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Patch by Pablo Galindo Salgado. Now dict has more chance to be shrinked. The regression was introduced in 3. This fix also changed pydoc to add os. Convert an uncaught StopIteration in a generator into a return-statement. Previously emitted cover files only when --missing option was used. Patch by Michael Selik. Instead, modules that specifically need that preprocessor definition include it in their individual entries.

Consistently color as much of the prefix, starting at the right, as is valid. Revise and extend colorizer test. Based on patch by Oleg Krasnikov. A new test ensures that NULL bytes are not allowed. They have been refactored. Patch by Jamie Davis. Patch by Josh Bronson. Patch by Garvit Khatri. This fixes several minor issues and inconsistencies, and improves backwards compatibility with Python 3. This is an improvement over looking up a string, and then testing that string to see what to do. Only attributes from the frozen dataclass cannot be assigned to.

Require all dataclasses in a hierarchy to be either all frozen or all non-frozen. Queue when a pickling error occurs. Patch by Nir Soffer. Process if the standard streams are closed or None at exit. Patch by Cheryl Sabella. Connection now exposes a backup method, if the underlying SQLite library is at version 3. Patch by Lele Gaifax. Patch by Jon Foster and Berker Peksag.

Patch by Himanshu Lakhara. The This means that the Python 3. Like Python, IDLE optionally runs one startup file in the Shell window before presenting the first interactive input prompt. IDLE now does the same when run normally, without the -n option. This restriction will be relaxed at a future date.

Patch by Joffrey Fuhrer. The constructors were never documented, tested, or designed as public constructors. Users were suppose to use ssl. It is a speedup module with C implementations for various functions and methods in abc. Condition issue which silently ignored cancellation after notifying and cancelling a conditional lock. Error reporting for invalid wildcards has been improved. Contributed by Oren Milman. Patch by Jake Davis. ChainMap preserves the order of the underlying mappings.

Currently they emit warnings. This bug appears to have been introduced in 3. The shared extension is now explicitly linked against libdl on platforms with dl. Lock safety issue which allowed acquiring and locking the same lock multiple times, without it being free. The SSLSocket has one less layer of indirection. Channel binding implementation has been simplified. Patch by Alan D Moore. Especially this speeds up socket. Patch by Terry Reedy. PurePath subclasses. Patch by Toby Harradine.

Patch by Nitish Chandra. Previously, the order was reversed. Instead, use Patch by Ben North. Patch by Sanyam Khurana. Python no longer re-enables ciphers that have been blocked by OpenSSL security update. Default cipher suite selection can be configured on compile time. Previously it would keep them alive for as long as the context manager was alive, even when not being used as a function decorator.

Patch by Martin Teichmann. BufferedProtocol provisional API. Patch by Xiang Zhang. SimpleQueue in places where it can be invoked from a weakref callback. Queue, when the queue has limited size and it is full, the cancelation of queue. ValuesView now inherits from collections. Use replacement libtirpc headers and library in nis module. It now waits a short amount of time for the child presumed to have also gotten the SIGINT to exit, before continuing the KeyboardInterrupt exception handling. This only works if the file object used to open the zipfile is seekable. ResourceReader as the unified API for reading resources contained within packages.

File-based and zipimport-based loaders both implement these APIs. ResourceLoader is deprecated in favor of these new APIs. Patch by Alexander Mohr and Ilya Kulakov. The args argument of subprocess. Popen can now be a path-like object. Same change for the str. They were there most likely for legacy reasons.

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Subject common name fallback can be disabled with SSLContext. IDNA internationalized host names are working since bpo has landed. IDNA are still broken. The module is primarily intended for more thorough testing of the existing subinterpreter support. Upgrade the supplied third-party libraries to OpenSSL 1. UTC singleton. Original patch by Michael Felt. This fixes also bpo Previously, the option was ignored. Moreover, sys. Increased limits for constants that can be produced in constant folding.

This should ensure siphash gives consistent results across platforms. Implemented by Ivan Levkivskyi. Python now supports invalidating bytecode cache files bashed on a source content hash rather than source last-modified time. Original patch by Eugene Toder. Pass them through to dataclass. Previously, None was always returned. Now it can only be set to False, or a ValueError is raised. Now, the latter is as fast. New transport. Fix socket. Also add importlib. Affected functions: loop. This makes them 4x faster.

Add helpers intended to be used by alternative task implementations: asyncio. Deprecate asyncio. This allows to distinguish an empty row from a row consisting of a single empty field. Patch by Licht Takeuchi. It was never enabled by default, never worked correctly on x, and it changed the Python ABI in ways that caused unexpected breakage of C extensions. Added types. ClassMethodDescriptorType for unbound class methods of builtin types.

Old styled yield from is still supported too. Pickles created with protocol 4 will require less memory for unpickling large bytes and str objects. Tests by Victor Stinner. Addition and subtraction of arbitrary numbers no longer allowed. Patch by Jelle Zijlstra. ProcessPoolExecutor when task arguments or results cause pickling or unpickling errors. This lets 2to3 and lib2to3 work when run from a zipfile. It was added by mistake and actually never worked in the limited C API. This ensures it will be cleared automatically when additional cell references are injected into a modified code object and function.

They are still permitted in the definition of the outermost iterable, as that is evaluated directly in the enclosing scope. The duplication of the parentheses can be omitted only on calls. A generator expression always needs to be directly inside a set of parentheses and cannot have a comma on either side. Setting sys. In particular they now raise TypeError rather of returning a bogus result when an integer is passed as a separator. Patch by Ivan Levkivskyi. Previously, opcode events were emitted first, and therefore would occasionally see stale line numbers on the frame.

Patch by Zane Bitter. The functions now block waiting for events as expected. Previously, the call was incorrectly non-blocking. There was a write to freed memory after shrinking a memory block. Original PRs by Ivan Levkivskyi. Provides a decorator which adds boilerplate methods to classes which use type annotations so specify fields. In particular, RFC folding is now done correctly. Fixed hang of all threads with inaccessible NFS server. This makes a better guarantee for global uniqueness of UUIDs returned from uuid. If only locally administered MAC addresses are available, the first such one found is returned.

Patch by Mandeep Singh. Initial patch by Mark Mc Mahon. If it does not exist, FileNotFoundError is raised. Patch by Dimitri Merejkowsky. Traceback behave more like the traceback module, sorting the frames from oldest to most recent. Patch by Jesse Bakker. The distutils. Distribution class now warns when classifiers , keywords and platforms fields are not specified as a list or a string. This provides a simpler and faster alternative to ExitStack when handling optional context managers.

This makes it compatible with read methods of other file-like objects. Non-empty string can now be correctly found after matching an empty string. MemoryBIO is always used anyway. This will decrease the size of a pickle, speed up pickling and unpickling, and make these integers be unpickled as int instances in Python 2. These files can be produced in Python 2. Now the check is implemented correctly for all file-like objects. Patch by Marat Sharafutdinov. Based on patch by Steve Fink. Patch by Masayuki Yamamoto. See also the PEP The pure SSE2 implementation is slower than the pure C reference implementation.

To support applications that cannot tolerate such exceptions, the new methods itermonthdays3 and itermonthdays4 are added. The new methods return tuples and are not restricted by the range supported by datetime. This was done using the os. IPv6Network and ipaddress.

Patch by Michel Albert and Cheryl Sabella. It was introduced in Python 2. Patch by Andrew Clegg. Patch by Mario Corchero. Cursor object more than once. ASCII, re. This method was previously modifying a wrong reference to the protocol. Patch by Vincent Michel.

Patch by Riccardo Coccioli. If it crashes, restart it when necessary. Patch by Vitor Pereira.


'Omega and Alpha,' part 1: In the second-to-the-last issue of Locke & Key, the damned and the saved alike will make their final stand in the Drowning Cave, in a. The finale to Locke & Key! A story so big, it needs two extra-size issues to tell it! 32 pages of story plus bonus material! Only ONE issue of Locke.

A fix was merged into the kernel 4. Skip tests with test. It prevents false alarms when hunting reference leaks. Close method to help closing MSI database objects. EMPTY traceback context is no longer added to tk event exception tracebacks. The traceback is now the same as when event handling is driven by user code. Patch based on a suggestion by Serhiy Storchaka. Use of TabbedPageSet in configdialog was replaced by ttk. Patch mostly by Cheryl Sabella.

Editor and output windows only see an empty last prompt line. This simplifies the code and fixes a minor bug when newline is inserted. Changes persist while IDLE remains open. The code module uses sys. Ditto for ps2. To make room for the expanded sample, frames on the Font tab are re-arranged. This simplifies the interpreter and fixes a couple of obscure bugs caused by having swap exception state when entering or exiting a generator. This singleton is persistent and its members being never cleared may cause a segfault during finalization of the interpreter.

See also bpo In effect, this enables great copy-on-write stability at fork. Patch by Stefan Behnel. By default this imports pdb and calls pdb. The original value of the hook is saved in sys. Based on a patch from Armin Rigo. Pattern and re. This adds information in pydoc output for the re module. Allow whitespace around predicate parts, i.

For example, set x for x in [], is now allowed. ProcessPoolExecutor constructor. Also, free job resources in concurrent. ProcessPoolExecutor earlier to improve memory usage when a worker waits for new jobs. Thus, the sqlite module now requires sqlite version at least 3. This matches behaviour in Python 2. As of 3. If given, this is printed to the console just before debugging begins. Patch by Brad Smith. The one with underscores are only kept for back-compatibility. Passing a widget instead of an flist with a root widget opens the option of creating a browser frame that is only part of a window.

Passing a full file name instead of pieces assumed to come from a. The original module-level class and method browser became a module browser, with the addition of module-level functions, years ago. Nested classes and functions were added yesterday. Original patches for code and tests by Guilherme Polo and Cheryl Sabella, respectively. PEP written by Erik M. Bray, patch by Masayuki Yamamoto. Prevent passing other environment variables and command arguments. Popen on Windows, in case the env argument has a bad keys method.

Also introduce more uniformity in other code that deals with sys. This helps reduce complications when working on sys. This allows later support for all dict subclasses and other Mapping implementations. This fixes tools like flake8 from showing warnings on the wrong line typically the first line of the file.

This improves discoverability of the runtime state. Previously any exception was replaced with a KeyError exception. Relative import from non-package now fails with ImportError rather than SystemError. This means our signal delivery logic had defects some signals could be lost. Patch by Martijn Pieters. This means that when a suitable coercion target locale is available, both the core interpreter and locale-aware C extensions will assume the use of UTF-8 as the default text encoding, rather than ASCII. Patch by Lisa Roach. Based on patches by Duane Griffin and Tim Mitchell.

Based on patch by Eryk Sun. ValueError always is raised rather than OverflowError for negative counts. Shifting zero with non-negative count always returns zero. This makes it easier to identify each subinterpreter. In a future versions of Python this can be an error. The first argument of int can now be passes only as positional argument. Patch by Brian Coleman. It should raise TypeError when kwargs is not a dict. Patch by Matthieu Dartiailh. Patch by Serhiy Storchaka. Reverted in bpo Patch by Mircea Cosbuc.

Warnings could be emitted at compile time. Patch by Robert Xiao. Based on patch by Michael Layzell. Patch written by Chi Hsuan Yen. This gives less confusing error messages when both methods are missing. Patch by Jonathan Ellington. Patch by Adrian Wielgosik. Patch by Serhiy Storchaka and Eric Smith. Original patch by Yury Selivanov.

Calling iter on range instance is the only way. Original patch by Niklas Koep. Patch by Soumya Sharma. Now it is converted to exact tuple. Thanks Oren Milman. Visual Studio can properly optimize memcpy. The exception contains more information about the error. This fixes support for all bytes-like object. It is also more efficient and avoids costly copies. Template subclasses can optionally define braceidpattern if they want to specify different placeholder patterns inside and outside the braces.

If None the default it falls back to idpattern. Path objects. Non-string keys and values in the defaults dictionary are now being implicitly converted to strings. Patch by James Tocknell. Patch is based on research from Gustavo Serra Scalet. Process are now joined on child exit. Patch by George Collins based on diagnosis by Luciano Ramalho. This change fixes two of the most potentially problematic ones, since they are in error-reporting code, in the multiprocessing. It also makes more informative a ValueError message.

Smith drallensmith on github. It is now from 10x up to 70x faster when comparing arrays holding values of the same integer type. The LabeledScale. Patch by Shane Harvey. This is similar to os. Patch by Cooper Ry Lees. StreamHandler to allow the stream to be set after creation. Based on patch by Christian Heimes. Shared memory used anonymous memory mappings in 2. Patch by Aaron Gallagher.

OptionMenu radiobuttons to be unique across instances of OptionMenu. Tiny values such as 1e-6 are valid non-zero values for setitimer , which is specified as taking microsecond-resolution intervals. However, on some platform, our conversion routine could convert 1e-6 into a zero interval, therefore disabling the timer instead of re- scheduling it. The doc claims multiprocessing. Condition behaves like threading. As in some special FIPS build environments.

They now always return bytes. Patched by Dong-hee Na. Patch by Nathaniel Smith. Patch by Alexandru Ardelean. Patch by Roy Williams. Patch by Nikolay Kim. Patch by Mathieu Sornay. Patch by Aaron Hall. Patch by Yuan Liu. SysLogHandler cannot handle IPv6 addresses. Patch by Mariatta Wijaya. Based on patch by Ma Lin. Previously they could point into inners of the re module if emitted from inside of groups or conditionals.

This error occurs sometimes on SSL connections. Dict values in the result of functions readPlist and readPlistFromBytes are now normal dicts. You no longer can use attribute access to access items of these dictionaries. This increased the performance of matching some patterns up to 25 times. Now allowed several subsequential inline modifiers at the start of the pattern e. In verbose mode whitespaces and comments now are allowed before and between inline modifiers e. Original patch by Ma Lin. Patch by Pierre Quentel. Misusing them could cause memory leaks or crashes.

Only the locale at matching time affects the result of matching. NoReturn type, use WrapperDescriptorType, minor bug-fixes. FileIO now set the internal seekable attribute to avoid one syscall on open in buffered or text mode.

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Patch by Nate Soares. Patch by Bryan Olson. Patch by Armin Rigo. Patch by Siddharth Velankar. Patch by Aviv Palivoda. Writing to a closed writer now always produces a ValueError. Patch by Sanjay Sundaresan. Now using them emits a deprecation warning. Patch by Davin Potts and Xiang Zhang. Patch by Christophe Zeitouny. Patch by Michael Seifert. Sequence now check identity before checking equality when do comparisons. Patch by Nathaniel J. Patch by David Ellis. SubprocessStreamProtocol no longer closes before all pipes are closed. Patch by Petr Motejlek.

Patch by Sayan Chowdhury. Patch by Christian Theune and Ratnadeep Debnath. Patch by Anthony Zhang. SafeUUID and uuid. Some deprecated methods now emit DeprecationWarnings and have better descriptive messages. Thanks Andrew Nester. Counter, typing. ChainMap, improved ABC caching, etc. Based on patch by WGH. Summary: Learn how to remove an air lock in a water pipe. We've focused on the concept that you can create even if you have never touched video editing software, eliminating the complex elements and configuration inherent of such software.

Can version 6 bring it the popularity it deserves? Edius is an interesting programme in many ways. So, just again, Edius doesn't require you to have assets in the Asset bin for you to add them to a sequence to start cutting. Grass Valley Edius 6. The intent is to reveal how various Edius Pro 8 features can be combined and leveraged in real-world examples so that they can be applied to creative projects right away. To open a project created in another program, click the file format that you want in the list to the right of the File name box, and then double-click the file name in the folder list.

FAQ I cannot save the project because there is an invisible open dialog or minimized dialog. The box will automatically relock after 7 seconds. When applying a transition or audio cross fade by dragging them using the right button of the mouse, you can select [Custom] and control the placement.

In the Confirm Password dialog box, type the password again, and then click OK. The numbers in the file are date and time when the backup was created. If turning on your tap produces poor flow or no water at all then there could be an airlock in the supply pipe. Open a project from Project Web App. Thakur Digital code lock systems are most common on security systems.

Work efficiently by using Shortcuts I edit my videos on Adobe Premiere or even Edius and I want to build a linux based render farm for rendering my projects. Most are things that have not been an issue for me although I did notice the way the primary colour corrector sliders changed when I adjusted them.

Lock your PRD system for using by all users. Scratch is a free programming language and online community where you can create your own interactive stories, games, and animations. You can also just open a clip, which is the same as double-clicking, Show in Player and you can add directly to the timeline. Windows can't open this file: example.

New working tool available now. Y ou will be prompted for your login credentials for access. The Adafruit Let us build a Secret Knock Detecting Door Lock using Arduino which can detect the pattern of your knocks at the door and will only open the lock if the knocking pattern matches with the correct pattern.

Windows 10 Has a Secret Start Menu. For a summary of lock picking laws across the country, see here. Put your cell phone up close to the lock of the car and have them press the unlock To open a project in a Project database, click Project Databases in the list to the right of the File name box, and then click Open.

Quick Fixes for Front and Sliding Door Locks It's important to keep your home under lock and key, and incredibly frustrating when those two elements don't work together. Connect to the Team Projects service. You can have several sequences open at once and sequences can be put inside other sequences for multi-layered effects. Find these and other hardware projects on Arduino Project Hub. If you want to delete your EDIUS license from the license list, delete it with below procedure: 1 Request returning the license to your regional GV tech support along with target serial number and product name.

How to Downgrade iOS One way you can do is, if you ensure that no postings were done for the open period. With MXFserver editors experience the freedom to open projects in different editing systems simultaneously. However, sometimes you will be given a spare key remote as well, and fortunately, these fobs use radio waves to open the locks much like a garage door opener.

By double clicking on the related playlist, a new Inspector window will be opened showing the project clips. Then, unscrew and remove the set plate, which is the piece of metal that faces the doorframe. Windows Display Quality Troubleshooter will help you if you find that, on your Windows 7 computer, the display is not good and the readability of text is poor too.

Windows can go online to look it up automatically, or you can manually select one from a list of programs that are installed on your computer. How to change the barrel of a Yale lock or other night latches. Enjoy this burning open source software Review Mozilla Firefox is a highly customizable open source Internet browser which offers full-featured tools for improving your experience surfing the Download Microsoft Visual Studio Team Foundation Server Free for Windows. EDIUS 9. Army Corps of Engineers. In addition, Adobe has expanded project types to include both Team Projects your project is in the cloud and shared projects your project is local.

While starting, you have to access the main window where you can generate a project file by specifying a name, select the size, choose the frame rate and bit value. Home made door lock sensor. Just be a decent human being. In the crystalline state as well as in solution these macrorings preferentially adopt less symmetric conformations through an alternating succession of gauche and anti geometries of the constituent meso-butanetetrol residues. In all cases — i.

Large-ring Crown Acetals from Cyclodextrins.

Joe Hill Interview Hill House Comics and Netflix's 'Locke & Key'

Flexible Non-glucose Cyclooligosaccharides. Immel, th Proc. Rigidified Bridged Cyclodextrins The introduction of flexibility into the cyclodextrins described so far, is opposed by the approach to increase the rigidity of the macrocycles through intramolecular bridging between the glucose residues. From these simulations, the observed gluco-configured product not only emerged as being thermodynamically more stable than the alternate altro-configured stereoisomer, but also being the favored product on geometrical considerations.

In the environment of the crystal lattice, the three n-propanol molecules are distributed in the cavity of a dimeric unit of the host. Based on comparisons of the crystal structure with molecular dynamics simulations of this compound in water, the cyclodextrin derivative undergoes no significant conformational changes upon dissolution.


Synthesis, Structure, and Properties 15 In addition to the intramolecular bridging of cyclodextrins described above, intermolecular bridging represents an appropriate approach towards rigidified cyclodextrin dimers with extended cavities. Although cyclodextrin dimers and oligomers have been studied in the past, this work focuses on the option to introduce the shortest possible single-atom linkages between individual cyclodextrin units. For the first time, the solid-state structure of such a bridged cyclodextrin has been solved in the form of its hydrated methanol inclusion complex.

Moreover, the rather rigid linkage of this host molecule with two separated cavities may allow to study included guest molecules and their long-range interactions at well-defined distances. Molecular Modelling of Saccharides This Chapter describes molecular modelling studies on various saccharides not related to the concept of creating more flexible or rigidified molecular host-guest systems.

However, the studies presented are of interest for evaluating the chemical, stereochemical, conformational as well as biological properties of low-molecular weight saccharides. Ellagitannins represent a class of polyphenolic natural products contained in higher plants, their common structural element being hexahydroxydiphenoyl HHDP substituted D-glucopyranosides with varying substitution patterns, and these tannin- components exhibit a broad range of biological activities. The axially chiral diphenoyl units occur with specific configurations depending on the positions of attachment.

For the 2,3- and 4,6-O-diphenoyl bridged glucosides the S -diphenoyl configuration is energetically highly preferred, whereas for the 3,6- and 2,4-O-linked diphenoyl glucosides the opposite R -configuration is favored. All the results are in full accord with the absolute configurations found in the natural products, and thus provide explanations for the observed chirality on the basis of geometrical reasons. The results explain the enzymatic differences in selectivity on the basis of the substrate properties.

This program was developed for the purpose of simple automated analysis and 3D fitting of molecular structures, calculation of numerous geometry parameters, as well as providing the possibility to visualize organic and inorganic structures with different modes wire models, capped-sticks, ball-and-stick models, CPK-type models. Solid-state crystal structures and packings including thermal anisotropic ellipsoids and Hirshfeld surfaces , coordination polyhedra, molecular orbitals and surfaces with color-coded mapped properties, 3D grid and density data, and ribbon models of arbitrary including non-protein structures can be represented.

Options are included to generate molecular animations for sets of molecular configurations along reaction coordinates or molecular dynamics simulations. The packing of the macrocycles in the crystal lattice is of cage herringbone-type with an extensive intra- and intermolecular hydrogen bonding network. The ready formation of a nitromethane inclusion complex in aqueous nitromethane, and the subtleties of its molecular structure amply demonstrate the ease with which water is expelled from the a-CD cavity by a more hydrophobic co-solvent.

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Keywords: a-Cyclodextrin; Nitromethane inclusion complex reagent, has not been reported to complex 1. Introduction with a-CD or any of the other cyclodextrins [5,6]. Here we report on the ready preparation Various small organic molecules have been of a a-CD—CH3NO2 inclusion complex 1 shown to be readily included into the apolar and its topography on its X-ray based cavity of a-cyclodextrin a-CD, Scheme 1 , structure. Results and discussion solid-state structures. For Part 22, tromethane inclusion complex 1 are shown see Ref. The E-mail address: fwlicht sugar.

Nakagawa et al. The CD macrocycles are arranged in a of six adjacent glucose residues cf. However, the solid-state geometry is, for example, also found in the three a-CD displays an extensive three-dimensional hydro- hydrate solid-state structures [7—9]. All hydroxyl groups satisfy realized in a large variety of related complexes their hydrogen-bonding requirements through [6,10,11]. The glucose units are in the corresponding two nitrogen positions coincide rather rigid 4C1 conformation with standard in one fully occupied site.

Side-view cross-sectional cuts through these surfaces Fig. Obvi- ously, the guest is held in the cavity by van der Waals contacts to a circular array of the pyranose hydrogens at C-3 and C Although the NO2 group is not involved in hydrogen bonds with the hydroxyl groups of the host, it Scheme 1. The glucose units of a-CD are labeled A—F cf. The nitromethane guest molecule shows excessive thermal motions and is disordered over two sites with equal occupancies; the statistical disordering of the NO2 oxygen atoms is approximated by six atomic positions.

The disordered nitromethane molecules are visualized as CPK-models, and the unit cell boundaries are indicated by solid cyan lines. Conclusions whereas the antiparallel arrangement of dipoles of host and guest would lead to the The solid-state structure of the a-CD—ni- opposite regioselectivity. Found: C, Scheme of intra- and intermolecular hydrogen bonds in the solid-state structure of the a-CD — nitromethane pentahydrate inclusion complex 1.

The nitromethane guest molecule is not involved in the hydrogen-bonding pattern. Chapter 1 25 T. Symmetry operations: bx, y, z. Crystal structure determination. A colorless sin- difference synthesis. Acknowledgements The authors thank the Fonds der Chemis- chen Industrie, Frankfurt, for support of this work, Mrs Sabine Foro for collecting the crys-. References [1] H. Hingerty, W. Saenger, J. Harata, Bull. Harata, in J. Szejtli, T. Osa Eds. Topology of the a-CD—nitromethane inclusion com- , pp. Rekharsky, Y. Inoue, Chem. Top: Contact surfaces in dotted form with particularly Table 1.

Chacko, W. Klar, B. Saenger, Acta Crystallogr. B, 36 — Lindner, W. B, 38 — Lipkowitz, Chirality, 4 — Lichtenthaler, S. Immel, Liebigs Ann. Immel, J. Brickmann, F. Lichtenthaler, Liebigs The molecular graphics of Figs. Cremer, J. Pople, J. Jeffrey, J. Yates, Carbohydr. Jeffrey, W. Connolly, J. Supplementary material M. Connolly, Science, , — CCDC Lichtenthaler, Darmstadt Germany Two polymorphs of amylose, the native double-helical A-form and the lose, in accord with its water solubility, has a pronouncedly hydrophilic single-stranded VH counterpart, as well as the amylose polyiodide com- outside surface with an as distinctly hydrophobic channel.

Their detailed hydrophobic regions of guest and host. Thus, the MLPs provide sub- analysis revealed the double-stranded A-form to be a rather compact stantive credence to the view, that not only the amylose-iodine complex structure with an irregular distribution of hydrophilic and hydrophobic formation is mediated to an essential degree by hydrophobic attractions regions over the entire outer surface, with the interior of the double he- at the guest-host interface, but that the same factors determine the sta- lix being inaccessible even for small molecules.

By contrast, VH-amy- bility of this unique supramolecular assembly. The results [2] are subject of this pa- channel or not, this sketchy formulation of a single-stranded per. Single helixes of 2 Experimental the type depicted above, with six glucose units per turn, are only obtainable in the form of inclusion complexes with di- 2. The close analogy allows to consider VH-amylose as a tubular analog of the cyclodextrins.

All mol- ecular parameters discussed within this study cf. Molecular geometries of VH-type amylose upper structure and MLPs were computed after removal of all iodine species and A-amylose lower entry [21]. Surfaces for the inclusion com- gauche arrangement of all hydroxymethyl groups in relation to their plexes were generated for the guest and host molecules sep- pyranoid rings. As VH-amylose top represents a single helix of arately, and were subsequently reassembled to the complex; symmetry, i. Visualization of the MLP surface tact surfaces roughly equivalent to the solvent-accessible surfaces [19, qualities was done by color-coded projection of the comput- 20], i.

Scaling of the molecular hydrophobicity patterns diameter to decrease to Thus, it is easily understood, that the water of ly, and no absolute values are displayed. Apart from strong van der Waals attractive forces that 3 Results and Discussion must be an important factor for establishing the distinctly different folding patterns — for the two intertwined single 3.


The resulting struc- cose units of different strands Fig. In VH-amylose, however, their molecular contact surfaces [18, 19] — closely resem- not only 2-O … O-6 hydrogen bonds between spatially close bling the solvent water accessible surfaces [20] — molded glucose residues of the next spiral turn Fig. This basic dis- [22] energetically highly favorable [23] and, by conse- similarity of the two forms is even more lucidly illustrated in quence, must be considered as an important factor in stabi- the projections along the helix axis Fig.

Hydrogen bonding patterns yellow lines within the double he- lices of A-type starch left and the single helical VH-type amylose right , calculated from the heavy atom positions of the crystal struc- tures. The letters refer to different types of hydrogen bonds, of which the geometry parameters are listed in Tab. These MLPs [24] were calculated and mapped onto the cor- responding molecular contact surfaces of Fig.

As is apparent from the color-coded representations in Fig. The latter exhibits an irregular distribution of hy- drophobic and hydrophilic outer surface areas Fig. Molecular surfaces view along the helix axis of VH-amylose drophobic yellow. This distinctive inside-outside separa- top and A-amylose bottom , illustrating the molecular geometries of tion of hydrophobic and hydrophilic domains obviously pre- Fig. Calculated hydrogen bond geometries distances and angles for the A- and VH-form of amylose.

The letters denote the different types of H-bonds as marked in Fig. Hydrophobic topographies for the amylose fraction of starch [21]: the MLP pattern blue: hydrophilic surface regions, yellow: hy- drophobic areas on the contact surface of single-stranded VH-amylose upper structures each is set against the parallel-stranded double-heli- cal A-form lower model, respectively. The outside surface area of VH-type amylose is uniformly hydrophilic in conformity with its solubility in water whereas the center channel is as distinctly hydrophobic-predestined to incorporate equally hydropho- bic guests such as iodine or fatty acids.

By contrast, the double-helical A-form of amylose, devoid of a center channel, exhibits an irregular distribution of hydrophilic and hydrophobic regions over the entire sur- face [26]. The cf. Accord- sphere located at the interstice. Bottom: Surface cross-section cut ingly, the generation of the molecular lipophilicity profiles through the center of the dimer assembly exposing the five iodine and an assessment of the complementarity of the hydropho- atoms included. However, when taking into account the packing of these dimeric units in the crystal lattice, a surprisingly close similarity emerges: infi- nite stacks with the elaboration of a somewhat uneven nano- tube into which a nearly linear, continuous polyiodide chain is embedded as exemplified in Fig.

That this is material- ized despite the alternating hydrophobic and hydrophilic zones along these nanotube channels is a strong indication for the pronounced proclivity of iodine or polyiodide species to associate with suitable hosts to polymeric supramolecular assemblies. Right: Side-view models repre- erative way by slow formation of stable I— nuclei inside senting the hydrophobic topographies of the dimeric units.

The location the helices and rapid linear propagation [33]. With increas- of the lithium ion is indicated by the isolated pink ball at the lower, half- opened models. C6H10O5 The enthalpy of the coded projection onto the contact surfaces given in Fig. The computation and visualization of hydrophobic and hydrophilic surface regions described here for amylose and its iodine inclusion complex not only permits — for the first time — a genuine and reproducible localization and differen- tiation of these regions.

As significant is that the importance of complementary hydrophilic and hydrophobic surface do- mains at the guest-host interface is imposingly verified, their interplay thus being a decisive element in incorporation of the guest into the host. Finally, the insights provided by these novel views at amylose — substantiated by similar results described else- where on the cyclodextrins [14, 15, 41], cyclomannins [41], cyclorhamnins [42], cycloaltrins [43—45], cyclogalactins [41, 46], cyclofructins [47], and on sucrose [48] — may not only provide a viable base for the preparation of new, useful inclusion complexes of amylose, but also for the design of new ensuing reactions towards a targeted exploitation of the Fig.

Top: half-opened model based on its solid- state structure [16] with the linear polyiodide chain pink balls in the Acknowledgements channel; the hydrophobicity distribution is essentially identical to that The authors are grateful to Prof. Part T. Generation of the contact surfaces of VH-amylose and its [2] Portions of this work have been used by F. Lichtenthaler and S. Immel: Computersimulation of in Fig. Sugar J. Collins and R. Ferrier: Monosaccharides, their chemistry corporation and alignment of the iodine species. Superimpo- and their roles in natural products.

Wu and A. Sarko: The double-helical molecular structure documents the sterically perfect correspondence. The ideal of crystalline A-amylose. Imberty, H. Chanzy, S. Sarko: The double-helical molecular structure matching of their hydrophobic domains. Imberty and S. Biopolymers 27 , — French and H. Zobel: X-Ray diffraction of oriented substantial degree — is mediated by the operation of attrac- amylose fibers. The amylose-dimethyl sulfoxide complex. Winter and A. Sarko: Crystal and molecular structure of unique supramolecular assembly. Rundle and F. Edwards: The configuration of the starch- 4 Conclusion iodine complex.

An X-ray diffraction investigation of butanol-pre- cipitated amylose. Hellert and H. Chanzy: Single crystals of V amylose com- The hydrophobic nature of the tubular channel in VH- plexed with n-butanol or n-pentanol: structural features and prop- amylose and of the conical cavity in the cyclodextrins has erties.

Zaslow, V. Murphy, and A. French: V-amylose-water sys- their molecular structural features began to unravel about 60 tem. Structural changes resulting from hydration. Biopolymers 13 years ago [37—39]. Zugenmaier and A.

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Sarko: Packing analysis of carbohydrates and polysaccharides. Rappenecker and P. Zugenmaier: Detailed Refinement of the involved in inclusion complex formation, such as guest-host crystal structure of VH-amylose. Lichtenthaler: On the hydrophobic characteris- [30] F. Cramer, U.

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Bergmann, P. Manor, M. Noltemeyer, and W. Liebigs Ann. Kristallographische Daten und Vergleiche mit dem blauen [15] F. Betzel, B. Hingerty, M. Noltemeyer, G. Weber, W. Saenger, and 48 , — Bluhm and P. Zugenmaier: Detailed structure of the VH-amy- Spatial fitting of a polyiodide chain to a given matrix. Inclusion lose-iodine complex: A linear polyiodide chain. James, D. French, and R. Rundle: Schardinger dextrins. Murdoch: The amylose-iodine complex.

Structure of the cyclohexaamylose-iodine complex. Acta Crystal- , — B 12 , — Thompson and E. The major part the amylose-iodine reaction. Benegas, and D. Louis, USA. Brickmann: Molecular graphics — how to see a molecular , — Minick, K. Fotta, and A. Khan: Polyiodine units in starch-io- — Biopolymers 31 , [18c] J. Brickmann, T. Goetze, W. Heiden, G. Moeckel, S. Reiling, 57— Vollhardt, and C. In: Data Visualiza- [35] [35a] G. Gilbert and J. Marriot: Starch-iodine complexes. Faraday Soc. Bowie , Addison-Wesley Publ. Handa, H. Yajima, and T.

Kajiura: On the blue color of 83— Raman spectra of blu- [19] M. Connolly: Solvent-accessible surfaces of proteins and nucle- ing species in amylose.

Biopolymers 19 , — Science , — Banks, C. Greenwood, and K. Khan: The interac- [20] B. Leek and F. Richards: Interpretation of protein structures: es- tion of linear amylose oligomers with iodine. Jerian, and S. Saule: Physicochemical studies oc. Yajima, T. Yamamura, T. Ishii, and H. Aikawa: [22] G. Jeffrey and W. Saenger: Hydrogen bonding in biological Enthalpy change of amylose triiodide formation. Freudenberg, E. Schaaf, G. Dumpert, and Th. Ploetz: [23] I. Tvaroska and S. Freudenberg and H. Boppel: Die Lage der Verzwei- , — Moeckel, and J.

Brickmann: A new approach to — French and R. Rundle: The molecular weights of the on molecular surfaces MLP. Teschner, C. Henn, H. Vollhardt, S. Reiling, and J. Brickmann: [38b] R. Rundle: The configuration of starch in the starch-io- Texture mapping, a new tool for molecular graphics. Fourier-projections from X-ray diagrams. Graphics 12 , 98— Marchessault and A.

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Sarko: X-ray structure of polysaccha- count [2], has been used as the frontispiece of a book: Carbohy- rides. Voragen: VCH Publ. Blokzijl and J. Engeberts: Hydrophobic effects, opinion Carlson, K. Larsson, N. Dinhguyen, and N. Krog: A Int. Immel: Cyclodextrins, cyclomannins, [27b] R.

Stute and G. Raphaelides and J. Karkalas: Thermal dissociation of ty potential profiles. Tetrahedron Asymmetry 5 , — amylose-fatty acid complexes. Immel: The lipophilicity patterns of cy- [27d] G. Wulff and S. Kubik: Helical amylose complexes with or- clodextrins and non-glucose cyclooligosaccharides. Inclusion ganic ligands.

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Kubik: Circular dichroism and UV spec- [43] Y. Lichtenthaler: Synthesis, struc- 1— Kubik and G. McMullan, W. Fayos, and D. Mootz: Topography [44] S. Lichtenthaler: Solution geometries of cyclodextrin inclusion complexes. Fujioka, [29] M. Noltemeyer and W. Saenger: Structural chemistry of linear M. Mihyshi, S. Tetrahedron Asymmetry 10 , — Lichtenthaler: Conformations and iouthi, J.

Kanters, and G. Address of authors: Professor Dr. Frieder W. Lichtenthaler [48] F. Immel: Sucrose, sucralose, and fructose: and Dr. Stefan Immel. X assignments, in: Sweet Taste Chemoreception. Math- Received: August 23, Lichtenthaler,a Hans J. Together with water, the macrocycle and its guest assemble into a unique solid-state architecture, featuring layers of head-to-head dimers of the macrocycle with its guest, separated by equally distinct layers of water molecules, which are engaged in an intense hydrogen bonding network with the 6-CH2 OH and the propanol-OH groups.

The overall guest—host topography is thus reverse to that of the respective ethanol inclusion complex. Of the two protocols that have been advanced for this conversion,4,5 the one allowing sulfonation and epoxide formation to proceed in a one-pot operation, i. E-mail: lemmi sugar. For Part 25, see Immel et al. Immel et al. Indeed, when recrystallized from aqueous ethanol, 6 was shown to accumulate as a hydrate with ethanol included in its cavity Fig.

We wish to report here the peculiar finding that simply by enlarging the guest molecule by a CH2 group, i. The geometry of the complex Fig. Top: solvent-accessible surfaces in dotted form, with the oxirane rings pointing towards the front and the 6-CH2 OH groups to the rear; disordered atomic positions and water molecules of crystallization have been left off for clarity.

Center: single surface slice through the complexes to visualize the opposite mode of inclusion of ethanol and 1-propanol approx. All epoxide rings are lined up on the larger aperture of the cone-shaped molecule with their oxygens directed towards the outside of the macro-ring. The overall shapes of the macrocycle and the hexose residues are almost identical to the geometry realized in the ethanol complex;1 some geometry parameters are listed and compared for both inclusion complexes in Table 1.

In the propanol complex, the 6- CH2 OH groups adopt gauche—trans and gauche—gauche conformations with statistical weights of As illustrated by the solvent-accessible surface Fig. Table 2. Most notably, the 1-propanol guest is not engaged in hydrogen bonding to the pyranose 6-CH2 OH groups, but forms a distinct H-bond towards a water molecule labeled OW4 in Fig. The inclusion complex is shown perpendicular top and parallel bottom to the ring plane of the macrocycle water molecules of crystallization are omitted for clarity.

The crystal water molecules shown as blue spheres likewise form distinct layers alternating with those of dimeric macrocycles, this unique crystal engineering obviously being effected by an intense hydrogen-bonding texture with the primary 6-OH groups of the macrocyclic host and the 1-propanol-OH. The unique packing features become more comprehensible on analyzing the molecular lipophilicity patterns MLPs of guest and host.

The hydrophilic blue domains are centered on the opposite side around the 6-hydroxyl groups. The three components involved — a cyclooligosaccharide, an alcohol, and water — self-assemble to substantially different superstructures by enlarging the alcohol component to be enclosed in the cavity by as little as one CH2 group cf. The smaller ethanol occupies the cavity in an inverse way, whereby the non-complementarity in non-polar guest—host interactions is coun- terbalanced by the establishment of hydrogen-bonding between the cavity-inserted ethanol-OHs. This resulted in the generation of well-formed crystals having m.

Bottom: comparative sketch of the opposite directional modes with which ethanol left1 and 1-propanol right are embedded into the macrocyclic cavity, resulting in distinctly different interactions with the respective water layers c 0. C, The prismatic crystal used for the X-ray structure analysis, of the dimensions 0.

Computation and scaling of the MLPs was done separately for the guest and host, followed by reassembly of the complex. Left: view onto the wider opening of the macrocycle with the six oxirane rings, displaying the hydrophobic yellow side. The front-opened version center with the ball-and-stick model insert exposes the distinctly hydrophilic blue rear side bearing the 6-CH2 OH groups. All hydroxyl groups were treated as idealized HO groups, the hydroxyl proton of 1-propanol was subsequently positioned geometrically.

Sabine Foro for collecting the X-ray crystallographic data, and to Prof. References 1. Takeo, K. Zhang, P. Nogami, Y. Cyclomannins: a Mori, M. Tetrahedron Lett. Tetrahedron: Asymmetry , 5, — molecular geometry and lipophilicity profile. Cyclorhamnins: a Nishizawa, M. Pharm Bull. Cyclooligosaccharides composed of alternating D-mannose and L-rhamnose units: a Ashton, P. Lichtenthaler, F. Graphics , 12, 98— Sheldrick, G. Inclusion Complexes of Cycloaltrins S. Immel and K. Table 1 lists the corresponding K complex formation constants obtained by non-linear regression along with their standard deviations, respectively.