Do Sulfonamides Interact with Aromatic Rings?

Aromatic rings form energetically favorable interactions with many polar groups in chemical and biological systems. Recent molecular studies have shown that sulfonamides can chelate metal ions and form hydrogen bonds, however, it is presently not established whether the polar sulfonamide functionality also interacts with aromatic rings. Here, synthetic, spectroscopic, structural, and quantum chemical analyses on 2,6-diarylbenzenesulfonamides are reported, in which two flanking aromatic rings are positioned close to the central sulfonamide moiety. Fine-tuning the aromatic character by substituents on the flanking rings leads to linear trends in acidity and proton affinity of sulfonamides. This physical-organic chemistry study demonstrates that aromatic rings have a capacity to stabilize sulfonamides via through-space NH–π interactions. These results have implications in rational drug design targeting electron-rich aromatic rings in proteins.     

Synthesis of 4,6‐Dimethyldibenzothiophene and 1,2,3,4‐Tetrahydro‐4,6‐dimethyldibenzothiophene via Tilak Annulation

1,2,3,4‐Tetrahydro‐4,6‐dimethyldibenzothiophene was prepared by coupling 2‐bromo‐3‐methylcyclohexanone with 2‐methylbenzenethiol and annulating the product with the aid of polyphosphoric acid. A mixture of 1,2,3,4‐tetrahydro‐4,6‐dimethyldibenzothiophene and 4,6‐dimethyldibenzothiophene was prepared by coupling 2‐bromo‐3‐methylcyclohex‐2‐en‐1‐one with 2‐methylbenzenethiol and annulating the product with the aid of polyphosphoric acid. 2‐Bromo‐3‐methylcyclohexanone was synthesized by conjugate addition of Me₃Al to 2‐bromocyclohex‐2‐en‐1‐one with CuBr as catalyst and 2‐bromo‐3‐methylcyclohex‐2‐en‐1‐one by bromination? elimination of 3‐methylcyclohex‐2‐en‐1‐one. 1,2,3,4,4a,9b‐Hexahydro‐4,6‐dimethyldibenzothiophene was prepared by reduction of 1,2,3,4‐tetrahydro‐4,6‐dimethyldibenzothiophene with Zn and CF₃COOH.     

On-chip parametric amplification with 26.5 dB gain at telecommunication wavelengths using CMOS-compatible hydrogenated amorphous silicon waveguides

We present what we believe to be the first study of parametric amplification in hydrogenated amorphous silicon waveguides. Broadband on/off amplification up to 26.5?dB at telecom wavelength is reported. Measured nonlinear parameter is 770?W(-) m(-1), nonlinear absorption 28?W(-1) m(-1), bandgap 1.61?eV.     

2,6-二甲基二苯并噻吩加氢脱硫中间体的合成

以2-溴代-3-甲基环己酮和2-溴代-5-甲基环己酮混合物及2-甲基苯硫酚为原料,经耦合、环化及纯化制得1,2,3,4-四氢-2,6-二甲基二苯并噻吩(3);3在三氟乙酸中经锌粉还原合成了1,2,3,4,4a,9b-六氢-2,6-二甲基二苯并噻吩(4).3和4的结构经1H NMR,13C NMR和GC-MS确证.     

Robust maximum weighted independent-set problems on interval graphs

We study the maximum weighted independent-set problem on interval graphs with uncertainty on the vertex weights. We use the absolute robustness criterion and the min–max regret criterion to evaluate solutions. For a discrete scenario set, we find that the problem is NP-hard for each of the robustness criteria; we also provide pseudo-polynomial time algorithms when there is a constant number of scenarios and show that the problem is strongly NP-hard when the set of scenarios is unbounded. When the scenario set is a Cartesian product, we prove that the problem is equivalent to a maximum weighted independent-set problem on the same interval graph but without uncertainty for the first objective function and that the scenario set can be reduced for the second objective function.     

Demonstration of defect modes in coupled microresonator arrays fabricated in silicon-on-insulator technology

We show experimentally the existence of defect modes in mutually coupled microring resonator arrays fabricated in silicon-on-insulator technology. The movements of donor-like and acceptor-like modes are demonstrated for various defect lengths, in good agreement with earlier theoretical prediction.     

Artifact formation due to ethyl thio-incorporation into silylated steroid structures as determined in doping analysis

Trimethylsilylation of target substances in a mixture of N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA), ammonium iodide and ethanethiol is frequently applied for the application of gas chromatography-mass spectrometry (GC-MS) in steroid analysis. However, artifacts were formed when using this mixture to silylate the steroids androsterone and etiocholanolone obtained from a urine matrix. The artifacts were identified as ethyl thio-containing products of the respective trimethylsilyl derivatives. The conversion of the studied products increased slowly as a function of time, was dependent on the presence of the urine matrix and was significantly accelerated by adding diethyl disulfide to the reagent before incubation. Also ethyl thio-incorporation into testosterone and epitestosterone was established. A mechanism for ethyl thio-incorporation is proposed. The conversion achieved after 120-h sample storage at room temperature was insufficient to significantly influence the analysis of androsterone and etiocholanolone under the studied conditions. However, the results provide fundamental insight into the mechanism of silylation and the occurring side-reactions. Moreover, when investigating the formation of new metabolites, the ethyl thio-incorporation can lead to misinterpretation.     

An acoustic description of the vowels of Northern and Southern Standard Dutch

A database is presented of measurements of the fundamental frequency, the frequencies of the first three formants, and the duration of the 15 vowels of Standard Dutch as spoken in the Netherlands (Northern Standard Dutch) and in Belgium (Southern Standard Dutch). The speech material consisted of read monosyllabic utterances in a neutral consonantal context (i.e., /sVs/). Recordings were made for 20 female talkers and 20 male talkers, who were stratified for the factors age, gender, and region. Of the 40 talkers, 20 spoke Northern Standard Dutch and 20 spoke Southern Standard Dutch. The results indicated that the nine monophthongal Dutch vowels /a [see symbol in text] epsilon i I [see symbol in text] u y Y/ can be separated fairly well given their steady-state characteristics, while the long mid vowels /e o ?/ and three diphthongal vowels /epsilon I [see symbol in text]u oey/ also require information about their dynamic characteristics. The analysis of the formant values indicated that Northern Standard Dutch and Southern Standard Dutch differ little in the formant frequencies at steady-state for the nine monophthongal vowels. Larger differences between these two language varieties were found for the dynamic specifications of the three long mid vowels, and, to a lesser extent, of the three diphthongal vowels.