Edge Functionalization of Bulk γ-Graphyne Facilitates Mechanical Exfoliation and Modulates the Mode of Sheet Stacking.

We have successfully achieved selective and efficient functionalization of sheet edges in microcrystalline multilayer γ-graphyne through two methods: cross-coupling with residual bromide edge groups and copper-catalyzed azide-alkyne cycloaddition (CuAAC) with edge terminal alkyne groups. This modification significantly enhances the ease of mechanical exfoliation and dispersibility of the sheets of γ-graphyne. Specifically, C18-grafted γ-graphyne forms stable dispersions in compatible organic solvents, allowing for the imaging of atomically thin layers of γ-graphyne for the first time. Additionally, we have discovered that phenylacetylide edge groups alter the preferred stacking mode of γ-graphyne sheets. Few-layer flakes of Ph-edge γ-graphyne exhibit a preference for the R3m space group, contrasting with the aperiodic stacking of Br-edge γ-graphyne. These results open the door for scalable exfoliation of few-layer flakes of γ-graphyne with a high aspect ratio, enabling potential applications in carbon electronics.

Scalable Synthesis and Characterization of Multilayer γ-Graphyne, New Carbon Crystals with a Small Direct Band Gap.

γ-Graphyne is the most symmetric sp2/sp1 allotrope of carbon, which can be viewed as graphene uniformly expanded through the insertion of two-carbon acetylenic units between all the aromatic rings. To date, synthesis of bulk γ-graphyne has remained a challenge. We here report the synthesis of multilayer γ-graphyne through crystallization-assisted irreversible cross-coupling polymerization. A comprehensive characterization of this new carbon phase is described, including synchrotron powder X-ray diffraction, electron diffraction, lateral force microscopy, Raman spectroscopy, infrared spectroscopy, and cyclic voltammetry. Experiments indicate that γ-graphyne is a 0.48 eV band gap semiconductor, with a hexagonal a-axis spacing of 6.88 Å and an interlayer spacing of 3.48 Å, which is consistent with theoretical predictions. The observed crystal structure has an aperiodic sheet stacking. The material is thermally stable up to 240 °C but undergoes transformation at higher temperatures. While conventional 2D polymerization and reticular chemistry rely on error correction through reversibility, we demonstrate that a periodic covalent lattice can be synthesized under purely kinetic control. The reported methodology is scalable and inspires extension to other allotropes of the graphyne family.

Time-Domain Analysis of Molecular Dynamics Trajectories Using Deep Neural Networks: Application to Activity Ranking of Tankyrase Inhibitors.

Molecular dynamics simulations provide valuable insights into the behavior of molecular systems. Extending the recent trend of using machine learning techniques to predict physicochemical properties from molecular dynamics data, we propose to consider the trajectories as multidimensional time series represented by 2D tensors containing the ligand-protein interaction descriptor values for each time step. Similar in structure to the time series encountered in modern approaches for signal, speech, and natural language processing, these time series can be directly analyzed using long short-term memory (LSTM) recurrent neural networks or convolutional neural networks (CNNs). The predictive regression models for the ligand-protein affinity were built for a subset of the PDBbind v.2017 database and applied to inhibitors of tankyrase, an enzyme of the poly(ADP-ribose)-polymerase (PARP) family that can be used in the treatment of colorectal cancer. As an additional test set, a subset of the Community Structure-Activity Resource (CSAR) data set was used. For comparison, the random forest and simple neural network models based on the crystal pose or the trajectory-averaged descriptors were used, as well as the commonly employed docking and molecular mechanics Poisson-Boltzmann surface area (MM-PBSA) scores. Convolutional neural networks based on the 2D tensors of ligand-protein interaction descriptors for short (2 ns) trajectories provide the best accuracy and predictive power, reaching the Spearman rank correlation coefficient of 0.73 and Pearson correlation coefficient of 0.70 for the tankyrase test set. Taking into account the recent increase in computational power of modern GPUs and relatively low computational complexity of the proposed approach, it can be used as an advanced virtual screening filter for compound prioritization.

Amplification of chirality through self-replication of micellar aggregates in water.

We describe a system in which the self-replication of micellar aggregates results in a spontaneous amplification of chirality in the reaction products. In this system, amphiphiles are synthesized from two "clickable" fragments: a water-soluble "head" and a hydrophobic "tail". Under biphasic conditions, the reaction is autocatalytic, as aggregates facilitate the transfer of hydrophobic molecules to the aqueous phase. When chiral, partially enantioenriched surfactant heads are used, a strong nonlinear induction of chirality in the reaction products is observed. Preseeding the reaction mixture with an amphiphile of one chirality results in the amplification of this product and therefore information transfer between generations of self-replicating aggregates. Because our amphiphiles are capable of catalysis, information transfer, and self-assembly into bounded structures, they present a plausible model for prenucleic acid "lipid world" entities.

Perceptual validation of sound environment reproduction inside an aircraft mock-up.

Auditory comfort evaluations are garnering increased attention in engineering and particularly in the context of air transportation. Being able to produce sound environments corresponding to various flight conditions in aircraft mock-ups would be a valuable tool to investigate acoustic comfort inside aircrafts in controlled environments. Before using such mock-ups, they must be developed and validated in physical and perceptual terms. This paper provides a perceptual validation of sound environment reproduction inside aircraft mock-up. To provide a faithfully reproduced sound environment, time, frequency and spatial characteristics should be preserved. Physical sound field reproduction approaches for spatial sound reproduction are required while properly preserving localization cues at the listener's ears to recreate a realistic and immersing sound environment. We report a perceptual validation of a sound field reproduction system developed in an aircraft mock-up based on multichannel least-square methods and equalization. Twenty participants evaluated reproduced sound environments relative to a reference sound environment in an aircraft cabin mock-up equipped with a 41-actuator multichannel sound reproduction system. Results indicate that the preferred reproduction corresponds to the best physical reconstruction of the sound environment.

Thiols make for better catalysts: Au nanoparticles supported on functional SBA-15 for catalysis of Ullmann-type homocouplings.

A strategy for arraying small gold nanoparticles on a mesoporous support modified with single-component or mixed self-assembled monolayers is described. The use of mixed surface modifiers allows easy access to a range of surface chemistries and modalities of interaction between nanoparticles and supports. A combination of thiol groups and linear semifluorinated chains effectively stabilized the nanoparticles against aggregation, while preserving their catalytic activity. The thiol-fluorous-supported catalyst was found active in Ullmann-type homocoupling of aryl halides and showed exceptional selectivity in this reaction.

Cooperative organocatalysis of Mukaiyama-type aldol reactions by thioureas and nitro compounds.

A unique organocatalytic system for Mukaiyama-type aldol reactions based on the cooperative action of nitro compounds and thioureas has been identified. This system is compatible with a wide range of substrates and does not require low temperatures, inert atmospheres, or an aqueous workup. A catalytic mechanism based on nitro group-mediated silyl cation transfer has been proposed.

Palladium N-Heterocyclic Carbene Precatalyst Site Isolated in the Core of a Star Polymer.

An approach for supporting a Pd-NHC complex on a soluble star polymer with nanoscale dimensions is described. The resulting star polymer catalyst exhibits excellent activity in cross-coupling reactions, is stable in air and moisture, and is easily recoverable and recyclable. These properties are distinct and unattainable with the small-molecule version of the same catalyst.

Cooperative catalysis with block copolymer micelles: a combinatorial approach.

A rapid approach to identifying complementary catalytic groups using combinations of functional polymers is presented. Amphiphilic polymers with "clickable" hydrophobic blocks were used to create a library of functional polymers, each bearing a single functionality. The polymers were combined in water, yielding mixed micelles. As the functional groups were colocalized in the hydrophobic microphase, they could act cooperatively, giving rise to new modes of catalysis. The multipolymer "clumps" were screened for catalytic activity, both in the presence and absence of metal ions. A number of catalyst candidates were identified across a wide range of model reaction types. One of the catalytic systems discovered was used to perform a number of preparative-scale syntheses. Our approach provides easy access to a range of enzyme-inspired cooperative catalysts.

The Monte Carlo method based on eclectic data as an efficient tool for predictions of endpoints for nanomaterials - two examples of application.

The theoretical predictions of endpoints related to nanomaterials are attractive and more efficient alternatives for their experimental determinations. Such type of calculations for the "usual" substances (i.e. non nanomaterials) can be carried out with molecular graphs. However, in the case of nanomaterials, descriptors traditionally used for the quantitative structure--property/activity relationships (QSPRs/QSARs) do not provide reliable results since the molecular structure of nanomaterials, as a rule, cannot be expressed by the molecular graph. Innovative principles of computational prediction of endpoints related to nanomaterials extracted from available eclectic data (technological attributes, conditions of the synthesis, etc.) are suggested, applied to two different sets of data, and discussed in this work.

[Xanthogranulomatous cholecystitis]. / Colecistitis xantogranulomatosa.

Ten cases of xanthogranulomatous cholecystitis are presented, 5 women and 5 men, from a total of 439 cholecystectomies (2.2%). In 50% of cases the clinical course was consistent with acute cholecystitis; in 30%, gallbladder cancer was suspected preoperatively; and in 70% of cases cancer was suspected during surgery but intraoperative biopsies showed no malignancy. Definitive pathological findings included early carcinoma of the gallbladder in two patients, and a cholecystocolic fistula in one patient. A perforated gallbladder was found in one patient. The incidence of postoperative septic complications was 18.1%, a figure that doubles that of elective biliary surgery in our hospital.

One-pot synthesis of Au@SiO(2) catalysts: a click chemistry approach.

Using the copper-catalyzed azide-alkyne cycloaddition "click" reaction, a library of triazole amphiphiles with a variety of functional polar "heads" and hydrophobic or superhydrophobic "tails" was synthesized. The amphiphiles were evaluated for their ability to stabilize small Au nanoparticles, and, at the same time, serve as templates for nanocasting porous SiO2. One of the Au@SiO2 materials thus prepared was found to be a highly active catalyst for the Au nanoparticle-catalyzed regioselective hydroamination of alkynes.

Transition-metal-free catalytic synthesis of 1,5-diaryl-1,2,3-triazoles.

1,5-Diarylsubstituted 1,2,3-triazoles are formed in high yield from aryl azides and terminal alkynes in DMSO in the presence of catalytic tetraalkylammonium hydroxide. The reaction is experimentally simple, does not require a transition-metal catalyst, and is not sensitive to atmospheric oxygen and moisture.

Benzimidazole and related ligands for Cu-catalyzed azide-alkyne cycloaddition.

Tris(2-benzimidazolylmethyl)amines have been found to be superior accelerating ligands for the copper(I)-catalyzed azide-alkyne cycloaddition reaction. Candidates bearing different benzimidazole N-substituents as well as benzothiazole and pyridyl ligand arms were evaluated by absolute rate measurements under relatively dilute conditions by aliquot quenching kinetics and by relative rate measurements under concentrated conditions by reaction calorimetry. Benzimidazole-based ligands with pendant alkylcarboxylate arms proved to be advantageous in the latter case. The catalyst system was shown to involve more than one active species, providing a complex response to changes in pH and buffer salts and the persistence of high catalytic rate in the presence of high concentrations of coordinating ligands. The water-soluble ligand (BimC4A)3 was found to be especially convenient for the rapid and high-yielding synthesis of several functionalized triazoles with 0.01-0.5 mol % Cu.

Ligand-accelerated Cu-catalyzed azide-alkyne cycloaddition: a mechanistic report.

The experimental rate law for the Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction was found to vary in complex ways with concentration, the presence of chloride ion, and the presence of accelerating ligands. Several examples of discontinuous ("threshold behavior") kinetics were observed, along with a decidedly nonlinear correlation of electronic substituent parameter with the rate of CuAAC reaction with p-substituted arylazides. The previously observed tendency of the CuAAC reaction to provide ditriazoles from a conformationally constrained 1,3-diazide was found to be affected by a class of polybenzimidazole ligands introduced in the accompanying article. Various lines of evidence suggest that the standard tris(triazolylmethyl)amine ligand binds less strongly to Cu(I) than its benzimidazole analogues. On the basis of these observations, it is proposed that (a) a central nitrogen donor provides electron density at Cu(I) that assists the cycloaddition reaction, (b) the three-armed motif bearing relatively weakly coordinating heterocyclic ligands serves to bind the metal with sufficient strength while providing access to necessary coordination site(s), (c) at least two active catalysts or mechanisms are operative under the conditions studied, and (d) pendant acid or ester arms in the proper position can assist the reaction by speeding the protiolysis step that cleaves the Cu-C bond of a Cu.triazolyl intermediate.

[Alteration of serum enzyme activity after trauma and/or bacterial infection (author's transl)]. / Veränderungen der Enzymaktivität im Serum nach Trauma und/oder bakterieller Infektion.

Our clinical and experimental study is based on the evaluation of the changes in enzymatic activity produced by surgical, traumatic and infectious agression. To this end we have evaluated the activity of the transaminase (GOT-GPT), malic dehydrogenase (MDH), lactic dehydrogenase (LDH) and creatine phosphokinase (CPK). The details of our study are based on a total of 175 patients and 82 animals (dogs). Our results show that the highest rate of enzymatic activity was in proportion to the seriousness of the wound (lesion) produced. The clinical course-index developed from the activity of CPK and MDH allows us to evaluate and predetermine the course which our patients and our animals were to follow.

Non-chromaffin paraganglioma of the orbit. Case report.

The non chromaffin paraganglioma of the orbit is a relatively rare tumor. To our knowledge only 25 cases have been reported in the world literature. We report on the case of a 39-year-old woman who was treated surgically for the removal of an orbital paraganglioma 10 years ago. She had complained of proptosis and her right eyeball was slightly displaced upwards and laterally. A transcranial operation was performed and the tumor, located medically and weighing 9'5 grs., was completely removed; it was encapsulated. 10 years after this total excision there was no evidence of recurrence. From a histological point of view the tumor cells closely resembled those of paragangliomas of the carotid body and glomus jugulare.

[Is appendiceal surgery performed by residents safe?]. / Es segura la cirugía apendicular realizada por residentes?

An evaluation was made of the participation of residents in appendicular surgery as compared to staff surgeons, the evolution of results over the residency period and the influence of the presence of experienced surgeons together with residents during the emergency operation. Seven groups were made according to the surgeons involved. Parietal, intraabdominal and general complications of each group were quantitated, as well as postoperative hospitalization and mortality. Statistical study revealed similar results for the different groups.