Identifying aspirin polymorphs from combined DFT-based crystal structure prediction and solid-state NMR

A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated ¹H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs.     

3-D vertical ray shooting and 2-D point enclosure, range searching, and arc shooting amidst convex fat objects

We present a new data structure for a set of n convex simply-shaped fat objects in the plane, and use it to obtain efficient and rather simple solutions to several problems including (i) vertical ray shooting—preprocess a set of n non-intersecting convex simply-shaped flat objects in 3-space, whose xy-projections are fat, for efficient vertical ray shooting queries, (ii) point enclosure—preprocess a set C of n convex simply-shaped fat objects in the plane, so that the k objects containing a query point p can be reported efficiently, (iii) bounded-size range searching— preprocess a set C of n convex fat polygons, so that the k objects intersecting a “not-too-large” query polygon can be reported efficiently, and (iv) bounded-size segment shooting—preprocess a set C as in (iii), so that the first object (if exists) hit by a “not-too-long” oriented query segment can be found efficiently. For the first three problems we construct data structures of size O(λ_s(n)log³n), where s is the maximum number of intersections between the boundaries of the (xy-projections) of any pair of objects, and λ_s(n) is the maximum length of (n, s) Davenport-Schinzel sequences. The data structure for the fourth problem is of size O(λ_s(n)log²n). The query time in the first problem is O(log⁴n), the query time in the second and third problems is O(log³n + klog²n), and the query time in the fourth problem is O(log³n).

We also present a simple algorithm for computing a depth order for a set as in (i), that is based on the solution to the vertical ray shooting problem. (A depth order for , if exists, is a linear order of , such that, if K₁, K₂ and K₁ lies vertically above K₂, then K₁ precedes K₂.) Unlike the algorithm of Agarwal et al. (1995) that might output a false order when a depth order does not exist, the new algorithm is able to determine whether such an order exists, and it is often more efficient in practical situations than the former algorithm.     

弱(L_1,L_2)-BLD映射的正则性

本文首先将文［１］中的ＢＬＤ映射推广为弱（Ｌ１，Ｌ２）－ＢＬＤ映射，并证明了如下正则性结果：存在两个可积指数 Ｐ１＝Ｐ１（ｎ，Ｌ１，Ｌ２）＜ｎ＜ｑ１＝ｑ１（ｎ，Ｌ１，Ｌ２），使得对任意弱（Ｌ１，Ｌ２）－ＢＬＤ映射ｆ∈（Ω，Ｒｎ），都有ｆ∈（Ω，Ｒｎ），即ｆ为（Ｌ１，Ｌ２）－ＢＬＤ映射．     

Synthesis of lanthanum–strontium manganites by oxalate-precursor co-precipitation methods in solution and in reverse micellar microemulsion

Nanostructured lanthanum–strontium manganites were synthesized using two different co-precipitation approaches, one in bulk solution, and the other in reverse micelles of CTAB/1-hexanol/water microemulsion. In both cases, precursor cations were precipitated by using oxalic acid. The properties of the materials synthesized by using these two methods were compared in order to reveal potential advantages of the microemulsion-assisted approach. The influence of the annealing conditions on the properties of synthesized manganites was investigated by using X-ray diffraction, transmission electron microscopy, differential thermal analysis, thermogravimetric analysis and magnetic measurements.     

A competitive algorithm in searching for many edges in a hypergraph

We give a competitive algorithm to identify all d defective edges in a hypergraph with d unknown. Damaschke did the d=1 case for 2-graphs, Triesch extended the d=1 case to r-graphs, and Johann did the general d case for 2-graphs. So ours is the first attempt to solve the searching for defective edges problem in its full generality. Further, all the above three papers assumed d known. We give a competitive algorithm where d is unknown.     

Reverse micellar synthesis and properties of nanocrystalline GMR materials (LaMnO3, La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3): Ramifications of size considerations

Nanoparticles of complex manganites (viz. LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃) have been synthesized using the reverse micellar route. These manganites are prepared at 800‡C and the monophasic nature of all the oxides has been established by powder X-ray diffraction studies. TEM studies show an average grain size of 68, 80 and 50 nm for LaMnO₃, La_0.67Sr_0.33MnO₃ and La_0.67Ca{0.33}MnO₃respectively. Ferromagnetic ordering is observed at around 250 K for LaMnO₃, 350 K for La_0.67Sr_0.33MnO₃ and 200 K for La_0.67Ca{0.33}MnO₃. These Curie temperatures correspond well with those reported for bulk materials with similar composition.     

The <Emphasis Type="Italic">M</Emphasis>/<Emphasis Type="Italic">G</Emphasis>/∞ system revisited: finiteness,summability, long range dependence,and reverse engineering

We explore M/G/∞ systems ‘fed’ by Poissonian inflows with infinite arrival rates. Three processes – corresponding to the system's state, workload, and queue-size – are studied and analyzed. Closed form formulae characterizing the system's stationary structure and correlation structure are derived. And, the issues of queue finiteness, workload summability, and Long Range Dependence are investigated. We then turn to devise a ‘reverse engineering’ scheme for the design of the system's correlation structure. Namely: how to construct an M/G/∞ system with a pre-desired ‘target’ workload/queue auto-covariance function. The ‘reverse engineering’ scheme is applied to various examples, including ones with infinite queues and non-summable workloads. AMS Subject Classifications Primary: 60K25; Secondary: 60G55, 60G10     

Studies on the self-assembly behavior of the amphiphilic block copolymer of PSt-b-PAA in apolar solvents with polar fluorescent probe

The block copolymer of polystyrene-b-poly(butyl acrylate) (PSt-b-PBA) with a well-defined structure was synthesized by atom transfer radical polymerization (ATRP); its structure was characterized, and the living polymerization was also validated by gel permeation chromatography, Fourier transform infrared, and ¹H NMR measurements. Then, the amphiphilic block copolymer of polystyrene-b-poly(acrylic acid) (PSt-b-PAA) has been prepared by hydrolysis of PSt-b-PBA, and copolymers of PSt-b-PAA with longer PSt blocks and shorter PAA blocks were obtained by controlling the conditions of ATRP polymerization. The reversed micelle solution of PSt-b-PAA in toluene was prepared by using the single-solvent dissolving method, and the reverse micellization behavior of PSt-b-PAA in toluene was mainly investigated in this paper. The fluorescent probe technique was used by using polar fluorescence compound N-(1-Naphthyl)ethylenediamine dihydrochloride (NEAH) as a polar fluorescent probe to study the reverse micellization behavior of PSt-b-PAA. It was found that the reverse micellization behaviors of PSt-b-PAA in toluene can be clearly revealed by using NEAH as a polar fluorescence probe, and the critical micelle concentrations (cmcs) can be well displayed. The experimental results showed that the self-assembling behavior of PSt-b-PAA in toluene depends apparently on the microstructure of the macromolecules and is also influenced by the temperature. For the copolymers of PSt-b-PAA with the same length of hydrophobic PSt blocks, the copolymer with a longer hydrophilic block PAA has lower cmc, and at higher temperature, the copolymer has lower cmc.