl)oxy]methylpiperazine-2,5-dione with aldehydes, followed by the treatment of the resultant coupling products with tetra-n-butylammonium fluoride. Compound 1a and its 16 derivatives 1b-q were prepared using this method. Furthermore, variecolorin H, a related alkaloid, was obtained by the acid treatment of 1a in MeOH. The antiviral evaluation of 1a and its derivatives revealed that 1a, 1c, 1d, 1h, 1j, 1l, and 1o exhibited both anti-HCV and anti-severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) activities. The results of this study indicate that the exomethylene moiety on the diketopiperazine ring is important for the antiviral activities.