A new insight into ortho-(dimesitylboryl)diphenylphosphines: applications in Pd-catalyzed Suzuki-Miyaura couplings and evidence for secondary π-interaction

ortho-(Dimesitylboryl)phenylphosphines 1 and 2 were applied in Pd-catalyzed Suzuki-Miyaura C-C couplings. Coordination studies were performed in order to rationalize the relationship between structure and reactivity. Full characterization of a Pd(0) complex derived from 1 has evidenced a new coordination mode for phosphine-arylboranes involving secondary π-interaction between one of the mesityl groups at boron and the metal centre.     

Introducing axial chirality into mesoionic 4,4'-bis(1,2,3-triazole) dicarbenes

Mesoionic 4,4'-bis(1,2,3-triazole-5,5'-diylidene) Rh(I) complexes having a C2 chiral 4,4'-axis were accessed from 3-alkyltriazolium salts in virtually complete de. Their structure and configurational integrity were assessed by NMR spectroscopy, X-ray crystallography, and chiral HPLC. Computational analysis of the MICs involved in the reaction suggested the formation of a highly stable and unprecedented cation-carbene intermediate species, which could be evidenced experimentally by cyclic voltammetry analysis.     

Linear SPDEs Driven by Stationary Random Distributions

Using tools from the theory of stationary random distributions developed in It? (Mem. Coll. Sci., Univ. Kyoto, Ser. A: Math., 28:209?C223,?1954) and Yaglom (Theory Probab. Appl., 2:273?C320,?1957), we introduce a new class of processes which can be used as a model for the noise perturbing an SPDE. This type of noise is not necessarily Gaussian, but it includes the spatially homogeneous Gaussian noise introduced in Dalang (Electron. J. Probab. 4(6)?1999), and the fractional noise considered in Balan and Tudor (Stoch. Process. Appl., 120:2468?C2494,?2010). We derive some general conditions for the existence of a random field solution of a linear SPDE with this type of noise, under some mild conditions imposed on the Green function of the differential operator which appears in this equation. This methodology is applied to the study of the heat and wave equations (possibly replacing the Laplacian by one of its fractional powers), extending in this manner the results of Balan and Tudor (Stoch. Process. Appl., 120:2468?C2494,?2010) to the case H<1/2.     

Zero cancellation for general rational matrix functions

The problem of cancelling a specified part of the zeros of a completely general rational matrix function by multiplication with an appropriate invertible rational matrix function is investigated from different standpoints. Firstly, the class of all factors that dislocate the zeros and feature minimal McMillan degree are derived. Further, necessary and sufficient existence conditions together with the construction of solutions are given when the factor fulfills additional assumptions like being J-unitary, or J-inner, either with respect to the imaginary axis or to the unit circle. The main technical tool are centered realizations that deliver a sufficiently general conceptual support to cope with rational matrix functions which may be polynomial, proper or improper, rank deficient, with arbitrary poles and zeros including at infinity. A particular attention is paid to the numerically-sound construction of solutions by employing at each stage unitary transformations, reliable numerical algorithms for eigenvalue assignment and efficient Lyapunov equation solvers.     

Gammasphere上裂变丰中子核核结构若干前沿领域的新进展(Ⅱ:第三和第四部分)(英文)

使用Gammasphere多探测器系统对252Cf裂变源瞬发γ射线进行γ-γ-γ和γ-γ(θ)符合测量,A～100(Z～40,N56)丰中子核区关于形状过渡、形状共存和形状突变的深入研究获得了新的进展。奇-Z核的系统研究揭示了从Z=39(Y)同位素的轴对称大四极形变到Z=43(Tc),44(Ru)和45(Rh)同位素中具有中等四极形变之大三轴形变的过渡。Nb(Z=41)同位素具有过渡核的特征。根据邻近同位素和同中素带交叉信息的系统性及推转壳模型(CSM)计算,Tc和Rh偶-N同位素中观察到的带交叉产生于一对h11/2中子的转动顺排。首次观察到100Nb(Z=41,N=59)的高自旋能级纲图和形变态,从而证实了100Nb中的形状共存,并确认,在Nb同位素链上,基态形状突变发生于N=58(球形)到N=59(大形变);而在Sr(Z=38),Y(Z=39)和Zr(Z=40)各同位素链上,基态形状突变均发生于N=59(球形)到N=60(大形变)。100Nb具有大形变基态,同现有理论预言相矛盾,其大形变的基态及转动带所具有的很大的和不规则的转动惯量具有重要的理论意义。对奇-质子Cs(Z=55)和La(Z=57)丰中子同位素八极激发的详细研究,发现了141,143,144Cs同位素链上电二极矩D0随中子数增加而减小的急剧变化,此前在145,147La中观察到的电二极矩D0的较缓和的减小似乎亦很陡地下延至148La。在Cs和La同位素中观察到的电二极矩D0的急剧下降很可能同偶-质子核146Ba和224Ra中观察到的电二极矩D0的急剧下降相类似,后者已获反射非对称平均场壳修正理论的成功解释。实验证明,141Cs具有很大电二极矩D0。141Cs和142Xe中观测到的很大的电二极矩D0和仅在141Cs中观察到的电二极矩D0的simplex量子数相关性需要进一步的理论研究。根据转动频率比值ω-(I)/ω+(I)的检定,同Xe同位素一样,认定Cs同位素中包括号143Cs的八极激发为八极振动,而在La同位素中存在八极形变。     

0(gs)+ -->2(1)+ transition strengths in 106Sn and 108Sn

The reduced transition probabilities, B(E2; 0(gs)+ -->2(1)+), have been measured in the radioactive isotopes (108,106)Sn using subbarrier Coulomb excitation at the REX-ISOLDE facility at CERN. Deexcitation gamma rays were detected by the highly segmented MINIBALL Ge-detector array. The results, B(E2;0(gs)+ -->2(1)+)=0.222(19)e2b2 for 108Sn and B(E2; 0(gs)+-->2(1)+)=0.195(39)e2b2 for 106Sn were determined relative to a stable 58Ni target. The resulting B(E2) values are approximately 30% larger than shell-model predictions and deviate from the generalized seniority model. This experimental result may point towards a weakening of the N=Z=50 shell closure.     

High-Resolution Tandem Mass Spectrometry Identifies a Particular Ganglioside Pattern in Early Diabetic Kidney Disease of Type 2 Diabetes Mellitus Patients

Considering the valuable information provided by glycosphingolipids as molecular markers and the limited data available for their detection and characterization in patients suffering from Type 2 diabetic kidney disease (DKD), we developed and implemented a superior method based on high-resolution (HR) mass spectrometry (MS) and tandem MS (MS/MS) for the determination of gangliosides in the urine of DKD patients. This study was focused on: (i) testing of the HR MS and MS/MS feasibility and performances in mapping and sequencing of renal gangliosides in Type 2 DM patients; (ii) determination of the changes in the urine gangliosidome of DKD patients in different stages of the disease—normo-, micro-, and macroalbuminuria—in a comparative assay with healthy controls. Due to the high resolution and mass accuracy, the comparative MS screening revealed that the sialylation status of the ganglioside components; their modification by O-acetyl, CH₃COO⁻, O-fucosyl, and O-GalNAc; as well as the composition of the ceramide represent possible markers for early DKD detection, the assessment of disease progression, and follow-up treatment. Moreover, structural investigation by MS/MS demonstrated that GQ1d(d18:1/18:0), GT1α(d18:1/18:0) and GT1b(d18:1/18:0) isomers are associated with macroalbuminuria, meriting further investigation in relation to their role in DKD.     

Long-range response to transmission line disturbances in DC electricity grids

We consider a DC electricity grid composed of transmission lines connecting power generators and consumers at its nodes. The DC grid is described by nonlinear equations derived from Kirchhoff's law. For an initial distribution of consumed and generated power, and given transmission line conductances, we determine the geographical distribution of voltages at the nodes. Adjusting the generated power for the Joule heating losses, we then calculate the electrical power flow through the transmission lines. Next, we study the response of the grid to an additional transmission line between two sites of the grid and calculate the resulting change in the power flow distribution. This change is found to decay slowly in space, with a power of the distance from the additional line. We find the geographical distribution of the power transmission, when a link is added. With a finite probability the maximal load in the grid becomes larger when a transmission line is added, a phenomenon that is known as Braess’ paradox. We find that this phenomenon is more pronounced in a DC grid described by the nonlinear equations derived from Kirchhoff's law than in a linearised flow model studied previously in Ref. [1]. We observe furthermore that the increase in the load of the transmission lines due to an added line is of the same order of magnitude as Joule heating. Interestingly, for a fixed system size the load of the lines increases with the degree of disorder in the geographical distribution of consumers and producers.     

Evidence for excited states in 95Ag

The first evidence for excited states in ⁹⁵Ag is presented. ⁹⁵Ag is the heaviest T _z = 1/2 nucleus for which gamma-rays have been identified. The reaction ⁴⁰Ca(⁵⁸Ni, 1p2n)⁹⁵Ag was used in the experiment, which resulted in the assignment of three gamma-rays to ⁹⁵Ag. A detector system consisting of the detector arrays Euroball, Neutron Wall and Euclides was used to detect gamma-rays, neutrons and charged particles, respectively. Received: 31 May 2002 / Accepted: 8 July 2002     

Formation, characterization, and chemistry of undecanoic acid-terminated silicon surfaces: patterning and immobilization of DNA

This paper describes a simple strategy for DNA immobilization on chemically modified and patterned silicon surfaces. The photochemical modification of hydrogen-terminated Si(111) with undecylenic acid leads to the formation of an organic monolayer covalently attached to the surface through Si-C bonds without detectable reaction of the carboxylic acid group, providing indirect support of a free radical mechanism. Chemical activation of the acid function was achieved by a simple chemical route using N-hydroxysuccinimide (NHS) in the presence of N-ethyl-N'-(3-dimethylaminopropyl) carbodiimide hydrochloride. Single strand DNA with a 5'-dodecylamine group was then coupled to the NHS-activated surface by amide bond formation. Using a previously reported chemical patterning approach, we have shown that DNA can be immobilized on silicon surfaces in spatially well-resolved domains. Methoxytetraethyleneglycolamine was used to inhibit nonspecific adsorption. The resulting DNA-modified surfaces have shown good specificity and chemical and thermal stability under hybridization conditions. The sequential reactions on the surface were monitored by ATR-FTIR, X-ray Photoelectron Spectroscopy, and fluorescence spectroscopy.