410 research outputs found
Stereoselective Synthesis of Atropisomeric Acridinium Salts by the Catalyst-Controlled Cyclization of ortho-Quinone Methide Iminiums
Quinone methides are fundamental intermediates for a wide range of reactions in which catalyst stereocontrol is often achieved by hydrogen bonding. Herein, we describe the feasibility of an intramolecular Friedel-Crafts 6Ď€ electrocyclization through ortho-quinone methide iminiums stereocontrolled by a contact ion pair. A disulfonimide catalyst activates racemic trichloroacetimidate substrates and imparts stereocontrol in the cyclization step, providing a new avenue for selective ortho-quinone methide iminium functionalization. A highly stereospecific oxidation readily transforms the enantioenriched acridanes into rotationally restricted acridiniums. Upon ion exchange, the method selectively affords atropisomeric acridinium tetrafluoroborate salts in high yields and an enantioenrichment of up to 93 : 7 e.r. We envision that ion-pairing catalysis over ortho-quinone methide iminiums enables the selective synthesis of a diversity of heterocycles and aniline derivatives with distinct stereogenic units
Retrosynthetic polyketide disconnections for unnatural aromatics
Polyketide synthases are extraordinarily complex enzymatic machineries that govern the assembly and cyclization of poly-β-carbonyl intermediates to an enormous diversity of natural products. Captivatingly, this biosynthetic strategy is transferable to the retrosynthetic analysis of unnatural aromatics, enabling strategic biomimetic polyketide cyclizations to design an extensive range of otherwise unrelated aromatic products
Visually Adversarial Attacks and Defenses in the Physical World: A Survey
Although Deep Neural Networks (DNNs) have been widely applied in various
real-world scenarios, they are vulnerable to adversarial examples. The current
adversarial attacks in computer vision can be divided into digital attacks and
physical attacks according to their different attack forms. Compared with
digital attacks, which generate perturbations in the digital pixels, physical
attacks are more practical in the real world. Owing to the serious security
problem caused by physically adversarial examples, many works have been
proposed to evaluate the physically adversarial robustness of DNNs in the past
years. In this paper, we summarize a survey versus the current physically
adversarial attacks and physically adversarial defenses in computer vision. To
establish a taxonomy, we organize the current physical attacks from attack
tasks, attack forms, and attack methods, respectively. Thus, readers can have a
systematic knowledge of this topic from different aspects. For the physical
defenses, we establish the taxonomy from pre-processing, in-processing, and
post-processing for the DNN models to achieve full coverage of the adversarial
defenses. Based on the above survey, we finally discuss the challenges of this
research field and further outlook on the future direction
X-Ray Crystallographic Studies of Quasi-Racemates for Absolute Configuration Determinations
The determination of the absolute configuration of chiral molecular entities by means of X-ray crystallography is overall of central importance in stereochemistry. However, the growth of enantiopure single crystals often represents an unsurmountable and frustrating hurdle. Quasi-racemic crystals of biomacromolecules, for which the absolute configuration is predetermined by the chiral monomers, allowed the X-ray crystallographic analysis of systems that are difficult to crystallize as pure enantiomers, with aims other than the determination of the absolute structure. Taking advantage of the greater propensity of quasi-racemic mixtures to co-crystallize compared to growing enantiomerically pure crystals of a single compound, we herein describe the use of X-ray crystallography of quasi-racemates for the absolute configuration determination. We expect that this approach is particularly useful to establish the sense of selectivity in the development of stereoselective methods by simplified crystallizations, while confirming the consistent selectivity with a second molecular structure within the same measurement
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C-F bond activation under transition-metal-free conditions
The unique properties of fluorine-containing organic compounds make fluorine substitution attractive for the development of pharmaceuticals and various specialty materials, which have inspired the evolution of diverse C-F bond activation techniques. Although many advances have been made in functionalizations of activated C-F bonds utilizing transition metal complexes, there are fewer approaches available for nonactivated C-F bonds due to the difficulty in oxidative addition of transition metals to the inert C-F bonds. In this regard, using Lewis acid to abstract the fluoride and light/radical initiator to generate the radical intermediate have emerged as powerful tools for activating those inert C-F bonds. Meanwhile, these transition-metal-free processes are greener, economical, and for the pharmaceutical industry, without heavy metal residues. This review provides an overview of recent C-F bond activations and functionalizations under transition-metal-free conditions. The key mechanisms involved are demonstrated and discussed in detail. Finally, a brief discussion on the existing limitations of this field and our perspective are presented
The early design stage of a novel Solar Thermal Façade (STF) for building integration: energy performance simulation and socio-economic analysis
This paper provides a feasibility study of a new solar thermal façade (STF) concept for building integration from both technical and economic aspects in Shanghai area of China. The whole set of technical evaluation and economic analysis was investigated through simulation of a reference DOE residential building model in IES-VE software and a dedicated dynamic business model consisting of several critical financial indexes. In order to figure out the cost effectiveness of the STF concept, research work consisted of: (1) exploring the overall feasibility, i.e. energy load, energy savings, operational cost and environmental benefits, and (2) investigating the financial outputs for investment decisions within three different purchase methods. This paper presents a multidisciplinary research method that is expected to be beneficial and supportive for the strategic decision at the early design stage and it also offers a different angle to assess the economic performance of the STF application
Nanosecond pulsed electric field inhibits malignant melanoma growth by inducing the change of systemic immunity
Nanosecond pulsed electric fields (nsPEFs) showed an inhibitory effect on proliferation of malignant melanoma. In this study, the growth of melanoma were inhibited by changing the systemic immunity. C57BL/6 mice with B16 malignant were exposed to 200 pulses of 100 ns duration, 30kV/cm. The mice were executed four days later. T lymphocyte has been extracted from spleen. Cell viability was evaluated by CCK-8 assay. CD3+CD4+ T cells, CD3+CD8+ T cells, regulatory T cells (Treg) and myeloid-derived suppressor cells (MDSC) were analyzed by flow cytometry. TNF-?, IL-2, IL-10, TGF-?, IFN? ? levels in supernatants were assessed by ELISA. C57 malignant melanoma model were established successfully. After the treatment of nsPEFs(30 kV/cm 100 ns 200p), the numbers of T lymphocytes were increased.CD3+ CD4+ T cells changed from 48% to 51.2%;CD3+CD8+T lymphocytes increased from 39.6% to 40.4%.Treg cells reduced from 4.3% to 2.4%,MDSC decreased by 39.0% to 19.7% . In addition, the level of TNF-?, IL-2 were increased (P0.05). Tumor growth can be effectively inhibited by nsPEFs in vivo, which activate targets of immune respones, accumulation of inflammatory cells and immune cytokines
Enterprise Knowledge Creation Entropy Theoretical Analysis and Knowledge Entropy Model Study
Entering the 21st century, the knowledge economy as a new economic realizes the alternative of intellectual resources of material resources in the economic operational process, and it can greatly save energy and improve economic efficiency. Thus the value of existence of the enterprises in the context of knowledge economy is that the enterprises can conduct knowledge creation, transfer and use more efficient compared with the market. In essence, enterprises are the entity of knowledge production, the peculiarity of it owned to the difference between knowledge production ability and using ability. This paper used the similarity fundamental of the cross and comprehensive of natural science and social science, and imported the basic principles of entropy theory in thermodynamics to study the mechanism of knowledge creation, the key pathways and mechanisms, pointed out that the knowledge entropy can greatly save energy and improve economic efficiency. At the same time constructed a mathematical model of knowledge creation, and pointed out that any enterprises must continue to carry out knowledge creation and knowledge transfer to increase negative entropy to promote sustained and have a healthy development. Key words: Entropy theory; Knowledge creation; Mode
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